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WO2018142701A1 - Laminated sheet and decorative article in which same is used - Google Patents

Laminated sheet and decorative article in which same is used Download PDF

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Publication number
WO2018142701A1
WO2018142701A1 PCT/JP2017/039931 JP2017039931W WO2018142701A1 WO 2018142701 A1 WO2018142701 A1 WO 2018142701A1 JP 2017039931 W JP2017039931 W JP 2017039931W WO 2018142701 A1 WO2018142701 A1 WO 2018142701A1
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WO
WIPO (PCT)
Prior art keywords
laminated
sheet
layer
rigid layer
ink
Prior art date
Application number
PCT/JP2017/039931
Other languages
French (fr)
Japanese (ja)
Inventor
忠壮 谷口
重田　裕康
大智 林
卓志 光木
大地 濱
Original Assignee
Ｎｉｓｓｈａ株式会社
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Publication date
Application filed by Ｎｉｓｓｈａ株式会社 filed Critical Ｎｉｓｓｈａ株式会社
Publication of WO2018142701A1 publication Critical patent/WO2018142701A1/en

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    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to a laminated sheet and a decoration using the same.
  • a laminated sheet is bonded to the decorative object via an adhesive layer (for example, see Patent Document 1).
  • an adhesive layer for example, see Patent Document 1.
  • a first adhesive layer 41 is formed on a base sheet 40
  • a design layer 42 is formed on the first adhesive layer 41
  • a second adhesive layer 43 is formed on the design layer 42. Is formed (see FIG. 5).
  • the laminated sheet 4 is bonded to the surface of the object to be decorated 5 to obtain a decorated product 6.
  • the step caused by the design layer can be eliminated by the second adhesive layer even though the thickness of the adhesive layer is thin.
  • the conventional laminated sheet has a problem that the base sheet is easily bent, and the laminated sheet is easily peeled off from the end face of the decorated body after the laminated sheet is bonded to the decorated body.
  • This invention is made
  • the laminated sheet of the present invention is characterized in that a rigid layer, which is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet, and an adhesive layer are sequentially laminated on one surface of the substrate sheet.
  • the laminated sheet of the present invention is characterized in that a rigid layer that is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet is laminated on one surface of the substrate sheet, and an adhesive layer is laminated on the other surface. To do.
  • the rigid layer is made of ink.
  • the ink is a curable ink.
  • the curable ink is a thermosetting ink or an active energy ray curable ink.
  • thermosetting ink is a two-component mixed type
  • active energy ray curable ink is an ultraviolet curable type
  • the ink contains an acrylic or polyester resin.
  • the rigid layer is colored or transparent.
  • the rigid layer contains a pigment or filler.
  • the distribution of the pigment or filler is 20% by weight or more based on the total weight of the ink.
  • a design layer is further laminated between the base sheet and the adhesive layer or on the other surface of the base sheet.
  • a design layer is further laminated between the base sheet and the rigid layer or the adhesive layer, or on the surface of the rigid layer opposite to the surface in contact with the base sheet.
  • the decorative product of the present invention is a laminate sheet bonded to the surface of a resin molded product or a glass processed product via an adhesive layer.
  • the laminated sheet of the present invention was configured such that a rigid layer thinner than the base sheet and having a higher Young's modulus than the base sheet and an adhesive layer were sequentially laminated on one surface of the base sheet. Therefore, the laminated sheet of the present invention is hardly peeled off from the end face after being bonded to the object to be decorated.
  • the laminated sheet of the present invention is configured such that a rigid layer that is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet is laminated on one surface of the substrate sheet, and an adhesive layer is laminated on the other surface. . Therefore, the laminated sheet of the present invention is hardly peeled off from the end face after being bonded to the object to be decorated.
  • the decorative product of the present invention was configured such that the laminated sheet was bonded to the surface of a resin molded product or a glass processed product via an adhesive layer. Therefore, in the decorative product of the present invention, the laminated sheet bonded to the surface is difficult to peel off from the end surface.
  • a rigid layer 11 which is thinner than the base sheet 10 and has a higher Young's modulus than the base sheet 10 and an adhesive layer 13 are sequentially laminated on one surface of the base sheet 10 ( FIG. 1 (a)).
  • a rigid layer 11 that is thinner than the substrate sheet 10 and has a higher Young's modulus than the substrate sheet 10 is laminated on one surface of the substrate sheet 10, and an adhesive layer 13 is laminated on the other surface. (See FIG. 1 (b)).
  • the material of the base sheet 10 examples include thermoplastic resins such as polypropylene resins, polyethylene resins, polyamide resins, acrylic resins, olefin resins, polyester resins, vinyl chloride resins, polycarbonate resins, ABS resins, and the like. These laminated products can be mentioned.
  • the thickness of the base sheet 10 can be 5 ⁇ m to 500 ⁇ m.
  • the rigid layer 11 is thinner than the base sheet 10 and has a higher Young's modulus than the base sheet 10.
  • the material of the rigid layer 11 is resin, and the Young's modulus is a physical property value that indicates the difficulty of deformation due to external force.
  • the rigid layer 11 can be made thinner than the base sheet 10, the thickness of the laminated sheet 1 can be reduced. Therefore, when the laminated sheet 1 of the present invention is used, it is possible to contribute to reducing the weight and thickness of the decorative article 3 to which the laminated sheet 1 is bonded.
  • the rigid layer 11 may be applied to the base sheet with a resin having a higher Young's modulus than the base sheet 10 or may be bonded to the base sheet in the form of a film.
  • the rigid layer 11 is made of an ink containing one or more kinds of resins having a higher Young's modulus than the base sheet 10.
  • the rigid layer 11 made of ink may be colored or transparent.
  • the term “transparent” includes translucent and colored transparent.
  • the rigid layer 11 may have a Young's modulus smaller than that of the base sheet 10. Although it is a resin that easily deforms, by increasing the thickness to about 50 ⁇ m, the rigidity as a layer can be increased and the laminated sheet 1 can be made difficult to peel off.
  • the ink may be a curable ink. Further rigidity can be imparted to the laminated sheet 1 by curing the ink.
  • a thermosetting ink, an active energy ray (ultraviolet ray, electron beam or the like) curable ink, a one-component reaction type, or a two-component reaction type ink can be used.
  • it is a thermosetting ink or an active energy ray curable ink.
  • the thing which has a Young's modulus smaller than the material of the base sheet 10, for example, containing urethane type resin is excluded.
  • thermosetting ink when used, after the rigid layer 11 is formed and dried, the crosslink density of the ink is increased by heating and the adhesion between the base sheet 10 and the adhesive layer 13 is improved.
  • active energy ray curable ink when used, the crosslink density of the ink is increased by irradiating active energy rays such as ultraviolet rays and electron beams, and the adhesion between the base sheet 10 and the adhesive layer 13 is improved. Further, when the active energy ray curable ink is used, heat is not applied during the curing, and therefore, for example, the substrate sheet 10 can be processed without being deformed even when it is thin.
  • the thermosetting ink may be a two-component mixed thermosetting ink.
  • a two-component mixed thermosetting ink is used by mixing an ink and a curing agent at a certain ratio.
  • the ink preferably contains an acrylic or polyester resin.
  • the crosslinking density and adhesiveness can be arbitrarily controlled by the mixing ratio.
  • the active energy ray curable ink may be an ultraviolet curable ink.
  • ultraviolet curable ink for example, the rigid layer can be formed with a simpler apparatus than when using electron beam curable ink.
  • the ink may contain a pigment or a filler.
  • the pigment or filler distribution is preferably 20% by weight or more based on the total weight of the ink.
  • the Young's modulus of the rigid layer 11 increases. That is, if the laminated sheet 1 is forcibly bent and peeled off by an external force, the rigid layer 11 having an improved Young's modulus will crack. Based on this, not only the rigid layer 11 breaks, but also the base sheet 10 strongly bonded to the rigid layer 11 breaks. That is, the laminated sheet 1 having extremely high peel strength can be obtained.
  • the laminated sheet 1 may be obtained by further laminating a design layer 12 (see FIGS. 2 and 3).
  • FIG. 2 shows the laminated sheet 1 shown in FIG. 1A between the base sheet 10 and the adhesive layer 13 (see FIGS. 2A and 2B) or on the other surface of the base sheet 10. (Refer FIG.2 (c)) and the symbol layer 12 are further laminated
  • FIG. 3 is a cross-sectional view of the laminated sheet 1 shown in FIG. 1B between the base sheet 10 and the rigid layer 11 or the adhesive layer 13 (see FIGS. 3A and 3B) or the rigid layer 11.
  • the design layer 12 is further laminated on the surface opposite to the surface in contact with the base sheet 10 (see FIG. 3C).
  • the pattern layer 12 may be formed on the entire surface, or may be formed in an arbitrary pattern.
  • a normal printing method such as a gravure printing method, a screen printing method, an offset printing method, or a coating method such as a gravure coating method, a roll coating method, or a die coating method can be used.
  • the presence of the pattern layer 12 can improve the decorativeness of the object to be decorated.
  • the design layer 12 becomes the outermost surface (see FIGS. 2 (c) and 3 (c)), and the design layer 12 is formed in an arbitrary pattern.
  • the contrast of the rigid layer 11 under the pattern layer 12 can further improve the decorativeness of the object to be decorated.
  • the design layer 12 does not become the outermost surface when pasted on the object to be decorated (FIG. 2A, FIG. 2B, FIG. 3A, FIG. 3B), the rigid layer 11 When is transparent, since the rigid layer and / or the base sheet 10 is on the design layer 12, the sense of depth of the design can be improved.
  • a pressure sensitive adhesive PSA
  • PSA pressure sensitive adhesive
  • OCA optical transparent adhesive
  • the adhesive layer 13 on the rigid layer 11 the adhesive layer is preferably applied to the rigid layer after the rigid layer is dried or cured, or the film-like adhesive is bonded to the rigid layer.
  • the adhesive layer 13 on the design layer 12 the adhesive is preferably applied or bonded after the design layer is dried.
  • Other materials for the adhesive layer 13 include, for example, acrylic resin, polystyrene resin, polyamide resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin. Etc. can be appropriately selected and used.
  • a normal printing method such as a gravure printing method, a screen printing method, an offset printing method, or a coating method such as a gravure coating method, a roll coating method, or a die coating method is used. be able to.
  • the decorative product 3 of the present invention is obtained by bonding the above-described laminated sheet 1 of the present invention to the surface of a resin molded product or a glass processed product via an adhesive layer 13 (see FIG. 4).
  • the resin molded product or the glass processed product is a decorated body 2 to which the laminated sheet 1 is bonded.
  • casing (front panel, back cover, etc.) of electronic devices such as a smart phone, a tablet, a personal computer, a liquid crystal display etc. can be used, for example.
  • Example 1 Biaxially stretched polyethylene terephthalate (thickness 38 ⁇ m) was used as the base sheet.
  • the Young's modulus of the base sheet material was 3500 MPa
  • the Young's modulus of the rigid layer material was 3800 MPa.
  • Example 2 Biaxially stretched polyethylene terephthalate (thickness 38 ⁇ m) was used as the base sheet.
  • a two-component mixed thermosetting ink containing acrylic resin (thickness 14 ⁇ m, silver gray) was used to laminate a rigid layer by a coating method and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 ⁇ m) was bonded to the rigid layer as an adhesive layer.
  • the Young's modulus of the material of the rigid layer was 13000 MPa.
  • Example 3 Biaxially stretched polyethylene terephthalate (thickness 38 ⁇ m) was used as the base sheet.
  • a two-component mixed thermosetting ink (thickness 28 ⁇ m, camel) containing a polyester resin was used to laminate a rigid layer by a coating method and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 ⁇ m) was bonded to the rigid layer as an adhesive layer.
  • the Young's modulus of the material of the rigid layer was 9500 MPa.
  • Example 4 Biaxially stretched polyethylene terephthalate (thickness 38 ⁇ m) was used as the base sheet. On top of that, a rigid layer was laminated by a coating method using a two-component mixed thermosetting ink containing polyester resin (thickness 28 ⁇ m, black), and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 ⁇ m) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the material of the rigid layer was 3800 MPa.
  • Example 5 Biaxially stretched polyethylene terephthalate (thickness 38 ⁇ m) was used as the base sheet.
  • a rigid layer was laminated by a coating method using a two-component mixed thermosetting ink containing polyester resin (thickness 28 ⁇ m, black), and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 50 ⁇ m) was bonded to the rigid layer as an adhesive layer.
  • the Young's modulus of the material of the rigid layer was 3800 MPa.
  • Example 6 Biaxially stretched polyethylene terephthalate (thickness 38 ⁇ m) was used as the base sheet.
  • a two-component mixed thermosetting ink containing acrylic resin (thickness 14 ⁇ m, silver gray) was used to laminate a rigid layer by a coating method and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 50 ⁇ m) was bonded to the rigid layer as an adhesive layer.
  • the Young's modulus of the material of the rigid layer was 13000 MPa.
  • the laminated sheets of Examples 1 to 6 showed a peel strength of 0.9 to 1.39 N / mm, which was larger than 0.73 N / mm of Comparative Example 1. That is, it can be seen that the presence of the rigid layer makes it difficult for the laminated sheet to be peeled off from the object to be decorated as compared to the case without the rigid layer.
  • the base sheet was broken. These measured values are the peel strength at break. Therefore, it can be said that the laminated sheets of Examples 2 to 4 and Example 6 have high peel strength to the extent that the base sheet breaks.
  • the Young's modulus tended to increase as the distribution of the pigment or filler in the rigid layer increased. Further, when the thickness of the rigid layer is equal, the peel strength tends to increase as the Young's modulus increases. Even when the Young's modulus is the same, the greater the film thickness, the greater the rigidity and the greater the peel strength.
  • the first is that the rigidity of the laminated sheet itself is increased because the adhesive strength between the rigid layer and the base sheet and between the rigid layer and the adhesive layer is increased by heat-curing the rigid layer. .
  • the second is that the distribution of the pigment or filler is 20% by weight or more, and the rigid layer is difficult to stretch. Since the laminated sheet which is not easily deformed is peeled off, the rigid layer is cracked as it is peeled off. Based on the crack, the rigid layer is cracked, and the base sheet strongly bonded to the rigid layer is considered to break.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

[Problem] To provide a laminated sheet that does not readily peel from an edge thereof after being bonded to an article to be decorated, and a decorative article in which the same is used. [Solution] This laminated sheet is configured such that a rigid layer thinner than a base sheet and having a Young's modulus higher than that of the base sheet and an adhesive layer are laminated in the stated order on one surface of the base sheet. This laminated sheet is also configured such that a rigid layer thinner than the base sheet and having a Young's modulus higher than that of the base sheet is laminated on one surface of the base sheet and an adhesive layer is laminated on the other surface of the base sheet. This decorative article is configured such that the laminated sheet is bonded to the surface of a resin molded article or a glass processed article with an adhesive layer interposed therebetween.

Description

積層シートとそれを用いた加飾品Laminated sheet and decorative items using it
　本発明は、積層シートとそれを用いた加飾品に関する。 The present invention relates to a laminated sheet and a decoration using the same.
　ガラスや樹脂成形品などの被加飾体を加飾するために、接着層を介して被加飾体に積層シートを貼り合わせることが行われている（たとえば、特許文献１参照）。積層シート４は、基体シート４０の上に、第１の接着層４１が形成され、第１の接着層４１の上に図柄層４２が形成され、図柄層４２の上に第２の接着層４３が形成されたものである（図５参照）。この積層シート４を、被加飾体５の表面に貼り合わせて加飾品６を得る。この積層シートでは、接着層の厚みが薄いにもかかわらず、図柄層に起因する段差を第２の接着層によって解消できる。 In order to decorate a decorative object such as glass or a resin molded product, a laminated sheet is bonded to the decorative object via an adhesive layer (for example, see Patent Document 1). In the laminated sheet 4, a first adhesive layer 41 is formed on a base sheet 40, a design layer 42 is formed on the first adhesive layer 41, and a second adhesive layer 43 is formed on the design layer 42. Is formed (see FIG. 5). The laminated sheet 4 is bonded to the surface of the object to be decorated 5 to obtain a decorated product 6. In this laminated sheet, the step caused by the design layer can be eliminated by the second adhesive layer even though the thickness of the adhesive layer is thin.
特開２０１２－２２６１１１号公報JP 2012-226111 A
　しかし、従来の積層シートは基体シートがたわみやすく、積層シートを被加飾体に貼り合わせた後に、積層シートが被加飾体の端面から剥がれやすいという問題があった。 However, the conventional laminated sheet has a problem that the base sheet is easily bent, and the laminated sheet is easily peeled off from the end face of the decorated body after the laminated sheet is bonded to the decorated body.
　本発明は上記のような課題を解決するためになされたものであり、被加飾体に貼り合わせた後に端面から剥がれにくい積層シートと、それを用いた加飾品を提供することを目的とする。 This invention is made | formed in order to solve the above subjects, and it aims at providing the laminated sheet which is hard to peel from an end surface after bonding to a to-be-decorated body, and a decoration using the same. .
　以下に、課題を解決するための手段として複数の態様を説明する。これら態様は必要に応じて任意に組み合わせることができる。 Hereinafter, a plurality of modes will be described as means for solving the problem. These embodiments can be arbitrarily combined as necessary.
　本発明の積層シートは、基体シートの一方の面に、基体シートよりも薄く基体シートよりもヤング率が高い剛性層と、接着層が順に積層されていることを特徴とするものである。 The laminated sheet of the present invention is characterized in that a rigid layer, which is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet, and an adhesive layer are sequentially laminated on one surface of the substrate sheet.
　また、本発明の積層シートは、基体シートの一方の面に基体シートよりも薄く基体シートよりもヤング率が高い剛性層が積層され、他方の面に接着層が積層されていることを特徴とするものである。 Further, the laminated sheet of the present invention is characterized in that a rigid layer that is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet is laminated on one surface of the substrate sheet, and an adhesive layer is laminated on the other surface. To do.
　好ましくは、剛性層はインキからなるものである。 Preferably, the rigid layer is made of ink.
　さらに好ましくは、インキは硬化型インキである。 More preferably, the ink is a curable ink.
　さらに好ましくは、硬化型インキは熱硬化型インキまたは活性エネルギー線硬化型インキである。 More preferably, the curable ink is a thermosetting ink or an active energy ray curable ink.
　さらに好ましくは、熱硬化型インキは二液混合型であり、活性エネルギー線硬化型インキは紫外線硬化型である。 More preferably, the thermosetting ink is a two-component mixed type, and the active energy ray curable ink is an ultraviolet curable type.
　さらに好ましくは、インキはアクリル系またはポリエステル系の樹脂を含むものである。 More preferably, the ink contains an acrylic or polyester resin.
　さらに好ましくは、剛性層は着色され、または透明である。 More preferably, the rigid layer is colored or transparent.
　さらに好ましくは、剛性層は顔料またはフィラーが含まれているものである。 More preferably, the rigid layer contains a pigment or filler.
　さらに好ましくは、顔料またはフィラーの配分は、インキの総重量に対して２０重量％以上である。 More preferably, the distribution of the pigment or filler is 20% by weight or more based on the total weight of the ink.
　また、好ましくは、基体シートと接着層との間に、または基体シートの他方の面に、図柄層がさらに積層されているものである。 Preferably, a design layer is further laminated between the base sheet and the adhesive layer or on the other surface of the base sheet.
　また、好ましくは、基体シートと剛性層もしくは接着層との間に、または剛性層の基体シートと接する面と反対の面に、図柄層がさらに積層されているものである。 Further, preferably, a design layer is further laminated between the base sheet and the rigid layer or the adhesive layer, or on the surface of the rigid layer opposite to the surface in contact with the base sheet.
　本発明の加飾品は、積層シートが、接着層を介して樹脂成形品またはガラス加工品の表面に貼り合わされたものである。 The decorative product of the present invention is a laminate sheet bonded to the surface of a resin molded product or a glass processed product via an adhesive layer.
　本発明の積層シートは、基体シートの一方の面に、基体シートよりも薄く基体シートよりもヤング率が高い剛性層と、接着層が順に積層されているように構成した。したがって、本発明の積層シートは、被加飾体に貼り合わせた後に端面から剥がれにくい。 The laminated sheet of the present invention was configured such that a rigid layer thinner than the base sheet and having a higher Young's modulus than the base sheet and an adhesive layer were sequentially laminated on one surface of the base sheet. Therefore, the laminated sheet of the present invention is hardly peeled off from the end face after being bonded to the object to be decorated.
　また、本発明の積層シートは、基体シートの一方の面に基体シートよりも薄く基体シートよりもヤング率が高い剛性層が積層され、他方の面に接着層が積層されているように構成した。したがって、本発明の積層シートは、被加飾体に貼り合わせた後に端面から剥がれにくい。 The laminated sheet of the present invention is configured such that a rigid layer that is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet is laminated on one surface of the substrate sheet, and an adhesive layer is laminated on the other surface. . Therefore, the laminated sheet of the present invention is hardly peeled off from the end face after being bonded to the object to be decorated.
　本発明の加飾品は、積層シートが、接着層を介して樹脂成形品またはガラス加工品の表面に貼り合わされたように構成した。したがって、本発明の加飾品は、表面に貼り合わされた積層シートが端面から剥がれにくい。 The decorative product of the present invention was configured such that the laminated sheet was bonded to the surface of a resin molded product or a glass processed product via an adhesive layer. Therefore, in the decorative product of the present invention, the laminated sheet bonded to the surface is difficult to peel off from the end surface.
積層シートの一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of a lamination sheet. 図１（ａ）の積層シートにさらに図柄層が積層された積層シートの断面図である。It is sectional drawing of the lamination sheet by which the design layer was further laminated | stacked on the lamination sheet of Fig.1 (a). 図１（ｂ）の積層シートにさらに図柄層が積層された積層シートの断面図である。It is sectional drawing of the lamination sheet by which the design layer was further laminated | stacked on the lamination sheet of FIG.1 (b). 加飾品の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of decorating goods. 従来の積層シートと加飾品を示す断面図である。It is sectional drawing which shows the conventional laminated sheet and decorating goods.
　以下、本発明の積層シートと、それを用いた加飾品について、図面を参照しながら実施形態の一例を説明する。 Hereinafter, an example of an embodiment of the laminated sheet of the present invention and a decoration using the same will be described with reference to the drawings.
　本発明の積層シート１は、基体シート１０の一方の面に、基体シート１０よりも薄く基体シート１０よりもヤング率が高い剛性層１１と、接着層１３が順に積層されているものである（図１（ａ）参照）。また、本発明の積層シート１は、基体シート１０の一方の面に基体シート１０よりも薄く基体シート１０よりもヤング率が高い剛性層１１が積層され、他方の面に接着層１３が積層されているものである（図１（ｂ）参照）。 In the laminated sheet 1 of the present invention, a rigid layer 11 which is thinner than the base sheet 10 and has a higher Young's modulus than the base sheet 10 and an adhesive layer 13 are sequentially laminated on one surface of the base sheet 10 ( FIG. 1 (a)). In the laminated sheet 1 of the present invention, a rigid layer 11 that is thinner than the substrate sheet 10 and has a higher Young's modulus than the substrate sheet 10 is laminated on one surface of the substrate sheet 10, and an adhesive layer 13 is laminated on the other surface. (See FIG. 1 (b)).
　基体シート１０の材質は、たとえば、ポリプロピレン系樹脂、ポリエチレン系樹脂、ポリアミド系樹脂、アクリル系樹脂、オレフィン系樹脂、ポリエステル系樹脂、塩ビ系樹脂、ポリカーボネート系樹脂、ＡＢＳ系樹脂などの熱可塑性樹脂およびこれらの積層品を挙げることができる。基体シート１０の厚みは、５μｍ～５００μｍとすることができる。なお、ポリエチレンテレフタレート樹脂を用いて基体シートを製造する場合は、１４０℃以上で結晶化を進めるとよい。このようにすると、基体シート自体の剛性も上げることができる。 Examples of the material of the base sheet 10 include thermoplastic resins such as polypropylene resins, polyethylene resins, polyamide resins, acrylic resins, olefin resins, polyester resins, vinyl chloride resins, polycarbonate resins, ABS resins, and the like. These laminated products can be mentioned. The thickness of the base sheet 10 can be 5 μm to 500 μm. In addition, when manufacturing a base sheet using a polyethylene terephthalate resin, it is good to advance crystallization at 140 degreeC or more. If it does in this way, the rigidity of base sheet itself can also be raised.
　剛性層１１は、基体シート１０よりも薄く、基体シート１０よりもヤング率が高い層である。剛性層１１の材質は樹脂であり、ヤング率は外力による変形のしにくさを表す物性値である。基体シート１０よりも力に対して変形しにくい剛性層１１が積層されていることによって、積層シート１が力によって変形しにくくなる。したがって、被加飾体に積層シート１を貼り合わせた後、積層シートにたとえば曲げる力が加わっても、積層シート１が端面から剥がれにくくなる。また、剛性層１１は基体シート１０よりも薄くできるため、積層シート１の厚みを薄くできる。したがって、本発明の積層シート１を用いると、積層シート１を貼り合わせた加飾品３の軽量化および薄型化に貢献することができる。 The rigid layer 11 is thinner than the base sheet 10 and has a higher Young's modulus than the base sheet 10. The material of the rigid layer 11 is resin, and the Young's modulus is a physical property value that indicates the difficulty of deformation due to external force. By laminating the rigid layer 11 that is less likely to be deformed by force than the base sheet 10, the laminated sheet 1 is less likely to be deformed by force. Therefore, after laminating the laminated sheet 1 to the object to be decorated, even if a bending force is applied to the laminated sheet, the laminated sheet 1 is unlikely to peel off from the end face. Moreover, since the rigid layer 11 can be made thinner than the base sheet 10, the thickness of the laminated sheet 1 can be reduced. Therefore, when the laminated sheet 1 of the present invention is used, it is possible to contribute to reducing the weight and thickness of the decorative article 3 to which the laminated sheet 1 is bonded.
　剛性層１１は、基体シート１０よりもヤング率が高い樹脂を基体シートに塗工してもよく、フィルム状になったものを基体シートに貼り合わせてもよい。好ましくは、剛性層１１は、基体シート１０よりもヤング率が高い樹脂の１種または２種以上を含むインキからなるものである。インキからなる剛性層１１は、着色されていてもよく、透明であってもよい。ここで透明とは、半透明および着色透明を含むものである。インキで剛性層１１を形成する方法としては、グラビア印刷法、スクリーン印刷法、オフセット印刷法などの通常の印刷法や、グラビアコート法、ロールコート法、ダイコート法などのコート法を用いることができる。 The rigid layer 11 may be applied to the base sheet with a resin having a higher Young's modulus than the base sheet 10 or may be bonded to the base sheet in the form of a film. Preferably, the rigid layer 11 is made of an ink containing one or more kinds of resins having a higher Young's modulus than the base sheet 10. The rigid layer 11 made of ink may be colored or transparent. Here, the term “transparent” includes translucent and colored transparent. As a method for forming the rigid layer 11 with ink, a normal printing method such as a gravure printing method, a screen printing method, or an offset printing method, or a coating method such as a gravure coating method, a roll coating method, or a die coating method can be used. .
　なお、剛性層１１は基体シート１０の材質よりもヤング率が小さくてもよい。変形しやすい樹脂ではあるものの、５０μｍ程度まで厚くすることで層としての剛性を高め、積層シート１を剥がれにくくすることができる。 The rigid layer 11 may have a Young's modulus smaller than that of the base sheet 10. Although it is a resin that easily deforms, by increasing the thickness to about 50 μm, the rigidity as a layer can be increased and the laminated sheet 1 can be made difficult to peel off.
　インキは、硬化型インキであってもよい。インキが硬化することで積層シート１にさらに剛性を付与することができる。硬化型インキとしては、熱硬化型、活性エネルギー線（紫外線、電子線など）硬化型、一液反応型、二液反応型のインキを用いることができる。好ましくは、熱硬化型インキまたは活性エネルギー線硬化型インキである。ただし、基体シート１０の材質よりもヤング率が小さい、たとえばウレタン系樹脂を含むものは除く。熱硬化型インキを用いると、剛性層１１を形成して乾燥させた後、加熱することによってインキの架橋密度が上がるとともに、基体シート１０および接着層１３との接着性が向上する。活性エネルギー線硬化型インキを用いると、紫外線や電子線などの活性エネルギー線を照射することによってインキの架橋密度が上がるとともに、基体シート１０および接着層１３との接着性が向上する。また、活性エネルギー線硬化型インキを用いる場合は、硬化の際に熱が加わらないため、たとえば基体シート１０が薄いときでも変形させずに加工することができる。 The ink may be a curable ink. Further rigidity can be imparted to the laminated sheet 1 by curing the ink. As the curable ink, a thermosetting ink, an active energy ray (ultraviolet ray, electron beam or the like) curable ink, a one-component reaction type, or a two-component reaction type ink can be used. Preferably, it is a thermosetting ink or an active energy ray curable ink. However, the thing which has a Young's modulus smaller than the material of the base sheet 10, for example, containing urethane type resin is excluded. When the thermosetting ink is used, after the rigid layer 11 is formed and dried, the crosslink density of the ink is increased by heating and the adhesion between the base sheet 10 and the adhesive layer 13 is improved. When the active energy ray curable ink is used, the crosslink density of the ink is increased by irradiating active energy rays such as ultraviolet rays and electron beams, and the adhesion between the base sheet 10 and the adhesive layer 13 is improved. Further, when the active energy ray curable ink is used, heat is not applied during the curing, and therefore, for example, the substrate sheet 10 can be processed without being deformed even when it is thin.
　熱硬化型インキは、二液混合型の熱硬化型インキであってもよい。二液混合型の熱硬化型インキは、インキと硬化剤とを一定比率で混合して用いる。インキは、アクリル系またはポリエステル系の樹脂を含むものが好ましい。二液混合型の熱硬化型インキを用いると、混合比により架橋密度や接着性を任意に制御することができる。 The thermosetting ink may be a two-component mixed thermosetting ink. A two-component mixed thermosetting ink is used by mixing an ink and a curing agent at a certain ratio. The ink preferably contains an acrylic or polyester resin. When a two-component mixed thermosetting ink is used, the crosslinking density and adhesiveness can be arbitrarily controlled by the mixing ratio.
　活性エネルギー線硬化型インキは、紫外線硬化型であってもよい。紫外線硬化型インキを用いると、たとえば、電子線硬化型インキを用いる場合と比べて簡易な装置で剛性層を形成することができる。 The active energy ray curable ink may be an ultraviolet curable ink. When ultraviolet curable ink is used, for example, the rigid layer can be formed with a simpler apparatus than when using electron beam curable ink.
　剛性層１１をインキで形成する場合は、インキは顔料またはフィラーを含んでいてもよい。顔料またはフィラーの配分は、好ましくは、インキの総重量に対して２０重量％以上である。インキ中に顔料またはフィラーが含まれていると、剛性層１１のヤング率が上がる。つまり、外力によって無理に積層シート１を曲げて剥がそうとすると、ヤング率が向上した剛性層１１は亀裂を生じる。それを基点として剛性層１１が割れるだけでなく、剛性層１１に強力に接着した基体シート１０も破断する。つまり、剥離強度が極めて高い積層シート１にすることができる。 When the rigid layer 11 is formed with ink, the ink may contain a pigment or a filler. The pigment or filler distribution is preferably 20% by weight or more based on the total weight of the ink. When pigment or filler is contained in the ink, the Young's modulus of the rigid layer 11 increases. That is, if the laminated sheet 1 is forcibly bent and peeled off by an external force, the rigid layer 11 having an improved Young's modulus will crack. Based on this, not only the rigid layer 11 breaks, but also the base sheet 10 strongly bonded to the rigid layer 11 breaks. That is, the laminated sheet 1 having extremely high peel strength can be obtained.
　積層シート１は、図柄層１２をさらに積層したものであってもよい（図２、図３参照）。図２は、図１（ａ）の積層シート１において、基体シート１０と接着層１３との間（図２（ａ）、図２（ｂ）参照）に、または基体シート１０の他方の面に（図２（ｃ）参照）、図柄層１２がさらに積層されたものである。図３は、図１（ｂ）の積層シート１において、基体シート１０と剛性層１１もしくは接着層１３との間（図３（ａ）、図３（ｂ）参照）に、または剛性層１１の基体シート１０と接する面と反対の面（図３（ｃ）参照）に、図柄層１２がさらに積層されたものである。図柄層１２は全面に形成してもよく、任意のパターンで形成してもよい。図柄層１２の形成方法としては、グラビア印刷法、スクリーン印刷法、オフセット印刷法などの通常の印刷法や、グラビアコート法、ロールコート法、ダイコート法などのコート法を用いることができる。図柄層１２があることで、被加飾体の装飾性を向上させることができる。被加飾体に貼り合わせたときに図柄層１２が最表面となり（図２（ｃ）、図３（ｃ）参照）、図柄層１２が任意のパターンで形成されている場合は、図柄層１２と図柄層１２の下にある剛性層１１とのコントラストによって、より被加飾体の装飾性を向上させることができる。また、被加飾体に貼り合わせたときに図柄層１２が最表面とならず（図２（ａ）、図２（ｂ）、図３（ａ）、図３（ｂ））、剛性層１１が透明の場合は、図柄層１２の上に剛性層および／または基体シート１０があるため、図柄の奥行き感を向上させることができる。 The laminated sheet 1 may be obtained by further laminating a design layer 12 (see FIGS. 2 and 3). FIG. 2 shows the laminated sheet 1 shown in FIG. 1A between the base sheet 10 and the adhesive layer 13 (see FIGS. 2A and 2B) or on the other surface of the base sheet 10. (Refer FIG.2 (c)) and the symbol layer 12 are further laminated | stacked. FIG. 3 is a cross-sectional view of the laminated sheet 1 shown in FIG. 1B between the base sheet 10 and the rigid layer 11 or the adhesive layer 13 (see FIGS. 3A and 3B) or the rigid layer 11. The design layer 12 is further laminated on the surface opposite to the surface in contact with the base sheet 10 (see FIG. 3C). The pattern layer 12 may be formed on the entire surface, or may be formed in an arbitrary pattern. As a method for forming the pattern layer 12, a normal printing method such as a gravure printing method, a screen printing method, an offset printing method, or a coating method such as a gravure coating method, a roll coating method, or a die coating method can be used. The presence of the pattern layer 12 can improve the decorativeness of the object to be decorated. When it is bonded to the object to be decorated, the design layer 12 becomes the outermost surface (see FIGS. 2 (c) and 3 (c)), and the design layer 12 is formed in an arbitrary pattern. The contrast of the rigid layer 11 under the pattern layer 12 can further improve the decorativeness of the object to be decorated. In addition, the design layer 12 does not become the outermost surface when pasted on the object to be decorated (FIG. 2A, FIG. 2B, FIG. 3A, FIG. 3B), the rigid layer 11 When is transparent, since the rigid layer and / or the base sheet 10 is on the design layer 12, the sense of depth of the design can be improved.
　接着層１３としては、感圧性接着剤（Ｐｒｅｓｓｕｒｅ Ｓｅｎｓｉｔｉｖｅ Ａｄｈｅｓｉｖｅ：ＰＳＡ）を用いることができ、ＰＳＡに分類されるもののうち、光学透明接着剤（Ｏｐｔｉｃａｌ Ｃｌｅａｒ Ａｄｈｅｓｉｖｅ：ＯＣＡ）が好ましい。接着層１３を剛性層１１に積層する場合は、剛性層を乾燥させ、または硬化させた後に上記接着剤を剛性層に塗工し、またはフィルム状の上記接着剤を剛性層に貼り合わせるとよい。接着層１３を図柄層１２に積層する場合は、図柄層を乾燥させた後に上記接着剤を塗工し、または貼り合わせるとよい。また、接着層１３の他の材質としては、たとえば、アクリル系樹脂、ポリスチレン系樹脂、ポリアミド系樹脂、塩素化ポリオレフィン樹脂、塩素化エチレン‐酢酸ビニル共重合体樹脂、環化ゴム、クマロンインデン樹脂などを適宜選択して用いることができる。これら樹脂を接着層１３として形成する場合の方法としては、グラビア印刷法、スクリーン印刷法、オフセット印刷法などの通常の印刷法や、グラビアコート法、ロールコート法、ダイコート法などのコート法を用いることができる。 As the adhesive layer 13, a pressure sensitive adhesive (PSA) can be used, and among those classified as PSA, an optical transparent adhesive (Optical Clear Adhesive: OCA) is preferable. When laminating the adhesive layer 13 on the rigid layer 11, the adhesive layer is preferably applied to the rigid layer after the rigid layer is dried or cured, or the film-like adhesive is bonded to the rigid layer. . When laminating the adhesive layer 13 on the design layer 12, the adhesive is preferably applied or bonded after the design layer is dried. Other materials for the adhesive layer 13 include, for example, acrylic resin, polystyrene resin, polyamide resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin. Etc. can be appropriately selected and used. As a method for forming these resins as the adhesive layer 13, a normal printing method such as a gravure printing method, a screen printing method, an offset printing method, or a coating method such as a gravure coating method, a roll coating method, or a die coating method is used. be able to.
　本発明の加飾品３は、上記した本発明の積層シート１が、接着層１３を介して樹脂成形品またはガラス加工品の表面に貼り合わされたものである（図４参照）。 The decorative product 3 of the present invention is obtained by bonding the above-described laminated sheet 1 of the present invention to the surface of a resin molded product or a glass processed product via an adhesive layer 13 (see FIG. 4).
　樹脂成形品またはガラス加工品は、積層シート１が貼り合わされる被加飾体２である。被加飾体２としては、たとえば、スマートフォン、タブレット、パーソナルコンピュータなどの電子機器の筐体（前面パネル、背面カバーなど）、液晶ディスプレイなどを用いることができる。 The resin molded product or the glass processed product is a decorated body 2 to which the laminated sheet 1 is bonded. As the to-be-decorated body 2, a housing | casing (front panel, back cover, etc.) of electronic devices, such as a smart phone, a tablet, a personal computer, a liquid crystal display etc. can be used, for example.
（実施例１）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、ポリエステル系樹脂を含む二液混合型の熱硬化型インキ（厚み１４μｍ、黒色）を用い、コート法で剛性層を積層し、１６０℃の熱を２分間加え硬化させた。剛性層を硬化後に、接着層としてＯＣＡ（厚み２５μｍ）を剛性層に貼り合わせた。基体シートの材質のヤング率は３５００ＭＰａであり、剛性層の材質のヤング率は３８００ＭＰａであった。 Example 1
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. A two-component mixed thermosetting ink (thickness: 14 μm, black) containing a polyester-based resin was used to laminate a rigid layer by a coating method, and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 μm) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the base sheet material was 3500 MPa, and the Young's modulus of the rigid layer material was 3800 MPa.
（実施例２）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、アクリル系樹脂を含む二液混合型の熱硬化型インキ（厚み１４μｍ、シルバーグレー）を用い、コート法で剛性層を積層し、１６０℃の熱を２分間加え硬化させた。剛性層を硬化後に、接着層としてＯＣＡ（厚み２５μｍ）を剛性層に貼り合わせた。剛性層の材質のヤング率は１３０００ＭＰａであった。 (Example 2)
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. On top of that, a two-component mixed thermosetting ink containing acrylic resin (thickness 14 μm, silver gray) was used to laminate a rigid layer by a coating method and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 μm) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the material of the rigid layer was 13000 MPa.
（実施例３）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、ポリエステル系樹脂を含む二液混合型の熱硬化型インキ（厚み２８μｍ、キャメル）を用い、コート法で剛性層を積層し、１６０℃の熱を２分間加え硬化させた。剛性層を硬化後に、接着層としてＯＣＡ（厚み２５μｍ）を剛性層に貼り合わせた。剛性層の材質のヤング率は９５００ＭＰａであった。 (Example 3)
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. On top of that, a two-component mixed thermosetting ink (thickness 28 μm, camel) containing a polyester resin was used to laminate a rigid layer by a coating method and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 μm) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the material of the rigid layer was 9500 MPa.
（実施例４）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、ポリエステル系樹脂を含む二液混合型の熱硬化型インキ（厚み２８μｍ、黒色）を用い、コート法で剛性層を積層し、１６０℃の熱を２分間加え硬化させた。剛性層を硬化後に、接着層としてＯＣＡ（厚み２５μｍ）を剛性層に貼り合わせた。剛性層の材質のヤング率は３８００ＭＰａであった。 Example 4
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. On top of that, a rigid layer was laminated by a coating method using a two-component mixed thermosetting ink containing polyester resin (thickness 28 μm, black), and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 25 μm) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the material of the rigid layer was 3800 MPa.
（実施例５）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、ポリエステル系樹脂を含む二液混合型の熱硬化型インキ（厚み２８μｍ、黒色）を用い、コート法で剛性層を積層し、１６０℃の熱を２分間加え硬化させた。剛性層を硬化後に、接着層としてＯＣＡ（厚み５０μｍ）を剛性層に貼り合わせた。剛性層の材質のヤング率は３８００ＭＰａであった。 (Example 5)
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. On top of that, a rigid layer was laminated by a coating method using a two-component mixed thermosetting ink containing polyester resin (thickness 28 μm, black), and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 50 μm) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the material of the rigid layer was 3800 MPa.
（実施例６）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、アクリル系樹脂を含む二液混合型の熱硬化型インキ（厚み１４μｍ、シルバーグレー）を用い、コート法で剛性層を積層し、１６０℃の熱を２分間加え硬化させた。剛性層を硬化後に、接着層としてＯＣＡ（厚み５０μｍ）を剛性層に貼り合わせた。剛性層の材質のヤング率は１３０００ＭＰａであった。 (Example 6)
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. On top of that, a two-component mixed thermosetting ink containing acrylic resin (thickness 14 μm, silver gray) was used to laminate a rigid layer by a coating method and cured by applying heat at 160 ° C. for 2 minutes. After the rigid layer was cured, OCA (thickness 50 μm) was bonded to the rigid layer as an adhesive layer. The Young's modulus of the material of the rigid layer was 13000 MPa.
（比較例１）
　基体シートとして、二軸延伸ポリエチレンテレフタレート（厚み３８μｍ）を用いた。その上に、接着層としてＯＣＡ（厚み２５μｍ）を貼り合わせた。 (Comparative Example 1)
Biaxially stretched polyethylene terephthalate (thickness 38 μm) was used as the base sheet. On top of that, OCA (thickness 25 μm) was bonded as an adhesive layer.
　上記の実施例１～６、および比較例１の積層シートを１０ｍｍ幅にカットしたものを用いて、ＪＩＳ Ｚ ０２３７：２００９の規格に準拠した次の条件で剥離強度試験を行った。
　　試験板　　　　　　　　　　　：強化ガラス板 
　　試験板に対する引き剥がし方向：１８０°
　　引き剥がし速度　　　　　　　：３００ｍｍ／ｍｉｎ Using the laminate sheets of Examples 1 to 6 and Comparative Example 1 cut to a width of 10 mm, a peel strength test was performed under the following conditions based on the standard of JIS Z 0237: 2009.
Test plate: Tempered glass plate
Peeling direction from the test plate: 180 °
Peeling speed: 300mm / min
　剥離強度を測定した結果を、表１に示す。なお、測定値は、積層シート１ｍｍあたりの剥離強度に換算したものである。 The results of measuring the peel strength are shown in Table 1. In addition, a measured value is converted into peeling strength per 1 mm of laminated sheets.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記の結果から、実施例１～６の積層シートは０．９～１．３９Ｎ／ｍｍの剥離強度を示し、比較例１の０．７３Ｎ／ｍｍよりも大きい値であった。つまり、剛性層があることにより、剛性層がない場合と比べて、積層シートが被加飾体から剥がれにくくなることが分かる。なお、実施例２～４および実施例６においては、基体シートが破断した。これらの測定値は、破断時の剥離強度である。よって、実施例２～４および実施例６の積層シートは、基体シートが破断する程度までに剥離強度が大きいものといえる。また、剛性層中の顔料またはフィラーの配分が多いほどヤング率は大きくなる傾向があった。さらに、剛性層の厚みが等しい場合、ヤング率が大きいほど剥離強度が大きくなる傾向があった。また、ヤング率が等しい場合も、膜厚が大きいほど剛性が大きくなり、剥離強度は大きくなる傾向があった。 From the above results, the laminated sheets of Examples 1 to 6 showed a peel strength of 0.9 to 1.39 N / mm, which was larger than 0.73 N / mm of Comparative Example 1. That is, it can be seen that the presence of the rigid layer makes it difficult for the laminated sheet to be peeled off from the object to be decorated as compared to the case without the rigid layer. In Examples 2 to 4 and Example 6, the base sheet was broken. These measured values are the peel strength at break. Therefore, it can be said that the laminated sheets of Examples 2 to 4 and Example 6 have high peel strength to the extent that the base sheet breaks. In addition, the Young's modulus tended to increase as the distribution of the pigment or filler in the rigid layer increased. Further, when the thickness of the rigid layer is equal, the peel strength tends to increase as the Young's modulus increases. Even when the Young's modulus is the same, the greater the film thickness, the greater the rigidity and the greater the peel strength.
　基体シートが破断する程度までに剥離強度が上がった要因として、２つのことが考えられる。１つ目は、剛性層を加熱硬化したことにより、剛性層と基体シートとの間および剛性層と接着層との間の接着強度が上がったため、積層シート自体の剛性が上がったことが挙げられる。２つ目は、顔料またはフィラーの配分が２０重量％以上であり、剛性層が伸びにくいことが挙げられる。変形しにくい積層シートを剥離していくため、剥離するにつれて剛性層には亀裂が生じる。その亀裂を基点として、剛性層が割れていき、剛性層と強力に接着した基体シートが破断すると考えられる。 There are two possible causes for the peel strength increasing to such an extent that the base sheet breaks. The first is that the rigidity of the laminated sheet itself is increased because the adhesive strength between the rigid layer and the base sheet and between the rigid layer and the adhesive layer is increased by heat-curing the rigid layer. . The second is that the distribution of the pigment or filler is 20% by weight or more, and the rigid layer is difficult to stretch. Since the laminated sheet which is not easily deformed is peeled off, the rigid layer is cracked as it is peeled off. Based on the crack, the rigid layer is cracked, and the base sheet strongly bonded to the rigid layer is considered to break.
　　　１　：積層シート
　　１０　：基体シート
　　１１　：剛性層
　　１２　：図柄層
　　１３　：接着層
　　　２　：被加飾体
　　　３　：加飾品
　　　４　：加飾フィルム
　　４０　：基体シート
　　４１　：第１の接着層
　　４２　：図柄層
　　４３　：第２の接着層
　　　５　：被加飾体
　　　６　：加飾品 DESCRIPTION OF SYMBOLS 1: Laminated sheet 10: Base sheet 11: Rigid layer 12: Design layer 13: Adhesive layer 2: Decorated body 3: Decorated item 4: Decorated film 40: Base sheet 41: First adhesive layer 42: Design layer 43: Second adhesive layer 5: Decorated object 6: Decorated product

Claims (13)

  1. 　基体シートの一方の面に、前記基体シートよりも薄く前記基体シートよりもヤング率が高い剛性層と、接着層が順に積層されていることを特徴とする積層シート。 A laminated sheet characterized in that a rigid layer, which is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet, and an adhesive layer are sequentially laminated on one surface of the substrate sheet.
  2. 　基体シートの一方の面に前記基体シートよりも薄く前記基体シートよりもヤング率が高い剛性層が積層され、他方の面に接着層が積層されていることを特徴とする積層シート。 A laminated sheet characterized in that a rigid layer that is thinner than the substrate sheet and has a higher Young's modulus than the substrate sheet is laminated on one surface of the substrate sheet, and an adhesive layer is laminated on the other surface.
  3. 　前記剛性層はインキからなるものである請求項１または２に記載の積層シート。 The laminated sheet according to claim 1 or 2, wherein the rigid layer is made of ink.
  4. 　前記インキは硬化型インキである請求項３に記載の積層シート。 The laminated sheet according to claim 3, wherein the ink is a curable ink.
  5. 　前記硬化型インキは、熱硬化型インキまたは活性エネルギー線硬化型インキである請求項４に記載の積層シート。 The laminated sheet according to claim 4, wherein the curable ink is a thermosetting ink or an active energy ray curable ink.
  6. 　前記熱硬化型インキは二液混合型であり、前記活性エネルギー線硬化型インキは紫外線硬化型である請求項５に記載の積層シート。 The laminated sheet according to claim 5, wherein the thermosetting ink is a two-component mixed type, and the active energy ray curable ink is an ultraviolet curable type.
  7. 　前記インキはアクリル系またはポリエステル系の樹脂を含むものである請求項３から６のいずれか１項に記載の積層シート。 The laminated sheet according to any one of claims 3 to 6, wherein the ink contains an acrylic or polyester resin.
  8. 　前記剛性層は着色され、または透明である請求項３から７のいずれか１項に記載の積層シート。 The laminated sheet according to any one of claims 3 to 7, wherein the rigid layer is colored or transparent.
  9. 　前記剛性層は顔料またはフィラーが含まれているものである請求項８に記載の積層シート。 The laminated sheet according to claim 8, wherein the rigid layer contains a pigment or a filler.
  10. 　前記顔料または前記フィラーの配分は、インキの総重量に対して２０重量％以上である請求項９に記載の積層シート。 The laminated sheet according to claim 9, wherein the distribution of the pigment or the filler is 20% by weight or more based on the total weight of the ink.
  11. 　前記基体シートと前記接着層との間に、または前記基体シートの他方の面に、図柄層がさらに積層されている請求項１に記載の積層シート。 The laminated sheet according to claim 1, wherein a design layer is further laminated between the base sheet and the adhesive layer or on the other surface of the base sheet.
  12. 　前記基体シートと前記剛性層もしくは前記接着層との間に、または前記剛性層の前記基体シートと接する面と反対の面に、図柄層がさらに積層されている請求項２に記載の積層シート。 The laminated sheet according to claim 2, wherein a design layer is further laminated between the base sheet and the rigid layer or the adhesive layer, or on a surface of the rigid layer opposite to the surface in contact with the base sheet.
  13. 　請求項１から１２のいずれか１項に記載の積層シートが、前記接着層を介して樹脂成形品またはガラス加工品の表面に貼り合わされた加飾品。 A decorative product in which the laminated sheet according to any one of claims 1 to 12 is bonded to the surface of a resin molded product or a glass processed product via the adhesive layer.
PCT/JP2017/039931 2017-02-02 2017-11-06 Laminated sheet and decorative article in which same is used WO2018142701A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006142667A (en) * 2004-11-19 2006-06-08 Mitsubishi Chem Mkv Co Polyolefinic laminated film and pressure-sensitive adhesive film
JP2013516340A (en) * 2010-02-10 2013-05-13 エルジー・ハウシス・リミテッド Hard coating forming sheet
JP2013199522A (en) * 2012-03-23 2013-10-03 Kansai Paint Co Ltd Active energy ray curable composition and coating film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006142667A (en) * 2004-11-19 2006-06-08 Mitsubishi Chem Mkv Co Polyolefinic laminated film and pressure-sensitive adhesive film
JP2013516340A (en) * 2010-02-10 2013-05-13 エルジー・ハウシス・リミテッド Hard coating forming sheet
JP2013199522A (en) * 2012-03-23 2013-10-03 Kansai Paint Co Ltd Active energy ray curable composition and coating film

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