TW201532812A - In-mold transfer foil and molded article using same - Google Patents

In-mold transfer foil and molded article using same Download PDF

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Publication number
TW201532812A
TW201532812A TW103137335A TW103137335A TW201532812A TW 201532812 A TW201532812 A TW 201532812A TW 103137335 A TW103137335 A TW 103137335A TW 103137335 A TW103137335 A TW 103137335A TW 201532812 A TW201532812 A TW 201532812A
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TW
Taiwan
Prior art keywords
layer
transfer foil
mold transfer
resin
ultraviolet
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Application number
TW103137335A
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Chinese (zh)
Inventor
Manabu Watanabe
Yumi Hizume
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Toppan Printing Co Ltd
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Publication of TW201532812A publication Critical patent/TW201532812A/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B44C1/1729—Hot stamping techniques
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14827—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using a transfer foil detachable from the insert
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2509/00—Household appliances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles

Landscapes

  • Injection Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

This invention provides the following: an in-mold transfer foil that makes it possible to provide a molded article that has high surface strength while forming, on a decorative printed layer, a texture that has a 3D appearance; and a molded article using said in-mold transfer foil. This in-mold transfer foil (100) is obtained by layering the following on one surface of a base film (1), in this order: a release layer (2), a hard-coat layer (3) comprising a UV-curable resin that is post-cured, a texture formation layer (6) comprising a UV-curable resin, an ink reflection layer (7), and an adhesive layer (8). A UV-blocking layer (4) is inserted between the hard-coat layer (3) and the texture formation layer (6).

Description

模內轉印箔及使用其之成形品 In-mold transfer foil and molded article using the same

本發明係關於模內轉印箔，進一步詳言之，係關於適於工業製品之裝飾的模內轉印箔。 The present invention relates to an in-mold transfer foil, and more particularly to an in-mold transfer foil suitable for the decoration of industrial articles.

使用了模內轉印箔的成形品，被使用於日用品或生活用品等機器本體、食品或各種物品的容器類、電子裝置或事務用品等之外殼類等。 A molded article using an in-mold transfer foil is used for a machine body such as a daily necessities or a daily necessities, a container for foods or various articles, an outer casing such as an electronic device or a business article, and the like.

模內轉印箔，係指在成為基材的基底膜上，例如，形成了脫模層、印刷層、黏結層的塑膠加飾成形用的轉印箔。又，模內成形係於一對射出成形用鑄模間，供給模內轉印箔並填充經加熱加壓之成形樹脂在藉由射出成形用鑄模所形成的腔室，之後，剝離基底膜及脫模層，轉印印刷層於成形樹脂，進行裝飾的成形方法。 The in-mold transfer foil refers to a transfer foil for plastic decorative molding in which a release layer, a printing layer, and a bonding layer are formed on a base film to be a substrate. Further, the in-mold molding is performed between a pair of injection molding molds, and the in-mold transfer foil is supplied and filled with the heat-pressed molding resin in the chamber formed by the injection molding mold, and then the base film is peeled off and removed. The mold layer is a method of forming a decorative layer by transferring a printed layer to a molding resin.

以用以獲得表面強度高的成形品之模內轉印箔而言，即使在脫模層上無照射紫外線時，也是將屬固體的紫外線硬化樹脂形成作為硬塗層，在該層上，形成了加飾印刷層、黏結層等。此種型式之模內轉印箔，被稱為後固化型的模內轉印箔，在成形物表面以射出成形轉印硬塗層及加飾印刷層後，藉由照射紫外線來硬化硬塗層，而使箔的成形性(抗龜裂性)與硬度並存。此外，在此後固化型之模內轉印箔之情形，若在成形前照射紫 外線，使硬塗層硬化，則會損及成形性，而造成外觀不良。 In the in-mold transfer foil for obtaining a molded article having a high surface strength, even if no ultraviolet ray is irradiated on the release layer, a solid ultraviolet ray-curable resin is formed as a hard coat layer, and a layer is formed on the layer. The decorative layer, the bonding layer and the like are decorated. This type of in-mold transfer foil is called a post-curing in-mold transfer foil. After the transfer-molding hard coat layer and the decorative printed layer are formed on the surface of the molded article, the hard coat is hardened by irradiation with ultraviolet rays. The layer is formed so that the formability (crack resistance) of the foil and the hardness coexist. In addition, in the case of the post-cure type in-mold transfer foil, if the violet is irradiated before forming When the outer layer is hardened, the hard coat layer is hardened, and the formability is impaired, resulting in poor appearance.

先前技術之模內轉印箔，因僅在基底膜上將文字或圖案(pattern)等進行平面式印刷的結構，故在加飾表現上，有著缺乏立體感的問題。 In the in-mold transfer foil of the prior art, since a character, a pattern, or the like is printed on the base film only in a planar manner, there is a problem that the appearance of the decoration has a lack of a three-dimensional feeling.

對此問題，在表現立體感的方法方面，係有：成形品表面可為平滑，而有在加飾印刷層內形成凹凸，表現出立體感的方法(參照例如專利文獻1)。 In the method of expressing the three-dimensional feeling, the surface of the molded article can be smooth, and a method of forming a concavity and convexity in the decorative printed layer and exhibiting a three-dimensional effect (see, for example, Patent Document 1).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第3813799號公報 [Patent Document 1] Japanese Patent No. 3813799

但是，在專利文獻1記載之方法等，於立體表現之凹凸形成上，多為以紫外線硬化性之網印油墨(screening ink)進行網版印刷，在該印刷步驟進行紫外線照射，故被認為有無法使用後固化型之模內轉印箔的問題。 However, in the method described in Patent Document 1, the formation of irregularities in the three-dimensional expression is mostly screen printing by ultraviolet curable screen printing ink, and ultraviolet irradiation is performed in the printing step, so that it is considered to be The problem of the post-curing in-mold transfer foil cannot be used.

又，工業製品，因可預想經長時間的使用或嚴苛環境下之使用，故就使用於工業製品之加飾的模內轉印箔而言，係對於轉印後的成形品謀求表面強度高的轉印箔。 In addition, since industrial products are expected to be used for a long period of time or in a harsh environment, the in-mold transfer foil used for the decoration of industrial products is intended to have surface strength for the molded article after transfer. High transfer foil.

因此，期望將在脫模層上形成硬塗層，並在其上形成了印刷層、黏結層等的模內轉印箔，使用於工 業製品的加飾上。 Therefore, it is desirable to form a hard coat layer on the release layer and form an in-mold transfer foil on which a printing layer, a bonding layer, or the like is formed, for use in the work. The decoration of the products.

但是，多數在模內轉印箔所使用的硬塗層，因係由紫外線硬化樹脂所形成，故若使用紫外線硬化樹脂設置凹凸形成層時，則在成形前必須對模內轉印箔照射紫外線，而在成形前使包含紫外線硬化樹脂的硬塗層硬化。因此，會產生損及模內轉印箔的成形性，易於發生不良品等的問題。 However, most of the hard coat layer used in the in-mold transfer foil is formed of an ultraviolet curable resin. Therefore, when an uneven layer is provided by using an ultraviolet curable resin, the in-mold transfer foil must be irradiated with ultraviolet rays before molding. The hard coat layer containing the ultraviolet curable resin is hardened before forming. Therefore, the moldability of the in-mold transfer foil is impaired, and problems such as defective products are liable to occur.

本發明係謀求解決此種問題者，其目的係提供一種模內轉印箔及使用其之成形品，其可提供將具有立體感的凹凸形成於加飾印刷層，同時具有高表面強度的成形品。 The present invention has been made in an effort to solve such a problem, and an object thereof is to provide an in-mold transfer foil and a molded article using the same, which can provide a three-dimensionally formed unevenness on a decorative printed layer while having a high surface strength. Product.

為了達成上述目的，本發明之一態樣，係一種模內轉印箔，其係在基底膜之一面上，依照脫模層、包含後固化型式之紫外線硬化樹脂的硬塗層、包含紫外線硬化樹脂的凹凸形成層、反射層及黏結層的順序積層而成的模內轉印箔，在該硬塗層與該凹凸形成層之間，介插(inserting)有紫外線遮蔽層。 In order to achieve the above object, an aspect of the present invention is an in-mold transfer foil which is applied to one side of a base film, and which comprises a release coating layer, a hard coat layer containing a post-curing type ultraviolet curable resin, and ultraviolet curing. An in-mold transfer foil in which a resin uneven layer, a reflective layer, and a binder layer are laminated in this order, and an ultraviolet shielding layer is interposed between the hard coat layer and the uneven layer.

又，本發明之一態樣，係一種模內轉印箔，其特徵為該紫外線遮蔽層，係具有羥基及紫外線吸收性官能基的丙烯酸聚合物與異氰酸酯化合物之硬化物。 Further, an aspect of the invention is an in-mold transfer foil characterized in that the ultraviolet shielding layer is a cured product of an acrylic polymer and an isocyanate compound having a hydroxyl group and an ultraviolet absorbing functional group.

又，本發明之一態樣係一種模內轉印箔，其特徵為該凹凸形成層，係至少包含胺甲酸乙酯丙烯酸酯寡聚物、異氰酸酯化合物及體質顏料(extender pigment)的紫外 線硬化樹脂。 Further, an aspect of the present invention is an in-mold transfer foil characterized in that the uneven formation layer is an ultraviolet ray containing at least an urethane acrylate oligomer, an isocyanate compound, and an extender pigment. Line hardening resin.

又，本發明之一態樣係一種模內轉印箔，其特徵為該反射層係包含鋁充填劑及珍珠顏料(pearl pigment)中之至少一者。 Further, an aspect of the present invention is an in-mold transfer foil characterized in that the reflective layer comprises at least one of an aluminum filler and a pearl pigment.

又，本發明之一態樣，係一種模內轉印箔，其特徵為該反射層係錫蒸鍍膜，且全光線透過率為5%以上。 Further, an aspect of the invention is an in-mold transfer foil characterized in that the reflective layer is a tin-deposited film and has a total light transmittance of 5% or more.

又，本發明之一態樣，係一種成形品，其特徵為使用該模內轉印箔，並以模內射出成形法製造。 Further, an aspect of the invention is a molded article characterized in that the in-mold transfer foil is used and is produced by an in-mold injection molding method.

本發明之一態樣，並不藉由凹凸形成時之紫外線而進行硬塗層之交聯硬化，因可保持優異成形性(抗龜裂性等)，故可提供具有高表面強度，立體感優異的成形品。 In one aspect of the present invention, cross-linking hardening of a hard coat layer is not performed by ultraviolet rays at the time of formation of irregularities, and excellent moldability (crack resistance, etc.) can be maintained, so that high surface strength and three-dimensionality can be provided. Excellent molded product.

1‧‧‧基底膜 1‧‧‧ basement membrane

2‧‧‧脫模層 2‧‧‧ release layer

3‧‧‧硬塗層 3‧‧‧hard coating

4‧‧‧紫外線遮蔽層 4‧‧‧UV shielding layer

5‧‧‧加飾印刷層 5‧‧‧Plus printing layer

6‧‧‧凹凸形成層 6‧‧‧ uneven layer

7‧‧‧油墨反射層 7‧‧‧Ink reflection layer

8‧‧‧黏結層 8‧‧‧Bonded layer

9‧‧‧蒸鍍反射層 9‧‧‧ evaporated reflective layer

10‧‧‧底塗層 10‧‧‧Undercoat

11‧‧‧射出成形樹脂 11‧‧‧ Injection molding resin

100‧‧‧模內轉印箔 100‧‧‧In-mold transfer foil

200‧‧‧成形品 200‧‧‧Formed products

第1圖表示本發明第一實施形態的模內轉印箔之概要構成圖。 Fig. 1 is a view showing a schematic configuration of an in-mold transfer foil according to a first embodiment of the present invention.

第2圖表示使用本發明第一實施形態之模內轉印箔的成形品之概要構成圖。 Fig. 2 is a schematic view showing a configuration of a molded article using the in-mold transfer foil according to the first embodiment of the present invention.

第3圖表示本發明第二實施形態之模內轉印箔之概要構成圖。 Fig. 3 is a view showing the schematic configuration of an in-mold transfer foil according to a second embodiment of the present invention.

第4圖表示使用本發明第二實施形態之模內轉印箔的成形品之概要構成圖。 Fig. 4 is a view showing a schematic configuration of a molded article using an in-mold transfer foil according to a second embodiment of the present invention.

[實施發明之形態] [Formation of the Invention]

茲就本發明之實施形態，一面參照圖式，一面說明如下。 Embodiments of the present invention will be described below with reference to the drawings.

(第一實施形態) (First embodiment)

茲就本發明之第一實施形態(以下，稱為本實施形態)，一面參照圖式一面說明如下。 The first embodiment of the present invention (hereinafter referred to as the present embodiment) will be described below with reference to the drawings.

(模內射出成形法) (In-mold injection molding method)

模內射出成形法，係至少具有下列四步驟的射出成形法：準備模內轉印箔的步驟；將模內轉印箔***射出成形用鑄模內的步驟；藉由將樹脂進行射出成形於射出成形用鑄模，予以密接，而在樹脂表面轉印模內轉印箔的步驟；在樹脂冷卻後，打開射出成形用鑄模，並且剝離基底膜及脫模層，再取出成形品的步驟。此外，在本發明，紫外線與UV為相同意義。 The in-mold injection molding method is an injection molding method having at least the following four steps: a step of preparing an in-mold transfer foil; a step of inserting an in-mold transfer foil into an injection molding mold; and molding the resin into an injection molding The molding die is bonded to each other to transfer the in-mold transfer foil on the resin surface, and after the resin is cooled, the injection molding mold is opened, and the base film and the release layer are peeled off, and the molded article is taken out. Further, in the present invention, ultraviolet rays and UV have the same meaning.

(全體構成) (all components)

第1圖係表示本實施形態之模內轉印箔之概要構成圖，其係自側面觀察模內轉印箔的剖面示意圖。又，第2圖係表示使用了本實施形態之模內轉印箔的成形品之概要構成圖，其係自側面觀察成形品的剖面示意圖。 Fig. 1 is a schematic configuration view showing an in-mold transfer foil of the present embodiment, which is a schematic cross-sectional view of the in-mold transfer foil viewed from the side. In addition, FIG. 2 is a schematic configuration view of a molded article using the in-mold transfer foil of the present embodiment, and is a schematic cross-sectional view of the molded article viewed from the side.

如第1圖中所示，模內轉印箔100係具備基底膜1、脫模層2、硬塗層3、紫外線遮蔽層4、加飾印刷層5、凹凸形成層6、油墨反射層7及黏結層8。 As shown in FIG. 1, the in-mold transfer foil 100 includes a base film 1, a release layer 2, a hard coat layer 3, an ultraviolet shielding layer 4, a decorative printed layer 5, an unevenness forming layer 6, and an ink reflecting layer 7. And the bonding layer 8.

此外，在本實施形態，一例是如第1圖中所示，表示在紫外線遮蔽層4與凹凸形成層6之間，介插有固定層或彩色油墨所致之加飾印刷層5之情形，而模內轉印箔100之構成並非限定於此，例如在硬塗層3與紫外線遮 蔽層4之間，或油墨反射層7與黏結層8之間，介插有加飾印刷層5亦可。 Further, in the present embodiment, as shown in Fig. 1, a case where the decorative printed layer 5 is formed by interposing a fixing layer or a color ink between the ultraviolet shielding layer 4 and the unevenness forming layer 6 is shown. The configuration of the in-mold transfer foil 100 is not limited thereto, for example, in the hard coat layer 3 and the ultraviolet ray. Between the mask layers 4, or between the ink reflective layer 7 and the adhesive layer 8, a decorative printed layer 5 may be interposed.

又，如第2圖中所示，使用了模內轉印箔100的成形品200係具備射出成形樹脂11、具有模內轉印箔100的硬塗層3、紫外線遮蔽層4、凹凸形成層6、油墨反射層7、黏結層8。 Moreover, as shown in FIG. 2, the molded article 200 using the in-mold transfer foil 100 includes the injection molding resin 11, the hard coat layer 3 having the in-mold transfer foil 100, the ultraviolet shielding layer 4, and the uneven layer. 6. Ink reflective layer 7 and adhesive layer 8.

(模內轉印箔100、成形品200的具體構成) (Specific configuration of the in-mold transfer foil 100 and the molded article 200)

茲參照第1圖及第2圖，就模內轉印箔100及成形品200之具體構成說明如下。 The specific configurations of the in-mold transfer foil 100 and the molded article 200 will be described below with reference to Figs. 1 and 2 .

．基底膜1 . Basement membrane 1

以形成基底膜1之材料而言，可使用例如聚酯系樹脂、聚醯胺系樹脂、聚烯烴系樹脂、乙烯系樹脂、丙烯酸系樹脂、纖維素系樹脂、聚碳酸酯樹脂等。較佳者，由抗熱性、機械強度之觀點來看，最適者為聚對苯二甲酸乙二酯樹脂之薄膜。 For the material for forming the base film 1, for example, a polyester resin, a polyamide resin, a polyolefin resin, an ethylene resin, an acrylic resin, a cellulose resin, a polycarbonate resin or the like can be used. Preferably, from the viewpoint of heat resistance and mechanical strength, the most suitable one is a film of polyethylene terephthalate resin.

．脫模層2 . Release layer 2

脫模層2，係形成於基底膜1之一面(在第1圖中為下方之面)上。 The release layer 2 is formed on one surface (the lower surface in FIG. 1) of the base film 1.

以脫模層2之材質而言，只要是具備必要的脫模性的樹脂，則並無特別限定，不過，在本實施形態之模內轉印箔100，例如較佳為使用經烯烴轉化的丙烯酸三聚氰胺(acrylic melamine)樹脂或丙烯酸胺甲酸乙酯樹脂。又，以脫模層2之形成方法而言，可使用周知的印刷法或塗布法。 The material of the release layer 2 is not particularly limited as long as it has a releasable resin. However, in the in-mold transfer foil 100 of the present embodiment, for example, olefin conversion is preferably used. Acrylic melamine resin or urethane acrylate resin. Further, as a method of forming the release layer 2, a well-known printing method or coating method can be used.

．硬塗層3 . Hard coating 3

硬塗層3，係在轉印後剝離基底膜1時，成為成形品200的最表面層之層，其係含有後固化型之紫外線硬化樹脂之層。 The hard coat layer 3 is a layer which is the outermost layer of the molded article 200 when the base film 1 is peeled off after the transfer, and is a layer containing a post-curing type ultraviolet curable resin.

又，以硬塗層3之材料而言，例如為不黏著(tackfree)狀態，在轉印於被轉印物後，由藉照射紫外線而可交聯的樹脂所構成的材料為適當。在此，以轉印後進行交聯之理由而言，本實施形態之模內轉印箔100，大多被使用於射出成形或加熱轉印法，而在預先交聯時，因在轉印之延伸時易於產生龜裂，而造成外觀不良。 Further, the material of the hard coat layer 3 is, for example, in a tackless state, and a material composed of a resin which can be crosslinked by irradiation with ultraviolet rays after being transferred to the object to be transferred is suitable. Here, the in-mold transfer foil 100 of the present embodiment is often used for injection molding or heat transfer printing for the reason of crosslinking after transfer, and is transferred at the time of pre-crosslinking. It is prone to cracks when extended, resulting in poor appearance.

此外，以在轉印前實現不黏著(僅蒸發溶劑部分，而使膠黏性消失)之方法而言，主要有以下記載的三個方法(第一至第三方法)。 Further, there are mainly three methods (first to third methods) described below in order to achieve non-sticking (only evaporation of the solvent portion and disappearing of the adhesiveness) before transfer.

第一方法，係使用高分子型之丙烯酸酯或甲基丙烯酸酯之方法。 The first method is a method using a polymer type acrylate or methacrylate.

第二方法，係以例如異氰酸酯/多元醇樹脂或環氧樹脂/胺類等交聯系樹脂來使液狀或半液狀之紫外線硬化樹脂稍微硬化，作成不黏著之方法。 In the second method, a liquid or semi-liquid ultraviolet curable resin is slightly hardened by a crosslinking resin such as an isocyanate/polyol resin or an epoxy resin/amine to form a non-adhesive method.

第三方法，係例如稍微照射紫外線或電子束，成為半硬化狀態之方法。 The third method is, for example, a method of slightly irradiating ultraviolet rays or electron beams to a semi-hardened state.

又，在第一方法之情形，為了在不黏著且射出成形時讓樹脂不致流動，較佳為將含有重量平均分子量4萬以上，且玻璃轉移溫度為60℃以上的丙烯醯基或甲基丙烯醯基的丙烯酸樹脂(丙烯醯基丙烯酸酯)作為材料。此係因為在重量平均分子量小於4萬之情形，會有不黏著性並非充分，而除了於上塗性有問題，在成形時亦會易於發 生流失(wash out)所致。又，其係因為在重量平均分子量超過10萬之情形，自由基反應性降低，而會有無法提高交聯時之硬度之情況所致。此種丙烯醯基丙烯酸酯，一般而言，相較於使用於紫外線硬化樹脂的寡聚物或單體，有著不黏著或硬化收縮少等的優點。另一方面，丙烯醯基丙烯酸酯，因為是高分子樹脂，故紫外線硬化性傾向於劣化，即使用以補償表面硬度劣化，也有必要添加奈米矽石微粒於丙烯醯基丙烯酸酯。又，在其添加量相對於丙烯醯基丙烯酸酯樹脂為小於10重量%，則無法觀察到在硬度上之效果。另一方面，超過40重量%時，則變得過於脆弱，使得抗磨耗性(abrasion resistance)不良。因此，最適添加量係相對於丙烯醯基丙烯酸酯樹脂而在10重量%以上40重量%以下之範圍內。此外，重量平均分子量係藉由以GPC測定換算苯乙烯所計算的值。進一步，最適範圍係重量平均分子量在6萬以上8萬以下之範圍內，奈米矽石微粒量在15重量%以上且小於35重量%之範圍內。 Further, in the case of the first method, in order to prevent the resin from flowing during the non-adhesion and injection molding, it is preferred to contain an acrylonitrile group or a methacryl group having a weight average molecular weight of 40,000 or more and a glass transition temperature of 60 ° C or higher. A mercapto-based acrylic resin (acryloyl acrylate) is used as the material. This is because if the weight average molecular weight is less than 40,000, the non-adhesiveness is not sufficient, and in addition to the problem of the top coatability, it is easy to be formed during the forming. Caused by the loss of the wash. In addition, when the weight average molecular weight exceeds 100,000, the radical reactivity is lowered, and the hardness at the time of crosslinking may not be improved. Such an acryl methacrylate generally has an advantage of not adhering or having less hardening shrinkage than an oligomer or a monomer used for an ultraviolet curing resin. On the other hand, since acryl methacrylate is a polymer resin, ultraviolet curability tends to deteriorate, and even if it is used to compensate for deterioration of surface hardness, it is necessary to add nano sized vermiculite particles to acryl methacrylate. Moreover, when the amount added was less than 10% by weight based on the acryl acrylate resin, the effect on hardness could not be observed. On the other hand, when it exceeds 40% by weight, it becomes too weak, and the abrasion resistance is poor. Therefore, the optimum addition amount is in the range of 10% by weight or more and 40% by weight or less based on the acryl methacrylate resin. Further, the weight average molecular weight is a value calculated by converting styrene by GPC measurement. Further, the optimum range is that the weight average molecular weight is in the range of 60,000 or more and 80,000 or less, and the amount of the nano vermiculite particles is in the range of 15% by weight or more and less than 35% by weight.

此外，以硬塗層3之形成方法而言，可使用周知的印刷法或塗布法。 Further, as a method of forming the hard coat layer 3, a well-known printing method or coating method can be used.

．紫外線遮蔽層4 . UV shielding layer 4

以紫外線遮蔽層4之材料而言，例如，可使用具有與硬塗層3之密接性的材料，其係具有藉由吸收或反射光波長為200nm以上380nm以下範圍內的光，而可遮蔽或減少紫外線穿透的性能。 For the material of the ultraviolet shielding layer 4, for example, a material having adhesion to the hard coat layer 3 may be used, which has a light having a wavelength of 200 nm or more and 380 nm or less by absorbing or reflecting light, and can be shielded or Reduce the performance of UV penetration.

在此，以具有紫外線遮蔽能的材料而言，可 使用例如氧化鋅、氧化銫等金屬氧化物充填劑、苯并***系紫外線吸收劑、二苯酮系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、水楊酸酯系紫外線吸收劑、草醯替苯胺(oxanilide)系紫外線吸收劑等的有機紫外線吸收劑、或將該等紫外線吸收劑共價鍵結的樹脂。 Here, in the case of a material having ultraviolet shielding energy, For example, a metal oxide filler such as zinc oxide or cerium oxide, a benzotriazole ultraviolet ray absorbing agent, a benzophenone ultraviolet absorbing agent, a cyanoacrylate ultraviolet absorbing agent, a salicylate ultraviolet absorbing agent, and grass are used. An organic ultraviolet absorber such as an oxanilide ultraviolet absorber or a resin which is covalently bonded to the ultraviolet absorber.

但是，紫外線吸收劑，一般而言，多為屬低分子的材料，也易產生對硬塗層3或凹凸形成層6之轉移。藉此，在硬塗層3或凹凸形成層6之形成時，硬化成為不充分，例如會有各層間之密接性不良，或因結塊(blocking)、射出成形時之熱，而產生凹凸形狀變形的情形。 However, the ultraviolet absorber, in general, is a low molecular weight material, and is liable to cause transfer to the hard coat layer 3 or the uneven layer 6. Therefore, when the hard coat layer 3 or the uneven layer-forming layer 6 is formed, the hardening is insufficient, and for example, the adhesion between the layers is poor, or the heat is generated during blocking and injection molding, and the uneven shape is generated. The situation of deformation.

因此，以使用作為紫外線遮蔽層4之材料的樹脂而言，較佳為分子內具有紫外線吸收性之官能基的聚合物(紫外線吸收性聚合物)。進一步，由密接性之觀點觀之，紫外線遮蔽層4之材料，較佳為作成硬化物，其係具有羥基及紫外線吸收性之官能基的丙烯酸聚合物與異氰酸酯化合物之硬化物。 Therefore, the resin which is a material of the ultraviolet shielding layer 4 is preferably a polymer (ultraviolet absorbing polymer) having a functional group having ultraviolet absorbing properties in the molecule. Further, from the viewpoint of adhesion, the material of the ultraviolet shielding layer 4 is preferably a cured product which is a cured product of an acrylic polymer and an isocyanate compound having a hydroxyl group and a UV-absorbing functional group.

如此，藉由將紫外線遮蔽層4之材料作成二液硬化系丙烯酸樹脂，就可耐受射出成形時的熱，且與丙烯酸系紫外線硬化樹脂之親和性變高，密接性成為良好。 By using the material of the ultraviolet shielding layer 4 as the two-liquid curing acrylic resin, the heat during the injection molding can be withstood, and the affinity with the acrylic ultraviolet curing resin is increased, and the adhesion is good.

又，異氰酸酯化合物，係指例如二異氰酸甲苯酯(TDI)、二異氰酸二苯基甲酯(MDI)、二異氰酸亞二甲苯酯(XDI)、二異氰酸六亞甲酯(HDI)、二異氰酸異佛耳酮酯(IPDI)及該等的預聚物。 Further, an isocyanate compound means, for example, toluene diisocyanate (TDI), diphenyl methyl diisocyanate (MDI), xylene diisocyanate (XDI), hexamethylene diisocyanate. Ester (HDI), isophorone diisocyanate (IPDI) and such prepolymers.

以紫外線遮蔽能之標準而言，以i線(波長365nm)之透過率小於10%為理想。這是因為在以紫外線硬化樹脂進行凹凸形成時，有必要對凹凸形成層6照射500mJ/cm2以上1000mJ/cm2以下範圍內之光量的紫外線，此時，相對於所形成的硬塗層3，在射出成形前若照射了大致100mJ/cm2以上紫外線時，則因交聯反應之進行而無法追隨射出成形時之延伸，因此在硬塗層3發生了龜裂所致。 In terms of the ultraviolet shielding energy standard, it is preferable that the transmittance of the i-line (wavelength 365 nm) is less than 10%. This is because when the unevenness is formed by the ultraviolet curable resin, it is necessary to irradiate the unevenness forming layer 6 with ultraviolet light having a light amount of 500 mJ/cm 2 or more and 1000 mJ/cm 2 or less, and at this time, with respect to the hard coat layer 3 formed. When the ultraviolet rays of approximately 100 mJ/cm 2 or more are irradiated before the injection molding, the crosslinking reaction does not follow the elongation at the time of injection molding, and thus the hard coat layer 3 is cracked.

．加飾印刷層5 . Decorative printing layer 5

以加飾印刷層5之材料而言，例如係使用著色油墨，其含有適切顏色之顏料或染料來作為著色劑。 For the material of the decorative printed layer 5, for example, a colored ink containing a pigment or a dye of a suitable color as a coloring agent is used.

以加飾印刷層5之形成方法而言，可使用例如套版印刷法、凹版(gravure)印刷法、網版印刷法、噴墨法等通常之印刷法。較佳為，可多色印刷(multicolor printing)或表現灰階等級，且適於大量生產的凹版印刷法來印刷較好。 In the method of forming the decorative printed layer 5, a usual printing method such as a lithography method, a gravure printing method, a screen printing method, or an inkjet method can be used. Preferably, multicolor printing or gray scale grade is exhibited, and gravure printing suitable for mass production is preferred for printing.

．凹凸形成層6 . Concavo-convex formation layer 6

凹凸形成層6，例如可藉由UV塗厚(thick-walled)油墨所致網版印刷法或UV噴墨法、或以液狀紫外線硬化樹脂夾持脫模性凹凸薄膜與基底膜，並自脫模性凹凸薄膜側照射UV予以硬化，剝離脫模性凹凸薄膜，而形成。 The unevenness forming layer 6 can be, for example, a screen printing method or a UV inkjet method by a thick-walled ink, or a release-type uneven film and a base film by a liquid ultraviolet curing resin, and The release-preventing film side is irradiated with UV to be cured, and the release-preventing uneven film is peeled off to form.

凹凸形成層6之凹凸設計，例如只要是可表現出幾何學圖案或髮線(hairline)形狀等立體感之物，則可任意使用。此外，在脫模性凹凸薄膜所致凹凸形成之情形，例如，亦可進行立體圖像或光子結晶等的微細表現。 The concavo-convex design of the concavo-convex forming layer 6 can be arbitrarily used as long as it can exhibit a three-dimensional effect such as a geometric pattern or a hairline shape. Further, in the case where the unevenness is formed in the release-preventing film, for example, a fine expression such as a stereoscopic image or photonic crystal can be performed.

該等紫外線硬化樹脂所致凹凸形成，相較於熱硬化樹脂所致凹凸形成，凹凸形狀之再現性良好，可縮短製造時間。 The ultraviolet curable resin is formed by unevenness, and the unevenness is formed as compared with the thermosetting resin, and the reproducibility of the uneven shape is good, and the manufacturing time can be shortened.

以凹凸形成層6之材料而言，可使用紫外線硬化樹脂，其係由例如具有丙烯醯基或甲基丙烯醯基的單體、聚酯丙烯酸酯、丙烯酸環氧酯、胺甲酸乙酯丙烯酸酯等的寡聚物、因紫外線而發生自由基的聚合引發劑所構成。 As the material of the unevenness forming layer 6, an ultraviolet curable resin which is, for example, a monomer having an acrylonitrile group or a methacrylonitrile group, a polyester acrylate, an epoxy acrylate, or a urethane acrylate may be used. An oligomer such as an oligomer or a polymerization initiator which generates a radical due to ultraviolet rays.

又，以凹凸形成層6之材料而言，在上述材料中，以至少包含胺甲酸乙酯丙烯酸酯寡聚物、與異氰酸酯化合物、體質顏料的紫外線硬化樹脂最適合。一般而言，以使用於紫外線硬化樹脂的寡聚物而言，有例如聚酯丙烯酸酯、丙烯酸環氧酯、胺甲酸乙酯丙烯酸酯，而關於凹凸形成層6，由層間之密接性與成形時延伸性之觀點觀之，較佳則為胺甲酸乙酯丙烯酸酯。 Further, in the material of the unevenness forming layer 6, among the above materials, an ultraviolet curable resin containing at least an urethane acrylate oligomer, an isocyanate compound, and an extender pigment is most suitable. In general, as the oligomer used for the ultraviolet curable resin, there are, for example, polyester acrylate, epoxy acrylate, and urethane acrylate, and regarding the unevenness forming layer 6, the adhesion and formation between the layers are formed. From the standpoint of the extensibility, it is preferably urethane acrylate.

進一步，以凹凸形成層6之材料而言，為了提高層間之密接性，較佳為添加異氰酸酯化合物。以異氰酸酯化合物之添加量而言，相對於紫外線硬化性寡聚物，較佳為1重量%以上10重量%以下之範圍內。又，藉由添加體質顏料於凹凸形成層6，而具有：加諸散射成分於凹凸形狀，增加立體感的效果；因體質顏料之觸變性所致凹凸形成時的形狀穩定性效果；及因表面積增加所致密接性提高的效果。在此，體質顏料係指無色透明的顏料(或白色顏料)，例如，矽石或氧化鋁、碳酸鈣、硫酸鋇等微粒。 Further, in order to improve the adhesion between the layers, the material of the unevenness forming layer 6 is preferably an isocyanate compound. The amount of the isocyanate compound to be added is preferably in the range of 1% by weight to 10% by weight based on the ultraviolet curable oligomer. Further, by adding the extender pigment to the uneven layer forming layer 6, the effect of adding a scattering component to the uneven shape to increase the three-dimensional effect, the shape stability effect when the unevenness is formed due to the thixotropy of the extender pigment, and the surface area Increase the effect of improved adhesion. Here, the extender pigment means a colorless and transparent pigment (or white pigment), for example, fine particles such as vermiculite or alumina, calcium carbonate, barium sulfate or the like.

．油墨反射層7 . Ink reflective layer 7

油墨反射層7，係反射或散射光之層，若可使凹凸形成層6之凹凸結構可視化則佳。 The ink reflective layer 7 is a layer that reflects or scatters light, and it is preferable to visualize the uneven structure of the unevenness forming layer 6.

在將油墨反射層7之材料，製成例如如稀釋劑油墨(medium ink)或黑色油墨等般之材料之情形，凹凸結構被埋沒而幾乎無法觀察到。另一方面，在將油墨反射層7之材料作成例如鋁充填劑或珍珠顏料般之高輝性(high luminance)材料之情形，由於因凹凸結構而局部地使充填劑或顏料的配向紊亂，故凹凸結構可顯著的觀察到。 In the case where the material of the ink reflective layer 7 is made of a material such as a medium ink or a black ink, the uneven structure is buried and hardly observed. On the other hand, in the case where the material of the ink reflective layer 7 is made of a high luminance material such as an aluminum filler or a pearl pigment, since the alignment of the filler or the pigment is partially disturbed by the uneven structure, the unevenness is caused. The structure can be observed significantly.

又，在將油墨反射層7之材料，製成例如鋁充填劑或珍珠顏料般之高輝性材料之情形，由於如鋁蒸鍍膜般，並非是連續的反射膜，故成形時難以發生龜裂，且難以被識別。在此，鋁充填劑，係指例如包含鋁的鱗片(scaly)狀、非固定形狀的微粒，其除了表面未處理品以外，由於可提高耐久性或設計性，故亦有表面塗布的充填劑。又，珍珠顏料，係指例如將如氧化鈦、氧化鐵般之金屬氧化膜塗布於雲母的顏料，其在折射率高的金屬氧化膜層與折射率低的雲母及其周邊介質之邊界，光會進行反射/干涉的顏料。 Further, in the case where the material of the ink reflective layer 7 is made of a high-gloss material such as an aluminum filler or a pearl pigment, since it is not a continuous reflection film like an aluminum vapor deposition film, cracking is less likely to occur during molding. And difficult to be identified. Here, the aluminum filler refers to, for example, a scaly-like, non-fixed-shaped fine particle containing aluminum, which has a surface-coated filler because it can improve durability or design in addition to the surface untreated product. . Further, the pearl pigment refers to, for example, a pigment in which a metal oxide film such as titanium oxide or iron oxide is applied to mica, which is a boundary between a metal oxide film layer having a high refractive index and a mica having a low refractive index and a peripheral medium thereof. A pigment that will reflect/interfere.

．黏結層8 . Bonding layer 8

黏結層8，係在成形品200之表面黏結上述各層之物。 The adhesive layer 8 is bonded to the surface of the molded article 200 by the above layers.

以黏結層8之材料而言，可適宜使用例如適合於射出成形樹脂11的感熱性或感壓性之樹脂。 For the material of the adhesive layer 8, for example, a resin suitable for the heat-sensitive or pressure-sensitive property of the injection molding resin 11 can be suitably used.

以黏結層8之形成方法而言，可使用例如凹版印刷法 、網版印刷法等印刷法。尤其是，由膜厚/生產性之觀點觀之，以凹版印刷法印刷者為佳。此外，油墨反射層7對成形品200具有充分黏結性，在亦具備作為黏結層之效果之情形，不設置黏結層8亦可。 In the method of forming the adhesive layer 8, for example, gravure printing can be used. Printing methods such as screen printing. In particular, it is preferable to use a gravure printing method from the viewpoint of film thickness/productivity. Further, the ink reflective layer 7 has sufficient adhesion to the molded article 200, and may have an effect as a bonding layer, and the adhesive layer 8 may not be provided.

以上，係將各層如上述般積層，形成本實施形態之模內轉印箔100。 As described above, each layer is laminated as described above to form the in-mold transfer foil 100 of the present embodiment.

(成形品200之製造方法) (Manufacturing method of molded article 200)

茲參照第1圖及第2圖，就成形品200之製造方法加以說明。 A method of manufacturing the molded article 200 will be described with reference to Figs. 1 and 2 .

成形品200，係以使用了模內轉印箔100的射出成形來製造。 The molded article 200 is produced by injection molding using the in-mold transfer foil 100.

模內轉印箔100之射出成形，係依如下周知順序進行：藉由將模內轉印箔100***射出成形用鑄模內，並將射出成形樹脂11自模內轉印箔100之加飾印刷層5側射出成形至射出成形用鑄模之腔室內，而在射出成形樹脂11表面轉印模內轉印箔100；進一步，在冷卻射出成形樹脂11後，打開射出成形用鑄模，剝離模內轉印箔100之基底膜1及脫模層2，再取出成形品200。 The injection molding of the in-mold transfer foil 100 is carried out in the following order: by inserting the in-mold transfer foil 100 into the injection molding mold, and printing the injection molding resin 11 from the in-mold transfer foil 100 The layer 5 is injection-molded into the chamber of the injection molding mold, and the in-mold transfer foil 100 is transferred onto the surface of the injection molding resin 11; further, after the injection molding resin 11 is cooled, the injection molding mold is opened, and the mold is transferred. The base film 1 and the release layer 2 of the foil 100 are taken out, and the molded article 200 is taken out.

藉由該方法，而可製造具有立體感的成形品200(參照第2圖)。 According to this method, the molded article 200 having a three-dimensional feeling can be produced (see FIG. 2).

(第二實施形態) (Second embodiment)

其後，就本發明之第二實施形態(以下稱為本實施形態)，一面參照第1圖及第2圖，一面使用第3圖及第4圖加以說明。此外，就與上述第一實施形態相同之構成，會有省略說明之情形。 Hereinafter, the second embodiment (hereinafter referred to as the present embodiment) of the present invention will be described with reference to Figs. 3 and 4, with reference to Figs. 1 and 2 . In addition, the same configuration as that of the first embodiment described above will be omitted.

(全體構成) (all components)

第3圖表示本實施形態之模內轉印箔之概要構成圖，其係自側面觀察模內轉印箔的剖面示意圖。又，第4圖，係表示使用本實施形態之模內轉印箔的成形品之概要構成圖，其係自側面觀察成形品的剖面示意圖。 Fig. 3 is a view showing a schematic configuration of an in-mold transfer foil of the present embodiment, which is a schematic cross-sectional view of the in-mold transfer foil viewed from the side. In addition, FIG. 4 is a schematic cross-sectional view showing a molded article using the in-mold transfer foil of the present embodiment, and is a cross-sectional view of the molded article viewed from the side.

如第3圖中所示，模內轉印箔100係具備基底膜1、脫模層2、硬塗層3、紫外線遮蔽層4、加飾印刷層5、凹凸形成層6、黏結層8、蒸鍍反射層9及底塗層10。 As shown in FIG. 3, the in-mold transfer foil 100 includes a base film 1, a release layer 2, a hard coat layer 3, an ultraviolet shielding layer 4, a decorative printed layer 5, an uneven layer 6, and a bonding layer 8. The reflective layer 9 and the undercoat layer 10 are evaporated.

此外，在本實施形態，一例是如第3圖中所示，其係表示在紫外線遮蔽層4與凹凸形成層6之間，介插有固定層或彩色油墨所致加飾印刷層5之情形，不過模內轉印箔100之構成，並非限定於此，例如在硬塗層3及紫外線遮蔽層4之間，介插有加飾印刷層5亦可。 Further, in the present embodiment, an example is shown in Fig. 3, which shows a case where the decorative printed layer 5 is interposed between the ultraviolet shielding layer 4 and the unevenness forming layer 6 by interposing a fixed layer or a color ink. However, the configuration of the in-mold transfer foil 100 is not limited thereto. For example, the decorative printed layer 5 may be interposed between the hard coat layer 3 and the ultraviolet shielding layer 4.

又，如第4圖中所示，使用了模內轉印箔100的成形品200係具備射出成形樹脂11、具有模內轉印箔100的硬塗層3、紫外線遮蔽層4、凹凸形成層6、黏結層8、蒸鍍反射層9及底塗層10。 Moreover, as shown in FIG. 4, the molded article 200 using the in-mold transfer foil 100 includes the injection molding resin 11, the hard coat layer 3 having the in-mold transfer foil 100, the ultraviolet shielding layer 4, and the uneven layer. 6. The bonding layer 8, the vapor deposition reflective layer 9 and the undercoat layer 10.

(模內轉印箔100、成形品200之具體構成) (Specific configuration of in-mold transfer foil 100 and molded article 200)

茲參照第1圖至第4圖，就模內轉印箔100及成形品200之具體構成說明如下。 The specific configurations of the in-mold transfer foil 100 and the molded article 200 will be described below with reference to Figs. 1 to 4 .

．基底膜1 . Basement membrane 1

以基底膜1之材料而言，可使用例如聚酯系樹脂、聚醯胺系樹脂、聚烯烴系樹脂、乙烯系樹脂、丙烯酸系樹脂、纖維素系樹脂、聚碳酸酯樹脂等。較佳者，由抗熱性、機械強度之觀點來看，以聚對苯二甲酸乙二酯樹脂 之薄膜最佳。 As the material of the base film 1, for example, a polyester resin, a polyamide resin, a polyolefin resin, an ethylene resin, an acrylic resin, a cellulose resin, a polycarbonate resin or the like can be used. Preferably, from the viewpoint of heat resistance and mechanical strength, polyethylene terephthalate resin The film is the best.

．脫模層2 . Release layer 2

以脫模層2之材質而言，只要是具備必要的脫模性的樹脂，則並無特別限定，不過在本實施形態之模內轉印箔100，較佳為例如使用經烯烴轉化的丙烯酸三聚氰胺樹脂或丙烯酸胺甲酸乙酯樹脂。又，以脫模層2之形成方法而言，可使用周知的印刷法或塗布法。 The material of the release layer 2 is not particularly limited as long as it has a releasable resin. However, in the in-mold transfer foil 100 of the present embodiment, for example, an olefin-modified acrylic acid is preferably used. Melamine resin or urethane acrylate resin. Further, as a method of forming the release layer 2, a well-known printing method or coating method can be used.

．硬塗層3 . Hard coating 3

硬塗層3，係在轉印後剝離基底膜1時，成為成形品200之最表面層之層。 The hard coat layer 3 is a layer which is the outermost layer of the molded article 200 when the base film 1 is peeled off after the transfer.

又，硬塗層3之材料，例如可為不黏著狀態，在轉印於被轉印物後，由藉照射紫外線而可交聯的樹脂所構成者較合適。在此，以轉印後進行交聯之理由而言，該轉印箔，大多被使用在射出成形或加熱轉印法，不過在預先進行交聯時，在轉印之延伸時因易於產生龜裂，而造成外觀不良。又，以在轉印前實現不黏著性的方法而言，主要有以下所示三種方法(第一至第三方法)。 Further, the material of the hard coat layer 3 may be, for example, a non-adhesive state, and is preferably formed of a resin which can be crosslinked by irradiation with ultraviolet rays after being transferred to the object to be transferred. Here, the transfer foil is often used in an injection molding or a heat transfer method for the purpose of crosslinking after transfer. However, when crosslinking is performed in advance, it is easy to produce a turtle during the extension of the transfer. Cracked, resulting in poor appearance. Further, in terms of a method of achieving non-adhesiveness before transfer, there are mainly three methods (first to third methods) shown below.

第一方法係使用高分子型之丙烯酸酯或甲基丙烯酸酯之方法。 The first method is a method using a polymer type acrylate or methacrylate.

第二方法係例如以異氰酸酯/多元醇樹脂或環氧樹脂/胺類等交聯系樹脂來使液狀或半液狀之紫外線硬化樹脂稍微硬化，製成不黏著的方法。 The second method is a method in which a liquid or semi-liquid ultraviolet curable resin is slightly cured by, for example, an isocyanate/polyol resin or an epoxy resin/amine or the like to form a non-adhesive method.

第三方法係例如稍微照射紫外線或電子束，成為半硬化狀態之方法。 The third method is, for example, a method of slightly irradiating ultraviolet rays or electron beams to a semi-hardened state.

又，在第一方法之情形，為了在不黏著且射 出成形時不讓樹脂流動，較佳為重量平均分子量4萬以上，且玻璃轉移溫度為60℃以上的含有丙烯醯基或甲基丙烯醯基的丙烯酸樹脂(丙烯醯基丙烯酸酯)。此係因為在重量平均分子量小於4萬之情形，不黏著性並非充分，上塗性會有問題，除此以外，在成形時亦有易於發生流失問題所致。又，在重量平均分子量超過10萬之情形，因自由基反應性變低，而會有交聯時硬度無法提高之情形所致。此種丙烯醯基丙烯酸酯，一般而言，相較於紫外線硬化樹脂所使用的寡聚物或單體，會有不黏著性或硬化收縮少等的優點。另一方面，丙烯醯基丙烯酸酯因為是高分子樹脂，故紫外線硬化性傾向於劣化，即使為了補償表面硬度劣化，也有必要添加奈米矽石微粒於丙烯醯基丙烯酸酯。其添加量相對於丙烯醯基丙烯酸酯樹脂為小於10重量%時，則無法觀察到對硬度之效果，若超過40重量%，則變得過度脆弱，抗磨耗性不良。因此，最適添加量係相對於丙烯醯基丙烯酸酯樹脂，在10重量%以上40重量%以下之範圍內。此外，重量平均分子量，係以GPC測定換算苯乙烯所計算之值。進一步，最適範圍係重量平均分子量在6萬以上8萬以下之範圍內，奈米矽石微粒量在15重量%以上且小於35重量%之範圍內。 Also, in the case of the first method, in order not to stick and shoot The resin is not allowed to flow during molding, and is preferably an acrylic resin (acrylonitrile acrylate) containing an acrylonitrile group or a methacryl oxime group having a weight average molecular weight of 40,000 or more and a glass transition temperature of 60 ° C or higher. In this case, when the weight average molecular weight is less than 40,000, the non-adhesiveness is not sufficient, and the top coatability may be problematic, and in addition, there is a problem that the loss is liable to occur during molding. Further, when the weight average molecular weight exceeds 100,000, the radical reactivity is lowered, and the hardness may not be improved at the time of crosslinking. Such an acryl methacrylate generally has an advantage of being non-adhesive or having less hardening shrinkage than the oligomer or monomer used in the ultraviolet curable resin. On the other hand, since the acryl methacrylate is a polymer resin, the ultraviolet curability tends to deteriorate, and it is necessary to add the smectite particles to the acryl acrylate even in order to compensate for the deterioration of the surface hardness. When the amount added is less than 10% by weight based on the acryl methacrylate resin, the effect on hardness is not observed, and if it exceeds 40% by weight, the film is excessively weak and the abrasion resistance is poor. Therefore, the optimum addition amount is in the range of 10% by weight or more and 40% by weight or less based on the acryl methacrylate resin. Further, the weight average molecular weight is a value calculated by conversion of styrene by GPC measurement. Further, the optimum range is that the weight average molecular weight is in the range of 60,000 or more and 80,000 or less, and the amount of the nano vermiculite particles is in the range of 15% by weight or more and less than 35% by weight.

以硬塗層3之形成方法而言，可使用周知的印刷法或塗布法。 In the method of forming the hard coat layer 3, a well-known printing method or coating method can be used.

．紫外線遮蔽層4 . UV shielding layer 4

以紫外線遮蔽層4之材料而言，例如，可使用具有與硬塗層3之密接性的材料其係具有藉由吸收或反射光波 長為200nm以上380nm以下範圍內之光，而可遮蔽或減少紫外線穿透的性能。 In the case of the material of the ultraviolet shielding layer 4, for example, a material having adhesion to the hard coat layer 3 may be used to absorb or reflect light waves. The light is in the range of 200 nm or more and 380 nm or less, and can shield or reduce the performance of ultraviolet light penetration.

以具有紫外線遮蔽能之材料而言，例如可使用氧化鋅、氧化銫等金屬氧化物充填劑、苯并***系紫外線吸收劑、二苯酮系紫外線吸收劑、氰丙烯酸酯系紫外線吸收劑、水楊酸酯系紫外線吸收劑、草醯替苯胺系紫外線吸收劑等的有機紫外線吸收劑、或將該等紫外線吸收劑共價鍵結的樹脂。 For the material having ultraviolet shielding energy, for example, a metal oxide filler such as zinc oxide or cerium oxide, a benzotriazole ultraviolet absorbing agent, a benzophenone ultraviolet absorbing agent, a cyanoacrylate ultraviolet absorbing agent, or the like can be used. An organic ultraviolet absorber such as a salicylate-based ultraviolet absorber or a oxalic acid-based ultraviolet absorber, or a resin in which the ultraviolet absorber is covalently bonded.

但是，紫外線吸收劑，一般而言多為屬低分子的材料，易於產生對硬塗層3或凹凸形成層6之轉移。藉此，在硬塗層3或凹凸形成層6之形成時，硬化成為不充分，例如會有各層間之密接性不良或結塊、因射出成形時之熱引起凹凸形狀變形之情形。 However, the ultraviolet absorber is generally a low molecular material and is liable to cause transfer to the hard coat layer 3 or the uneven layer 6. Therefore, when the hard coat layer 3 or the uneven layer forming layer 6 is formed, the hardening is insufficient, and for example, there is a case where the adhesion between the layers is poor or agglomerated, and the uneven shape is deformed by the heat at the time of injection molding.

因此，以作為紫外線遮蔽層4之材料使用的樹脂而言，較佳為使用分子內具有紫外線吸收性之官能基的聚合物(紫外線吸收性聚合物)。進一步，由密接性之觀點觀之，以紫外線遮蔽層4之材料而言，較佳為製成硬化物，其係具有羥基及紫外線吸收性之官能基的丙烯酸聚合物與異氰酸酯化合物之硬化物。 Therefore, as the resin used as the material of the ultraviolet shielding layer 4, a polymer (ultraviolet absorbing polymer) having a functional group having ultraviolet absorbing properties in the molecule is preferably used. Further, from the viewpoint of the adhesion, the material of the ultraviolet shielding layer 4 is preferably a cured product which is a cured product of an acrylic polymer and an isocyanate compound having a hydroxyl group and a UV-absorbing functional group.

如此，藉由將紫外線遮蔽層4之材料製成二液硬化系丙烯酸樹脂，就可耐受射出成形時之熱，與丙烯酸系紫外線硬化樹脂之親和性亦變高，密接性良好。 By making the material of the ultraviolet shielding layer 4 into a two-liquid curing acrylic resin, the heat during injection molding can be withstood, and the affinity with the acrylic ultraviolet curing resin is also increased, and the adhesion is good.

又，異氰酸酯化合物，係指例如二異氰酸甲苯酯(TDI)、二異氰酸二苯基甲酯(MDI)、二異氰酸亞二甲苯酯(XDI)、二異氰酸六亞甲酯(HDI)、二異氰酸異佛耳酮 酯(IPDI)及該等預聚物。 Further, an isocyanate compound means, for example, toluene diisocyanate (TDI), diphenyl methyl diisocyanate (MDI), xylene diisocyanate (XDI), hexamethylene diisocyanate. Ester (HDI), isophora diisocyanate Esters (IPDI) and such prepolymers.

以紫外線遮蔽能之標準而言，以i線(波長365nm)之透過率小於10%為理想。這是因為在以紫外線硬化樹脂進行凹凸形成時，有必要對凹凸形成層6照射500mJ/cm2以上1000mJ/cm2以下範圍內之光量之紫外線，此時，對於所形成的硬塗層3，若在射出成形前照射大致100mJ/cm2以上之紫外線時，則因交聯反應之進行，而無法追隨射出成形時之延伸，因而在硬塗層3發生了龜裂。 In terms of the ultraviolet shielding energy standard, it is preferable that the transmittance of the i-line (wavelength 365 nm) is less than 10%. When the unevenness is formed by the ultraviolet curable resin, it is necessary to irradiate the unevenness forming layer 6 with ultraviolet light having a light amount of 500 mJ/cm 2 or more and 1000 mJ/cm 2 or less. In this case, for the hard coat layer 3 to be formed, When ultraviolet rays of approximately 100 mJ/cm 2 or more are irradiated before injection molding, the crosslinking reaction proceeds, and the elongation at the time of injection molding cannot be followed, and cracking occurs in the hard coat layer 3.

．加飾印刷層5 . Decorative printing layer 5

以加飾印刷層5之材料而言，例如係使用著色油墨，其含有適切的顏色之顏料或染料作為著色劑。 For the material of the decorative printed layer 5, for example, a colored ink containing a pigment or dye of a suitable color as a colorant is used.

以加飾印刷層5之形成方法而言，可使用例如套版印刷法、凹版印刷法、網版印刷法、噴墨法等通常的印刷法。較佳為可多色印刷或可表現灰階等級，且適合大量生產的凹版印刷法印刷者。 As a method of forming the decorative printed layer 5, a usual printing method such as a lithography method, a gravure printing method, a screen printing method, or an inkjet method can be used. It is preferably a multi-color printing or gray scale grade, and is suitable for mass production of gravure printers.

．凹凸形成層6 . Concavo-convex formation layer 6

凹凸形成層6，係例如藉由以UV塗厚油墨所致網版印刷法或UV噴墨法、或以液狀紫外線硬化樹脂夾持脫模性凹凸薄膜與基底膜，並自脫模性凹凸薄膜側照射UV，予以硬化，剝離脫模性凹凸薄膜，而可形成凹凸。 The unevenness-forming layer 6 is formed by, for example, a screen printing method or a UV ink-jet method by UV-coating an ink, or a release-type uneven film and a base film by a liquid ultraviolet-curable resin, and self-release embossing. The film side is irradiated with UV, hardened, and the release-preventing uneven film is peeled off to form irregularities.

凹凸形成層6之凹凸設計，例如只要是可表現出幾何學圖案或髮線(hairline)形狀等立體感之物，則可任意使用。此外，在藉由脫模性凹凸薄膜來形成凹凸之情形，例如亦可表現立體圖像或光子結晶等的微細表現。 The concavo-convex design of the concavo-convex forming layer 6 can be arbitrarily used as long as it can exhibit a three-dimensional effect such as a geometric pattern or a hairline shape. Further, in the case where the unevenness is formed by the release-preventing uneven film, for example, a fine expression such as a stereoscopic image or a photonic crystal can be expressed.

因該等紫外線硬化樹脂所致凹凸形成，相較於因熱硬化樹脂所致凹凸形成，凹凸形狀之再現性為良好，可縮短製造時間。 Since the unevenness is formed by the ultraviolet curable resin, the reproducibility of the uneven shape is good as compared with the formation of the unevenness due to the thermosetting resin, and the manufacturing time can be shortened.

以凹凸形成層6之材料而言，可使用紫外線硬化樹脂，其係由例如具有丙烯醯基或甲基丙烯醯基的單體、聚酯丙烯酸酯、環氧丙烯酸酯、胺甲酸乙酯丙烯酸酯等寡聚物、因紫外線而發生自由基的聚合引發劑所構成。 As the material of the unevenness forming layer 6, an ultraviolet curable resin which is, for example, a monomer having an acrylonitrile group or a methacryl fluorenyl group, a polyester acrylate, an epoxy acrylate, an urethane acrylate may be used. An oligomer, a polymerization initiator that generates a radical due to ultraviolet rays.

又，以凹凸形成層6之材料而言，在上述材料中，至少包含胺甲酸乙酯丙烯酸酯寡聚物、異氰酸酯化合物、體質顏料的紫外線硬化樹脂為最佳。一般而言，以使用於紫外線硬化樹脂的寡聚物而言，有例如聚酯丙烯酸酯、丙烯酸環氧酯、胺甲酸乙酯丙烯酸酯，而關於凹凸形成層6，由層間之密接性與成形時延伸性之觀點觀之，則較佳為胺甲酸乙酯丙烯酸酯。 Further, in the material of the unevenness forming layer 6, among the above materials, an ultraviolet curable resin containing at least an urethane acrylate oligomer, an isocyanate compound, and an extender pigment is preferable. In general, as the oligomer used for the ultraviolet curable resin, there are, for example, polyester acrylate, epoxy acrylate, and urethane acrylate, and regarding the unevenness forming layer 6, the adhesion and formation between the layers are formed. From the viewpoint of the extensibility, it is preferably urethane acrylate.

進一步，以凹凸形成層6之材料而言，為了提高層間之密接性，較佳為添加異氰酸酯化合物。以異氰酸酯化合物之添加量而言，較佳為相對於紫外線硬化性寡聚物，在1重量%以上10重量%以下之範圍內。又，藉由在凹凸形成層6添加體質顏料，而有下列效果：加諸散射成分於凹凸形狀，增加立體感之效果；因體質顏料之觸變性所致凹凸形成時之形狀穩定性效果；及因表面積增加所致密接性提高效果。在此，體質顏料係指無色透明的顏料(或白色顏料)，其係例如矽石或氧化鋁、碳酸鈣、硫酸鋇等微粒之意。 Further, in order to improve the adhesion between the layers, the material of the unevenness forming layer 6 is preferably an isocyanate compound. The amount of the isocyanate compound to be added is preferably in the range of 1% by weight or more and 10% by weight or less based on the ultraviolet curable oligomer. Further, by adding the extender pigment to the uneven layer forming layer 6, the effect of adding the scattering component to the uneven shape to increase the three-dimensional effect and the shape stabilizing effect when the unevenness is formed due to the thixotropy of the extender pigment; The adhesion improvement effect due to an increase in surface area. Here, the extender pigment means a colorless and transparent pigment (or white pigment) which is intended to be a fine particle such as vermiculite or alumina, calcium carbonate or barium sulfate.

．黏結層8 . Bonding layer 8

黏結層8係在成形品200表面黏結上述各層者。 The adhesive layer 8 is formed by adhering the above layers to the surface of the molded article 200.

以黏結層8之材料而言，例如可適宜使用適於射出成形樹脂11的感熱性或者感壓性之樹脂。 For the material of the adhesive layer 8, for example, a resin suitable for injecting the heat-sensitive or pressure-sensitive property of the molding resin 11 can be suitably used.

以黏結層8之形成方法而言，可使用例如凹版印刷法、網版印刷法等印刷法。尤其是由膜厚/生產性之觀點觀之，以凹版印刷法印刷者為理想。此外，底塗層10對成形品具有充分黏結性，在亦具備作為黏結層之效果的情形，不特別設置黏結層8亦可。 In the method of forming the adhesive layer 8, a printing method such as a gravure printing method or a screen printing method can be used. In particular, from the viewpoint of film thickness/productivity, it is desirable to use a gravure printing method. Further, the undercoat layer 10 has sufficient adhesion to the molded article, and may have an effect as a binder layer, and the adhesive layer 8 may not be particularly provided.

．蒸鍍反射層9 . Evaporation reflective layer 9

以蒸鍍反射層9而言，較佳為使用形成不連續膜(海島結構)的錫蒸鍍膜。 In the vapor deposition reflective layer 9, it is preferable to use a tin vapor deposition film which forms a discontinuous film (island structure).

在此，錫蒸鍍膜之全光線透過率小於5%之情形，則不為不連續膜，因導電性增加，電波透過性降低，故不佳。進一步，在錫蒸鍍膜之全光線透過率小於5%之情形，錫蒸鍍膜無法追隨成形時樹脂之延伸，易於發生龜裂，且易於被識別。 Here, when the total light transmittance of the tin vapor deposited film is less than 5%, the discontinuous film is not formed, and the electric conductivity is increased, and the radio wave permeability is lowered, which is not preferable. Further, when the total light transmittance of the tin vapor deposition film is less than 5%, the tin vapor deposition film cannot follow the elongation of the resin during molding, is prone to cracking, and is easily recognized.

另一方面，錫蒸鍍膜之全光線透過率超過25%時，則光反射性降低變得顯著，成為微暗外觀，設計性不佳。 On the other hand, when the total light transmittance of the tin vapor-deposited film exceeds 25%, the light reflectivity is remarkably lowered, and the appearance is dim, and the design property is not good.

因此，蒸鍍反射層9，特佳為藉由全光線透過率5%以上25%以下範圍內之錫蒸鍍膜而形成者。 Therefore, the vapor-deposited reflective layer 9 is preferably formed by a tin-deposited film having a total light transmittance of 5% or more and 25% or less.

．底塗層10 . Undercoat 10

以底塗層10而言，因與錫蒸鍍膜密接良好，可防止錫膜之氧化者較佳，故例如較佳為氯乙烯-乙酸乙烯酯系 樹脂或三聚氰胺系樹脂。又，蒸鍍反射層9，因為半蒸鍍(具有穿透性)，故若使用白色油墨於底塗層10，則成為接近鋁蒸鍍膜的明亮反射色，在底塗層10使用黑色油墨時，則成為接近鉻蒸鍍膜的偏暗反射色。 The undercoat layer 10 is preferably a vinyl chloride-vinyl acetate system because it is excellent in adhesion to the tin vapor deposition film and can prevent oxidation of the tin film. Resin or melamine resin. Further, since the vapor deposition reflective layer 9 is semi-vapor-deposited (having penetrability), when the white ink is used for the undercoat layer 10, it becomes a bright reflection color close to the aluminum vapor-deposited film, and when the undercoat layer 10 is made of black ink. , it becomes a dark reflection color close to the chromium vapor deposition film.

以上，係將各層如上述般積層，形成本實施形態之模內轉印箔100。 As described above, each layer is laminated as described above to form the in-mold transfer foil 100 of the present embodiment.

(成形品200之製造方法) (Manufacturing method of molded article 200)

茲參照第3圖及第4圖，就成形品200之製造方法加以說明。 The method of manufacturing the molded article 200 will be described with reference to Figs. 3 and 4 .

成形品200，係根據使用了模內轉印箔100的射出成形來製造。 The molded article 200 is produced by injection molding using the in-mold transfer foil 100.

模內轉印箔100之射出成形，係可依如下周知順序來進行：藉由將模內轉印箔100***射出成形用鑄模內，並將射出成形樹脂11自模內轉印箔100之加飾印刷層5側射出成形至射出成形用鑄模之腔室內，而轉印模內轉印箔100於射出成形樹脂11表面；進一步，將射出成形樹脂11冷卻後，打開射出成形用鑄模，並剝離模內轉印箔100之基底膜1及脫模層2，再取出成形品200。 The injection molding of the in-mold transfer foil 100 can be carried out in the following order: by inserting the in-mold transfer foil 100 into the injection molding mold, and applying the injection molding resin 11 from the in-mold transfer foil 100 The printing layer 5 is injection-molded into the cavity of the injection molding die, and the transfer in-mold transfer foil 100 is sprayed onto the surface of the molding resin 11; further, after the injection molding resin 11 is cooled, the injection molding die is opened and peeled off. The base film 1 and the release layer 2 of the in-mold transfer foil 100 are taken out, and the molded article 200 is taken out.

藉此方法，可製造具有立體感的成形品200(參照第4圖)。 According to this method, the molded article 200 having a three-dimensional feeling can be produced (see FIG. 4).

[實施例] [Examples]

茲就本發明之實施例，參照第1圖至第4圖，同時使用與比較例之比較結果加以說明。此外，以下係表示本發明之實施例及比較例，但本發明並非限定於此。 For the embodiment of the present invention, reference is made to Figs. 1 to 4, and the results of comparison with the comparative examples are used together. Further, the following examples and comparative examples of the present invention are shown, but the present invention is not limited thereto.

(實施例1) (Example 1)

作為基底膜1，是使用聚對苯二甲酸乙二酯樹脂薄膜(東麗製50T60)，並在基底膜1之上，形成了使用三聚氰胺系樹脂作為材料的脫模層2、及使用紫外線硬化性之丙烯酸系樹脂作為材料的硬塗層3。進一步，使用作為樹脂的二液硬化型紫外線吸收聚合物(新中村化學製Vanaresin UVA-55MHB)，並使用作為硬化劑的日本聚胺甲酸乙酯製Coronet L，形成紫外線遮蔽層4。 As the base film 1, a polyethylene terephthalate resin film (50T60 manufactured by Toray Industries, Inc.) was used, and a release layer 2 using a melamine resin as a material was formed on the base film 1, and ultraviolet curing was performed using ultraviolet rays. The acrylic resin is used as the hard coat layer 3 of the material. Further, a two-liquid curing type ultraviolet absorbing polymer (Vanaresin UVA-55MHB manufactured by Shin-Nakamura Chemical Co., Ltd.) as a resin and Coronet L made of Japanese polyurethane as a curing agent were used to form an ultraviolet shielding layer 4.

接著，作為加飾印刷層5，係以胺甲酸乙酯系彩色油墨(color ink)，用網版印刷法形成圖案。其後，用以下所示處方的UV塗厚油墨，以網版印刷法加以印刷，形成凹凸，隨即以照射紫外線(高壓汞燈累計光量800mJ/cm2)，將凹凸進行交聯硬化，使凹凸固定化，再形成凹凸形成層6。 Next, as the decorative printed layer 5, a pattern was formed by a screen printing method using an urethane color ink. Then, the UV-coated thick ink of the formulation shown below was printed by screen printing to form irregularities, and then the ultraviolet rays were irradiated (high-pressure mercury lamp integrated light amount: 800 mJ/cm 2 ), and the unevenness was cross-linked and hardened to make the unevenness After being fixed, the unevenness forming layer 6 is formed.

接著，以網版印刷法，形成以下所示反射油墨，而形成油墨反射層7。其後，以網版印刷法，形成丙烯酸/氯乙烯-乙酸乙烯酯系黏結劑，獲得實施例1之模內轉印箔100。 Next, the reflective ink shown below was formed by screen printing to form the ink reflective layer 7. Thereafter, an acrylic/vinyl chloride-vinyl acetate-based adhesive was formed by a screen printing method, and the in-mold transfer foil 100 of Example 1 was obtained.

．UV塗厚油墨 . UV coating thick ink

帝國油墨製UV塗厚油墨(UVFIX)．．．．．100重量份 Imperial ink UV thick ink (UVFIX). . . . . 100 parts by weight

富士Silysia製矽石粉末(Sylophobic 200)．．．5重量份 Fuji Silysia made vermiculite powder (Sylophobic 200). . . 5 parts by weight

旭化成化學製異氰酸酯化合物(24A100)．．．5重量份 Asahi Kasei Chemical isocyanate compound (24A100). . . 5 parts by weight

．反射油墨 . Reflective ink

東洋油墨製二液丙烯酸系網印油墨(SS16)．100重量份 Toyo Ink two-liquid acrylic screen printing ink (SS16). 100 parts by weight

默克製珍珠顏料(Iriodin 100)．．．．．．．5重量份 Merck pearl pigment (Iriodin 100). . . . . . . 5 parts by weight

將上述模內轉印箔100固定於射出成形用鑄模，予以夾緊，再將屬PC/ABS樹脂的射出成形樹脂11進行射出成形。接著，經冷卻後，打開射出成形用鑄模，並將模內轉印箔100之基底膜1與脫模層2一起自射出成形品剝離。其後，藉由在射出成形品表面，使用高壓汞燈，照射累計光量1000mJ/cm2之紫外線，將硬塗層3予以交聯硬化，而獲得具有高表面強度，且具有立體感的成形品200。 The in-mold transfer foil 100 is fixed to a mold for injection molding, clamped, and the injection molding resin 11 which is a PC/ABS resin is injection-molded. Then, after cooling, the injection molding mold is opened, and the base film 1 of the in-mold transfer foil 100 is peeled off from the injection molded article together with the release layer 2. Then, by irradiating the surface of the molded article with a high-pressure mercury lamp, ultraviolet rays having an integrated light amount of 1000 mJ/cm 2 are irradiated, and the hard coat layer 3 is cross-linked and hardened to obtain a molded article having high surface strength and having a three-dimensional effect. 200.

(實施例2) (Example 2)

基底膜1係使用聚對苯二甲酸乙二酯樹脂薄膜(東麗製50T60)，並在基底膜1之上，形成使用丙烯酸胺甲酸乙酯系樹脂作為材料的脫模層2、與使用紫外線硬化性之丙烯酸系樹脂作為材料的硬塗層3。進一步，使用作為樹脂的二液硬化型紫外線吸收聚合物(新中村化學製Vanaresin UVA-55MHB)，並使用作為硬化劑的日本聚胺甲酸乙酯製Coronet L，形成紫外線遮蔽層4。 In the base film 1, a polyethylene terephthalate resin film (50T60 manufactured by Toray Industries, Inc.) was used, and a release layer 2 using an urethane urethane resin as a material was formed on the base film 1, and ultraviolet rays were used. A hardenable acrylic resin is used as the hard coat layer 3 of the material. Further, a two-liquid curing type ultraviolet absorbing polymer (Vanaresin UVA-55MHB manufactured by Shin-Nakamura Chemical Co., Ltd.) as a resin and Coronet L made of Japanese polyurethane as a curing agent were used to form an ultraviolet shielding layer 4.

接著，作為加飾印刷層5，係以胺甲酸乙酯系彩色油墨，用網版印刷法形成圖案。其後，用以下所示處方的UV塗厚油墨，以網版印刷法印刷，形成凹凸，隨即以紫外線照射(高壓汞燈累計光量800mJ/cm2)，將凹凸予以交聯硬化，再將凹凸固定化，形成凹凸形成層6。 Next, as the decorative printed layer 5, a pattern was formed by a screen printing method using an urethane-based color ink. Thereafter, the UV-coated thick ink of the formulation shown below was printed by screen printing to form irregularities, and then irradiated with ultraviolet rays (the integrated light amount of high-pressure mercury lamp was 800 mJ/cm 2 ), and the unevenness was cross-linked and hardened, and then the unevenness was obtained. The surface of the unevenness forming layer 6 is formed by immobilization.

接著，將錫作為材料，以真空蒸鍍法使全光線透過率成為5%之方式進行形成，而形成蒸鍍反射層9。其後，用以下所示處方之底塗油墨，以凹版印刷法形成底塗 層10，其後，以網版印刷法形成丙烯酸/氯乙烯-乙酸乙烯酯系黏結劑，獲得實施例2之模內轉印箔100。 Next, tin was used as a material, and the total light transmittance was 5% by vacuum evaporation, and the vapor deposition reflective layer 9 was formed. Thereafter, the primer is applied by the primer shown below to form a primer by gravure printing. After the layer 10, an acrylic/vinyl chloride-vinyl acetate-based adhesive was formed by a screen printing method, and the in-mold transfer foil 100 of Example 2 was obtained.

．UV塗厚油墨 . UV coating thick ink

帝國油墨製UV塗厚油墨(UVFIX)．．．．．100重量份 Imperial ink UV thick ink (UVFIX). . . . . 100 parts by weight

富士Silysia製矽石粉末(Sylophobic 200)．．．5重量份 Fuji Silysia made vermiculite powder (Sylophobic 200). . . 5 parts by weight

旭化成化學製異氰酸酯化合物(24A100)．．．5重量份 Asahi Kasei Chemical isocyanate compound (24A100). . . 5 parts by weight

．底塗油墨 . Primer ink

東洋油墨製氯乙烯-乙酸乙烯酯胺甲酸乙酯系凹版油墨 白色(Finestar)．．．．．．．．．．．．．100重量份 Toyo Ink made of vinyl chloride-vinyl acetate urethane-based gravure ink White (Finestar). . . . . . . . . . . . . 100 parts by weight

旭化成化學製異氰酸酯化合物(24A100)．．．5重量份 Asahi Kasei Chemical isocyanate compound (24A100). . . 5 parts by weight

將上述模內轉印箔100固定於射出成形用鑄模，予以夾緊，再將屬PC/ABS樹脂的射出成形樹脂11射出成形。接著，經冷卻後，打開射出成形用鑄模，將模內轉印箔100之基底膜1與脫模層2一起自射出成形品剝離。其後，藉由在射出成形品表面，使用高壓汞燈，照射累計光量1000mJ/cm2之紫外線，並將硬塗層3予以交聯硬化，而獲得具有高表面強度，且具有立體感的成形品200。 The in-mold transfer foil 100 is fixed to a mold for injection molding, and is clamped, and the injection molding resin 11 which is a PC/ABS resin is injection-molded. Then, after cooling, the injection molding mold is opened, and the base film 1 of the in-mold transfer foil 100 is peeled off from the injection molded article together with the release layer 2. Thereafter, by irradiating the surface of the molded article with a high-pressure mercury lamp, ultraviolet rays having an integrated light amount of 1000 mJ/cm 2 are irradiated, and the hard coat layer 3 is cross-linked and hardened to obtain a molded article having high surface strength and having a three-dimensional effect. Product 200.

(比較例) (Comparative example)

基底膜1係使用聚對苯二甲酸乙二酯樹脂薄膜(東麗製50T60)，並在基底膜1之上，形成了使用丙烯酸胺甲酸乙酯系樹脂作為材料的脫模層2、與使用紫外線硬化性之丙烯酸系樹脂作為材料的硬塗層3。進一步，作為加飾印刷層5係以胺甲酸乙酯系彩色油墨，用網版印刷法形成圖案。 In the base film 1, a polyethylene terephthalate resin film (50T60 manufactured by Toray Industries, Inc.) was used, and on the base film 1, a release layer 2 using an urethane urethane resin as a material was formed and used. An ultraviolet curable acrylic resin is used as the hard coat layer 3 of the material. Further, as the decorative printed layer 5, an urethane-based color ink is used to form a pattern by a screen printing method.

其後，用帝國油墨製UV塗厚油墨(UVFIX)， 以網版印刷法印刷，形成凹凸，隨即以紫外線照射(高壓汞燈累計光量800mJ/cm2)，將凹凸交聯硬化，使凹凸固定化，形成凹凸形成層6。 Thereafter, UV ink thick ink (UVFIX) made of Imperial ink was printed by screen printing to form irregularities, and then ultraviolet rays were irradiated (high-pressure mercury lamp integrated light amount: 800 mJ/cm 2 ), and the unevenness was cross-linked and hardened to fix the irregularities. The unevenness forming layer 6 is formed.

接著，將鋁作為材料，以真空蒸鍍法蒸鍍，以使全光線透過率成為5%，而形成蒸鍍反射層9。進一步，用大日精化工業製VM-PEARL，以凹版印刷法形成底塗層10，其後，以網版印刷法形成丙烯酸/氯乙烯-乙酸乙烯酯系黏結劑，獲得比較例之模內轉印箔100。 Next, aluminum was used as a material, and vapor deposition was performed by a vacuum deposition method so that the total light transmittance was 5%, and the vapor deposition reflective layer 9 was formed. Further, the undercoat layer 10 was formed by gravure printing using VM-PEARL manufactured by Dai Ri Jing Chemical Co., Ltd., and thereafter, an acrylic/vinyl chloride-vinyl acetate-based binder was formed by screen printing to obtain a mold transfer of a comparative example. Printing foil 100.

將上述模內轉印箔100固定於射出成形用鑄模，予以夾緊，將屬PC/ABS樹脂的射出成形樹脂11予以射出成形。接著，經冷卻後，打開射出成形用鑄模，將模內轉印箔100之基底膜1與脫模層2一起自射出成形品剝離。其後，藉由在射出成形品之表面，使用高壓汞燈，照射累計光量1000mJ/cm2之紫外線，將硬塗層3予以交聯硬化，而獲得具有高表面強度，且具有立體感的成形品200。 The in-mold transfer foil 100 is fixed to a mold for injection molding, and is clamped, and the injection molding resin 11 which is a PC/ABS resin is injection-molded. Then, after cooling, the injection molding mold is opened, and the base film 1 of the in-mold transfer foil 100 is peeled off from the injection molded article together with the release layer 2. Thereafter, by irradiating the surface of the molded article with a high-pressure mercury lamp, ultraviolet rays having an integrated light amount of 1000 mJ/cm 2 are irradiated, and the hard coat layer 3 is cross-linked and hardened to obtain a molded body having high surface strength and having a three-dimensional appearance. Product 200.

(評估) (assessment)

針對實施例1、2及比較例，就成形性、密接性、立體感、電波透過性進行評估。評估結果如表1所示。 In Examples 1, 2 and Comparative Examples, the formability, the adhesion, the stereoscopic effect, and the radio wave permeability were evaluated. The evaluation results are shown in Table 1.

此外，各項目之評估方法係如以下所示。 In addition, the evaluation methods for each item are as follows.

．成形性：射出成形時無龜裂。 . Formability: no cracks during injection molding.

無龜裂：○ No cracks: ○

有龜裂：× Cracked: ×

．密接性：在進行1mm棋盤格之交叉切割(cross cut)後，嘗試以Nichiban製Cellotape(註冊商標)剝 離。 . Adhesiveness: After performing a cross cut of a 1 mm checkerboard, try peeling with Cellopape (registered trademark) manufactured by Nichiban from.

無剝離：○ No peeling: ○

有小於5%之剝離：△ Less than 5% peeling: △

有5%以上之剝離：× More than 5% of the stripping: ×

．立體感：目視評估。 . Three-dimensionality: visual assessment.

有立體感：○ Have a three-dimensional sense: ○

無立體感：× No stereoscopic effect: ×

．電波透過性：800MHz電波之衰減率(dB)小於1dB。 . Radio wave permeability: The attenuation rate (dB) of an 800 MHz radio wave is less than 1 dB.

衰減率小於1dB：○ The attenuation rate is less than 1dB: ○

衰減率1dB以上：× The attenuation rate is above 1dB: ×

在實施例1及實施例2，於成形性、密接性、立體感、電波透過性為優異，不過在比較例，除了立體感以外，其他並無法滿足規格。 In the first embodiment and the second embodiment, the moldability, the adhesion, the three-dimensional feeling, and the radio wave permeability were excellent. However, in the comparative example, the specifications were not satisfied except for the three-dimensional feeling.

藉此可確認到：實施例1及實施例2之模內轉印箔100及成形品200，相較於比較例之模內轉印箔100及成形品200，尤其是成形性、密接性、電波透過性優異。 In this way, it was confirmed that the in-mold transfer foil 100 and the molded article 200 of the first embodiment and the second embodiment are inferior in formability, adhesion, and in comparison with the in-mold transfer foil 100 and the molded article 200 of the comparative example. Excellent in radio wave permeability.

在此，雖然是一面參照有限數量之實施形態一面作說明，不過申請專利範圍並非限定於該等，根據上述之揭示，各實施形態之改變，對熟悉該項技藝人士應為顯而易見。 While the invention has been described with reference to a limited number of embodiments, the scope of the invention is not limited thereto, and modifications of the various embodiments will be apparent to those skilled in the art.

[產業上之可利用性] [Industrial availability]

依照本發明所得之轉印箔，可使用於例如家電製品、住宅機器、事務機器、汽車零件等所利用的面板構件等表面保護與加飾上。 The transfer foil obtained in accordance with the present invention can be used for surface protection and decoration of panel members used for, for example, home electric appliances, home appliances, business machines, automobile parts, and the like.

1‧‧‧基底膜 1‧‧‧ basement membrane

2‧‧‧脫模層 2‧‧‧ release layer

3‧‧‧硬塗層 3‧‧‧hard coating

4‧‧‧紫外線遮蔽層 4‧‧‧UV shielding layer

5‧‧‧加飾印刷層 5‧‧‧Plus printing layer

6‧‧‧凹凸形成層 6‧‧‧ uneven layer

7‧‧‧油墨反射層 7‧‧‧Ink reflection layer

8‧‧‧黏結層 8‧‧‧Bonded layer

100‧‧‧模內轉印箔 100‧‧‧In-mold transfer foil

Claims (6)

一種模內轉印箔，其係在基底膜之一面上，依脫模層、包含後固化型式之紫外線硬化樹脂的硬塗層、包含紫外線硬化樹脂的凹凸形成層、反射層及黏結層之順序積層而成的模內轉印箔，在該硬塗層與該凹凸形成層之間，介插有紫外線遮蔽層者。 An in-mold transfer foil which is applied to one surface of a base film, in accordance with a release layer, a hard coat layer containing a post-cure type ultraviolet curable resin, an uneven layer containing an ultraviolet curable resin, a reflective layer, and a bonding layer In the in-mold transfer foil laminated, an ultraviolet shielding layer is interposed between the hard coat layer and the uneven layer forming layer. 如請求項1之模內轉印箔，其中該紫外線遮蔽層係具有羥基及紫外線吸收性之官能基的丙烯酸聚合物與異氰酸酯化合物之硬化物。 The in-mold transfer foil of claim 1, wherein the ultraviolet shielding layer is a cured product of an acrylic polymer and an isocyanate compound having a hydroxyl group and a UV-absorbing functional group. 如請求項1或2之模內轉印箔，其中該凹凸形成層係至少包含胺甲酸乙酯丙烯酸酯寡聚物、異氰酸酯化合物及體質顏料(extender pigment)的紫外線硬化樹脂。 The in-mold transfer foil of claim 1 or 2, wherein the uneven formation layer is an ultraviolet curable resin containing at least an urethane acrylate oligomer, an isocyanate compound, and an extender pigment. 如請求項1至3中任一項之模內轉印箔，其中該反射層係包含鋁充填劑及珍珠顏料中之至少一者。 The in-mold transfer foil of any one of claims 1 to 3, wherein the reflective layer comprises at least one of an aluminum filler and a pearl pigment. 如請求項1至3中任一項之模內轉印箔，其中該反射層係錫蒸鍍膜，且全光線透過率為5%以上。 The in-mold transfer foil according to any one of claims 1 to 3, wherein the reflective layer is a tin-deposited film and has a total light transmittance of 5% or more. 一種成形品，其係使用如請求項1至5中任一項之模內轉印箔，並以模內射出成形法製造。 A molded article produced by using the in-mold transfer foil according to any one of claims 1 to 5, and by an in-mold injection molding method.
TW103137335A 2013-10-30 2014-10-29 In-mold transfer foil and molded article using same TW201532812A (en)

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