JP2006321179A - Decorative film and decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative film having improved tear resistance and excellent three-dimensionally curved surface workability. <P>SOLUTION: The decorative film comprises an acrylic resin-containing base layer (A) having a surface functioning as a coloring agent-accepting surface and a reverse surface facing to the surface, and a reinforcing layer (B) arranged on the reverse surface of the base layer, wherein the reinforcing layer is a layer composed of an amorphous polyester resin having a glass transition temperature of 50°C to 100°C and/or a urethane resin having a glass transition temperature of -50°C to 0°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative film and a decorative sheet, and more particularly to a decorative film and a decorative sheet that have greatly improved tear resistance and are excellent in three-dimensional curved surface construction. The decorative sheet of the present invention can be suitably used as a surface material for entrance doors, window frames, and the like, which are architectural interiors and architectural semi-exteriors.

  When polyvinyl chloride (PVC) resin is used for decorative sheets, harmful chlorine-based gas is generated during combustion, so in recent years, decorative sheets that do not contain PVC-containing resins such as PVC resins have been developed in view of environmental issues. Has been. Polyolefin resins such as polyethylene resins and polypropylene resins are used for decorative sheets as PVC substitute resins. However, these polyolefin resins are crystalline resins, so the softening temperature is high, and decorative sheets using polyolefin resins are used. When heated and pasted on a three-dimensional curved surface, there was a problem in workability because it showed uneven elongation locally.

Therefore, decorative sheets using acrylic resins with excellent workability (flexibility) have been developed as PVC substitute resins, and various decorative sheets have been disclosed (see Patent Document 1, Patent Document 2, Patent Document 3, etc.). ). However, when a decorative film is produced using an acrylic resin, the tear resistance of the obtained film is a problem of the acrylic resin itself, regardless of the film forming method (for example, calendar method, extrusion method, casting method). There was a problem that the film was torn during low-peeling and peeling at the time of construction.
JP 08-48014 A JP 2000-33675 A Japanese Patent Laid-Open No. 2003-236998

  An object of the present invention is to provide a decorative film and a decorative sheet that are excellent in tear resistance and workability (flexibility).

As a result of the study by the present inventors to achieve the above object, the tear resistance of the decorative film can be improved by providing a reinforcing layer on the base layer made of an acrylic resin excellent in workability (flexibility). Construction of a base layer made of an acrylic resin by forming the layer from an amorphous polyester resin having a glass transition point (Tg) of 50 ° C to 100 ° C and / or a urethane resin having a Tg of -50 ° C to 0 ° C It was found that the property (flexibility) can be maintained.
That is, the present invention includes (A) an acrylic resin-containing base layer having a surface functioning as a colorant receiving surface and a back surface facing the surface, and (B) a reinforcing layer disposed on the back surface of the base layer. The reinforcing layer is selected from the group consisting of an amorphous polyester resin having a glass transition point of 50 ° C to 100 ° C and a urethane resin having a glass transition point of -50 ° C to 0 ° C. A decorative sheet comprising a layer containing at least one kind of resin, and a decorative sheet comprising the decorative film and an adhesive layer provided on the back side of the reinforcing layer of the decorative film To do.

Hereinafter, preferred embodiments of the present invention will be described.
The base layer of the decorative film of the present invention uses an acrylic resin excellent in workability (flexibility). As the acrylic resin, conventionally known acrylic resins can be used. For example, one or two of methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and acrylate of butyl acrylate Examples include acrylic polymers obtained by polymerizing or copolymerizing the above. The alkyl group of these alkyl (meth) acrylates may be linear or branched and preferably contains 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. In addition to these alkyl (meth) acrylate monomers, the acrylic polymer may contain other monomers copolymerizable with alkyl (meth) acrylate as long as the effects of the present invention are not impaired.

The Tg of the acrylic resin used for the base layer is preferably 40 ° C. or higher and 80 ° C. or lower. When Tg is lower than 40 ° C., sufficient strength as a base layer cannot be obtained, and when it is higher than 80 ° C., flexibility may be inferior.
The thickness of the base layer is usually 20 μm to 200 μm, preferably 50 to 100 μm. If the thickness is less than 20 μm, the strength as the base layer is not sufficient, and a defect such as shrinkage may occur when the coloring material is received (printing process). If it is thicker than 200 μm, fire performance may be lowered.

A coloring material may be received on the surface of the base layer for the purpose of decoration or the like. The accepted colorant is usually toner or ink. The toner for forming an image includes a binder resin and a pigment dispersed in the binder resin. The binder resin is formed of at least one resin selected from the group consisting of a vinyl chloride-vinyl acetate copolymer, an acrylic resin, and a polyester resin, for example.
The colorant can be received on the surface of the base layer by a normal printing method such as gravure printing, screen printing, electrostatic printing or the like.

  The reinforcing layer contains an amorphous polyester resin having a Tg of 50 ° C. or more and 100 ° C. or less and / or a urethane resin having a Tg of −50 ° C. or more and 0 ° C. or less.

  As an amorphous polyester resin having a Tg of 50 ° C. or more and 100 ° C. or less used in the reinforcing layer of the present invention, for example, a copolymer polyester resin of a dicarboxylic acid component and a diol component is used as a main component, and heat treatment may be performed. This resin does not have crystallinity and does not cause changes in physical properties due to crystallization. Examples of such a resin include glycol-modified polyethylene terephthalate. The Tg of the amorphous polyester resin used for the reinforcing layer is usually 50 ° C. or higher and 100 ° C. or lower, preferably 60 ° C. or higher and 80 ° C. or lower. When Tg is lower than 50 ° C., the strength of the reinforcing layer may not be sufficiently high, and when Tg is higher than 100 ° C., there is a problem that the resulting decorative film is inferior in three-dimensional curved surface workability.

  Examples of the urethane resin having a Tg of −50 ° C. or more and 0 ° C. or less include a block type, a moisture curable type, an oil-modified type one-pack type urethane resin, a main component made of polyol, and a curing agent made of polyisocyanate 2 A liquid curable urethane resin can be used. If the Tg of the urethane resin is higher than 0 ° C., the resulting decorative film is inferior in tear resistance, and if the Tg is lower than −50 ° C., there is a problem that tack occurs and the workability is inferior.

  The thickness of the reinforcing layer is usually 5 μm to 100 μm, preferably 20 μm to 50 μm. If it is thinner than 5 μm, the effect of improving the tear resistance of the base layer is not sufficient, and if it is thicker than 100 μm, the workability of the decorative film may be adversely affected. In addition, since fireproof performance may be inferior when it is thicker than 50 μm, 50 μm or less is preferable in applications requiring fireproof performance.

  In addition, the glass transition point (Tg) in this specification uses a differential calorimeter (DSC) manufactured by Rigaku Co., Ltd. (model: Thermoplus 8230) as a measuring device, and a measuring temperature of −50 ° C. to 150 ° C., 10 ° C. This is a value obtained at a temperature increase rate of / min.

  For the purpose of protecting the surface of the base layer, a protective layer may be disposed on the surface of the base layer. The protective layer preferably has a high light transmittance as a whole. The light transmittance is usually 60% or more, preferably 70% or more, particularly preferably 80% or more. The “light transmittance” in the present specification means a total light transmittance measured using a spectrophotometer or a color meter also having a photometer function and using light of 550 nm.

  The resin used for the protective layer is preferably a fluororesin or an acrylic resin. The fluororesin is a polymer obtained by polymerizing a monomer containing a fluorine monomer. Preferable examples of the fluorine-based monomer include fluorine-based ethylene monomers such as vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, and trifluoroethylene chloride. In addition to fluorine-based monomers, one or more copolymerizable monomers such as methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, and acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate May be copolymerized. Moreover, you may form a protective layer from the resin composition which blended the fluororesin and the acrylic resin.

  When forming a protective layer, the thickness is 10-100 micrometers normally, Preferably it is 20-50 micrometers. This is because if it is thinner than 10 μm, the wear resistance and scratch resistance are insufficient as a protective layer, and if it is thicker than 100 μm, it is disadvantageous in terms of cost.

  The base layer, the reinforcing layer, and the optional protective layer can contain usual additives such as an ultraviolet absorber, a slip agent, an antifungal agent, a colorant and the like.

The decorative film of the present invention can be produced, for example, as follows.
First, the reinforcing layer is fixedly disposed on the back surface of the base layer so that the front surface thereof is opposed. The method for fixedly arranging the reinforcing layer on the back surface of the base layer is not particularly limited. However, as a preferable method, a reinforcing layer forming resin dissolved in a solvent is applied to the back surface of the base layer, and the solvent is removed to form the reinforcing layer. A method for forming, a method for forming a reinforcing layer by heating and melting a resin for forming a reinforcing layer, applying this to the back surface of the base layer and cooling to solidify the resin for forming the reinforcing layer, or already in a film form For example, a method in which the formed reinforcing layer and the base layer are pressure-bonded by heat lamination. In addition, a method is adopted in which a reinforcing layer is formed on the surface of the process film, the reinforcing layer and the base layer are pressure-bonded by thermal lamination, and the reinforcing layer is fixedly disposed on the back surface of the base layer, and then the process film is peeled off. You can also

  A primer layer can be provided between the base layer and the reinforcing layer to increase adhesion between the layers. This primer layer can also be arranged using a method similar to the method of arranging the reinforcing layer on the back surface of the base layer.

In the case where the protective layer is provided on the surface of the base layer, various methods can be used as described above.
Furthermore, embossing can be performed on the surface of the protective layer to produce a decorative film with high design properties. The embossing is performed by heating the embossing roll and the decorative film and pressing an arbitrary uneven pattern provided on the embossing roll on the decorative film, as in the case of embossing of a normal resin film.

  A decorative sheet can also be produced by bringing the adhesive layer into close contact with the back surface of the decorative film of the present invention. As a method of closely adhering the adhesive layer, after applying and solidifying a coating solution containing an adhesive on the back surface of the film, laminating so that the release surface of the liner faces the back surface of the adhesive layer, There is a method in which a coating liquid containing an adhesive is applied to the release surface and dried to form an adhesive layer with a liner, and then this adhesive layer with a liner is laminated on the back surface of the film.

  The adhesive is preferably a pressure-sensitive adhesive because of its ease of handling, and commonly used pressure-sensitive adhesives such as acrylic, synthetic rubber, and natural rubber can be used. From the viewpoint, an acrylic pressure-sensitive adhesive is preferably used.

  Moreover, as long as the effect of this invention is not impaired, you may arrange | position another layer, for example, the primer layer etc. which increase the adhesiveness of a film and an adhesive bond layer, between a decorative film and an adhesive bond layer.

  The thickness of the entire decorative sheet is usually 30 to 300 μm, preferably 50 to 200 μm. If the overall thickness of the decorative sheet is too thin, handling becomes difficult and the breaking strength may be reduced. On the other hand, if it is too thick, the workability is deteriorated due to the effect of the stiffness of the sheet, and the fireproof performance may be inferior. In addition, the decorative sheet according to the present invention can obtain a non-combustible level in a fire prevention test (heating rate test ISO 5660-1, metal (0.27 mm zinc steel sheet) base) of a fire wall covering material “plastic wallpaper” defined in the Building Standard Law. It is preferable that there is a degree of fire prevention performance.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these Examples.

The decorative film and decorative sheet of this example were produced as follows.
Production of decorative film:
First, an 80 μm-thick colored acrylic film (trade name COLORED ACRYLIC FILM, manufactured by Bando Chemical Co., Ltd.) having a Tg of 56 ° C. was prepared as a base layer.
As a reinforcing layer, prepare a 40 μm thick film made of an amorphous polyester resin with a Tg of 80 ° C. (manufactured by OSG Co., Ltd., product name PGS2008 (80 μm), and a prototype with a thickness of 40 μm). In order to increase adhesion to the base layer, apply a vinyl chloride-vinyl acetate ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name US ink) with a gravure printing machine on the surface facing the base layer using a solid plate did.

As a protective layer, a 20 μm-thick film (trade name: DX-14S0220, manufactured by Electrochemical Co., Ltd.) containing a fluororesin and an acrylic resin was prepared.
The reinforcing layer, the base layer, and the protective layer were laminated in this order and pressure-bonded by heat lamination, and then a texture pattern was applied to the surface of the protective layer by embossing to obtain a decorative film.

Production of decorative sheet:
A coating liquid containing an acrylic pressure-sensitive adhesive was applied to the release surface of the liner and dried to form an adhesive layer with a liner. Then, this adhesive with a liner was laminated on a film to obtain a decorative sheet.

  As a reinforcing layer, a 40 μm-thick film made of an amorphous polyester resin having a Tg of 56 ° C. (a prototype manufactured by Achilles Co., Ltd., trade name FIPY2003 (80 μm) and having a thickness of 40 μm) was used. A decorative film and a decorative sheet were produced in the same manner as in Example 1.

  As a reinforcing layer, a urethane resin having a Tg of −2 ° C. (made by Nippon Polyurethane Industry Co., Ltd., trade name NIPPOLAN YN-191) is prepared, and this is coated on a process substrate (made by 3M, trade name SCW200) with a knife coater. Was applied and dried to obtain a reinforcing layer having a thickness of 30 μm. After laminating the same base layer and protective layer as used in Example 1 on the process substrate on which the reinforcing layer is arranged and press-bonding with a thermal laminate, the surface of the protective layer is given a texture pattern by embossing. did. Thereafter, the process substrate was removed to obtain a decorative film.

Preparation of decorative sheet A coating liquid containing an acrylic pressure-sensitive adhesive was applied to the release surface of the liner, dried to form an adhesive layer with a liner, and then this adhesive with liner was laminated on a film to obtain a decorative sheet. It was.

  A decorative film and a decorative sheet were produced in the same manner as in Example 3 except that the thickness of the reinforcing layer was 50 μm.

[Comparative Example 1]
A decorative film and a decorative sheet were produced in the same manner as in Example 1 except that the reinforcing layer was not provided.

[Comparative Example 2]
Makeup in the same manner as in Example 1 except that a film made of crystalline polyester resin (trade name, single-sided easy-adhesion treated transparent polyester film: ST-20 (prototype) thickness 20 μm) made of crystalline polyester resin was used as the reinforcing layer. Films and decorative sheets were prepared.

[Comparative Example 3]
40 μm-thick film made of amorphous polyester resin mixed with polycarbonate resin with a Tg of 121 ° C. as the reinforcing layer (trade name CG030M super heat-resistant OS (100 μm) manufactured by Taihei Chemical Products Co., Ltd., having a thickness of 40 μm) A decorative film and a decorative sheet were produced in the same manner as in Example 1 except that the prototype) was used.

[Comparative Example 4]
As a reinforcing layer, a film composed of an acrylic urethane resin having a Tg of 35 ° C. (Commercial name Desmofen A365BA / X and Sumidur N75 manufactured by Sumitomo Bayer Urethane Co., Ltd. are blended so that NCO / OH = 1/1, and the thickness is 30 μm. A decorative film and a decorative sheet were produced in the same manner as in Example 3 except that the obtained product was used.

About the decorative sheet produced by the said Example and the comparative example, tear strength, three-dimensional curved surface workability, and combustion resistance were evaluated with the following method. The results are shown in Table 1.
(Tear strength)
The obtained decorative sheet was cut into a 63 mm × 75 mm shape, three sheets were stacked, and tear strength was measured by the Elmendorf tear method described in JIS K7128.
(Three-dimensional curved surface workability)
Use a hair dryer with an outlet temperature of 100 ° C to attach a decorative sheet to the round top plate via an adhesive layer and follow the curved surface part. When the sheet edge peeled off, it was set as “impossible”.
The specifications of the round top plate are as follows:
Material: MDF board Diameter: 490mm
Thickness: 25mm
Roundness of top plate edge: both ends of cross section: R5
Cross section center: R15
(Combustion resistance)
The flammability of the resulting decorative sheet was measured by the corn calorimeter method described in ISO 5660-1, and the total calorific value passed 8 MJ / m ² or less, and the maximum heat generation rate continued for 10 seconds or more. Therefore, those that did not exceed 200kW / m ² were accepted.

  As a result of the above test, the decorative film of Comparative Example 1 in which the reinforcing layer was not provided had a low tear strength. The decorative film of Comparative Example 2 provided with a reinforcing layer made of a crystalline polyester resin and the decorative film of Comparative Example 3 provided with a reinforcing layer containing an amorphous polyester resin having a Tg of 121 ° C. have sufficient tear strength. Although it had, it was inferior to three-dimensional curved surface workability. In Comparative Example 4, a reinforcing layer made of a urethane resin having a Tg higher than 0 ° C. was provided, but the tear strength remained low.

On the other hand, in the decorative films of Example 1, Example 2, Example 3 and Example 4, by providing a reinforcing layer made of a resin having appropriate characteristics, the tear strength is increased and at the same time, the reinforcing layer However, the decorative film had excellent three-dimensional curved surface workability without impairing the flexibility (workability) of the base layer containing the acrylic resin. In the case of Example 4, a flammability test was conducted with the thickness of the reinforcing layer being 50 μm, and from this result, a decorative film with a thin reinforcing layer was produced for applications that require fire prevention performance. It turns out to be advantageous.

Claims (5)

(A) an acrylic resin-containing base layer having a surface functioning as a colorant-receiving surface and a back surface facing the surface;
(B) a decorative film having a reinforcing layer disposed on the back surface of the base layer,
The reinforcing layer contains at least one resin selected from the group consisting of an amorphous polyester resin having a glass transition point of 50 ° C to 100 ° C and a urethane resin having a glass transition point of -50 ° C to 0 ° C. A decorative film comprising a layer to be applied.   The glass transition point of the acrylic resin is 40 ° C to 80 ° C.   The decorative film according to claim 1, further comprising a light-transmitting protective layer on the decorative film surface, wherein the protective layer is made of a resin composition containing a fluororesin and an acrylic resin.   A decorative sheet comprising the decorative film according to any one of claims 1 to 3 and an adhesive layer provided on the back side of the reinforcing layer of the decorative film. The decorative sheet according to claim 4, wherein the tear strength according to the Elmendorf tear method defined in JIS-K 7128 is 1.0 N or more.