JP6341493B2 - Manufacturing method of decorative sheet - Google Patents

Description

  The present invention relates to a method for manufacturing a decorative sheet.

  To improve the appearance and protect the surface of building materials such as building exterior walls, housing entrance doors, exterior / interior of automobiles, exterior / interior of vehicles / ships, signboards / signs, etc. It is used.

As a decorative sheet, generally, a laminate of various resin films mainly composed of vinyl chloride resin or polyethylene terephthalate resin is used.
Further, as a decorative sheet, one having a surface layer and a design layer is widely known, and a transparent layer (also referred to as “intermediate layer” in the present specification) is further provided between the surface layer and the design layer. ) May be laminated.

Examples of the method for attaching the resin films when laminating include a dry laminating method and a heat bonding method. Any sticking method is appropriately employed depending on the required appearance and durability of the decorative sheet.
Patent Documents 1 to 3 disclose a method for producing a decorative sheet mainly composed of a polyethylene terephthalate resin.

Specifically, in Patent Document 1, a hard coat film (surface layer) made of a biaxially stretched crystalline polyethylene terephthalate resin film coated with a hot-melt adhesive, and a transparent amorphous layer laminated on a design substrate layer A dry laminating method is employed for adhering to a transparent layer (intermediate layer) mainly composed of polyethylene terephthalate resin.
Patent Document 2 discloses a design layer of a colored resin material mainly composed of an amorphous or low crystalline polyester resin and a transparent layer (intermediate layer) composed mainly of an amorphous or low crystalline polyester resin. And a manufacturing method of a laminate of a polyethylene terephthalate film and a surface layer obtained by applying a transparent ink containing a vinyl chloride-vinyl acetate polymer. A heat bonding method using a heating drum is employed for adhering the surface layer and the transparent layer (intermediate layer) obtained by laminating the design layer.
In Patent Document 3, a dry laminating method is employed for adhering a decorative film mainly composed of a polyethylene terephthalate resin and a biaxially stretched (copolymerized) polyethylene terephthalate film. Moreover, the thermal lamination method is employ | adopted for sticking of the decorative film which has a polyethylene terephthalate type resin as a main component, and a clear film.

JP 2001-47582 A JP 2003-136666 A JP 2004-75924 A

  In the manufacturing method of the decorative sheet of patent documents 1-3, there existed a subject that the external appearance of the manufactured decorative sheet was inferior. There is also a problem that the manufacturing process is complicated.

The present inventors pressure-bond the surface layer to a design layer made of a melt-extruded polyethylene terephthalate resin, or a technique of pressure-bonding the surface layer and the design layer to an intermediate layer made of the melt-extruded polyethylene terephthalate resin. The method has been adopted and the present invention has been completed.
That is, the present invention has the following configuration.
[1] A method for producing a decorative sheet in which a design layer mainly comprising a polyethylene terephthalate resin and a surface layer mainly comprising a polyethylene terephthalate resin are laminated,
Including an extrusion laminating step for pressure-bonding the surface layer to the design layer formed by melt-extruding a polyethylene terephthalate-based resin into a film,
The surface layer includes a surface base material layer made of a stretched polyethylene terephthalate film, and an adhesive layer provided in advance on the side of the surface base material layer on which the design layer is pressure-bonded.
A method for producing a decorative sheet.
[2] The adhesive layer contains at least one heat-sealable resin selected from the group consisting of polyester resins, polyurethane resins, polyester-polyurethane resins, acrylic resins, and ethylene-vinyl acetate copolymers. [1] A method for producing a decorative sheet according to [1].
[3] The method for manufacturing a decorative sheet according to [1] or [2], wherein a hard coat layer is provided in advance on the side of the surface base material layer opposite to the side on which the design layer is pressure-bonded.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet excellent in the external appearance can be manufactured. In addition, the manufacturing process can be simplified.

It is the sectional side view schematic which showed an example of the decorative sheet manufactured by this invention. It is the schematic which showed an example of the manufacturing apparatus used for the manufacturing method of this invention. It is the schematic which showed the other example of the manufacturing apparatus used for the manufacturing method of this invention. It is the sectional side view schematic which showed the other example of the decorative sheet manufactured by this invention. It is the schematic which showed the other example of the manufacturing apparatus used for the manufacturing method of this invention. It is the sectional side view schematic which showed the other example of the decorative sheet manufactured by this invention.

FIG. 1 is a schematic side sectional view showing an example of a decorative sheet manufactured according to the present invention.
As shown in FIG. 1, a decorative sheet 1 manufactured according to the present invention includes a surface layer 10, a design layer 20, and an intermediate layer 30 positioned between these layers.

A. Surface Layer The surface layer 10 is a layer that prevents scratches and the like generated on the decorative sheet surface.
The surface layer 10 used in the present invention was formed on the surface base layer 11, the adhesive layer 12 formed on the side of the surface base layer 11 that adheres to the intermediate layer 30, and the outermost surface of the decorative sheet 1. And a hard coat layer 13 (FIG. 1).

(Surface base material layer)
As the surface base material layer 11, a film containing a polyethylene terephthalate resin as a main component is used. The film used for the surface base material layer 11 should be excellent in surface hardness, chemical resistance and transparency, and specifically, stretched polyethylene terephthalate film. Among these, a biaxially stretched polyethylene terephthalate film is preferable.
Moreover, the surface base material layer 11 may use a transparent thing, and may use what was colored in order to improve the designability.

  12-200 micrometers is preferable, as for the thickness of the surface base material layer 11, 20-100 micrometers is more preferable, and 30-70 micrometers is especially preferable. If the thickness of the surface base material layer 11 is not less than the lower limit value, it is easy to maintain the appearance and surface performance as a decorative sheet, and if it is not more than the upper limit value, it is advantageous in terms of price.

(Adhesive layer)
The surface layer 10 includes an adhesive layer 12 in advance so as to be excellent in the appearance and adhesion strength of the decorative sheet 1 of the present invention.
A heat-sealable resin is used as the adhesive constituting the adhesive layer 12. By providing the adhesive layer 12 containing a heat-sealable resin, the adhesiveness between the surface base material layer 11 and the intermediate layer 30 can be enhanced.
Examples of the heat sealable resin include polyester resins, polyurethane resins, polyester-polyurethane resins, acrylic resins, and ethylene-vinyl acetate copolymers. Of these, polyester-polyurethane resins are preferred. These may be used alone or in combination. The adhesive may contain a curing agent such as isocyanate.
As the adhesive used in the present invention, a polyester-polyurethane resin containing isocyanate as a curing agent is preferable from the viewpoint of the appearance and adhesion strength of the decorative sheet 1.

As a method of forming the adhesive layer 12, a method of applying a liquid (dispersion or solution) containing a heat-sealable resin to one surface of the surface base material layer 11 and aging is adopted.
Examples of the coating method include a gravure coating method (including a micro gravure coating method), a roll knife coating method, a die coating method, a reverse roll coating method, a roll coating method, and a cast coating method.
As an aging method, for example, it is performed by curing at 40 ° C. for 2 days.

  0.1-20 micrometers is preferable and, as for the thickness of the contact bonding layer 12, 1-8 micrometers is more preferable. If the thickness of the adhesive layer 12 is equal to or greater than the lower limit, the heat sealability is sufficiently high, and if the thickness is equal to or less than the upper limit, the adhesive layer 12 can be easily formed.

(Hard coat layer)
The surface layer 10 may include a hard coat layer 13 in advance in order to further enhance prevention of scratches and the like on the decorative sheet surface. The hard coat layer 13 is a layer whose pencil hardness is harder than HB, and is a layer formed of an active energy ray-curable resin that is polymerized by irradiation with an active energy ray (ultraviolet ray or electron beam).
Here, as the active energy ray curable resin, a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule, and a monofunctional (meth) methacrylate having one (meth) acryloyl group in the molecule. ) Acrylates.

As polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule, neopentyl glycol di (meth) acrylate, 1,6-hexanediol diacrylate, (meth) trimethylolpropane tri (meth) ) Polyol, poly ( (Meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, di (meth) acrylate of neopentyl glycol diglycidyl ether, 1,6-hexanediol jig Polyester (meth) acrylate obtained by esterifying epoxy (meth) acrylate such as di (meth) acrylate of sidyl ether, polyhydric alcohol and polyhydric carboxylic acid and / or anhydride thereof and (meth) acrylic acid , Urethane (meth) acrylate obtained by reacting polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing (meth) acrylate, polysiloxane poly (meth) acrylate, and the like.
Monofunctional (meth) acrylates include hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy Examples thereof include propyl (meth) acrylate and glycidyl (meth) acrylate.
These may be used individually by 1 type, and may mix and use 2 or more types.

  1-30 micrometers is preferable and, as for the thickness of the hard-coat layer 13, 2-20 micrometers is more preferable. If the thickness of the hard coat layer 13 is not less than the lower limit value, sufficiently high scratch resistance can be obtained, and if it is not more than the upper limit value, the occurrence of cracks in the hard coat layer 13 can be prevented.

B. Design Layer The design layer 20 is a layer that improves the design properties of the decorative sheet 1. In this example, the design base layer 21 and the print formed on the side of the design base layer 21 that adheres to the intermediate layer 30 are printed. And layer 22 (FIG. 1).

(Design substrate layer)
As the design base material layer 21 used in the production method of the present invention, a colored polyethylene terephthalate resin film is preferable. From the viewpoint of facilitating the secondary curved surface processing of the decorative sheet 1, a glycol-modified polyethylene terephthalate (hereinafter also referred to as “PETG”) film is more preferable.
Glycol-modified polyethylene terephthalate is a kind of polyethylene terephthalate. The glycol component of polyethylene terephthalate is ethylene glycol, whereas the glycol component is an amorphous polyester containing diol in addition to ethylene glycol.

  20-700 micrometers is preferable and, as for the thickness of the design base material layer 21, 50-500 micrometers is more preferable. If the thickness of the design base material layer 21 is equal to or greater than the lower limit value, the mechanical strength and concealment can be sufficiently increased, and if the thickness is equal to or less than the upper limit value, sufficient flexibility and printability can be ensured.

(Print layer)
In the printing layer 22, as a pattern or pattern formed by printing, for example, wood grain, stone pattern, cloth pattern, grain pattern, tiled pattern, brickwork pattern, leather pattern, geometric pattern, character, symbol, metallic, etc. Is mentioned. These patterns and patterns can be combined.
Examples of the printing method include screen printing, gravure printing, flexographic printing, and the like.
The ink used for the printing layer 22 contains a binder resin and a colorant.
Examples of the binder resin include acrylic resin, vinyl chloride-vinyl acetate copolymer, chlorinated polypropylene, polyester resin, cellulose resin, and urethane resin.
Examples of the colorant include inorganic pigments such as titanium white, zinc white, carbon black, iron black, petal, chrome vermillion, cadmium red, ultramarine, cobalt blue, yellow lead, and titanium yellow, phthalocyanine blue, and indanthrene. Examples thereof include organic pigments such as blue, isoindolinone yellow, benzylidine yellow, quinacridone red, polyazo red, berylene red, and aniline black, and pearlescent pigments such as scaly foil powder such as aluminum and brass. The colorants can be used alone or in combination of two or more.

  At least one of the resin film constituting the design base material layer 21 and the ink used for the printing layer 22 includes, as necessary, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a storage stabilizer, Additives such as plasticizers, lubricants and fillers may be included.

C. Intermediate Layer The intermediate layer 30 is a layer for further improving the design properties of the decorative sheet 1 such as adding depth to the design applied to the design layer 20.
As the intermediate layer 30, polyethylene terephthalate resin is used. PETG is preferable because it facilitates the quadric surface processing of the decorative sheet 1.
The intermediate layer 30 may be transparent or colored.

For example, when transparent PETG is used, the thickness of the intermediate layer 30 is preferably 100 to 600 μm. When using colored PETG, 100-700 micrometers is preferable and 200-550 micrometers is more preferable.
D. Production method

The present invention is a manufacturing method to which an extrusion laminate is applied.
In the present invention, “extruded laminate” refers to a resin obtained by heating and melting a polyethylene terephthalate resin using an extruder and extruding it from a T-die to form a film. It means sticking to a film, inserting between rolls, and laminating.

  Here, it is preferable that the resin extruded from the T-die and formed into a film is maintained in a molten state until it is attached to another film. Alternatively, the resin extruded from the T die and formed into a film shape may be pasted on the other film as long as it does not affect the adhesion between the resin extruded from the T die and formed into a film shape. It may be semi-solidified before it is worn.

In FIG. 2, an example of the manufacturing apparatus 60 used for the manufacturing method of this invention is shown.
The manufacturing apparatus 60 includes an extruder 40, a surface layer sending unit 51, a design layer sending unit 52, and pressure bonding rolls 50a and 50b.
The extruder 40 includes a T die 41 that discharges the film-like intermediate layer 30.
The surface layer delivery means 51 supplies the surface layer 10 toward the pressure roll 50a. The crimping roll 50 a winds the surface layer 10 and crimps the wound surface layer 10 to the first surface 30 a of the intermediate layer 30.
The design layer sending means 52 supplies the design layer 20 toward the pressure-bonding roll 50b. The crimping roll 50 b winds the design layer 20 and crimps the wound design layer 20 to the second surface 30 b of the intermediate layer 30.
The crimping rolls 50a and 50b are located downstream of the T-die 41 and the crimping roll 50a is located downstream of the crimping roll 50b.

  In the manufacturing method of the present invention using the manufacturing apparatus 60 of FIG. 2, the surface layer 10 is formed on the first surface 30a of the intermediate layer 30 formed by discharging a polyethylene terephthalate resin from the T die 41 of the extruder 40 into a film shape. And an extrusion laminating process in which the design layer 20 is pressure-bonded to the second surface 30b of the intermediate layer 30.

In forming the intermediate layer 30, a transparent resin mainly composed of polyethylene terephthalate resin is melted in the extruder 40. The molten resin is discharged from the T die 41 of the extruder 40 in the form of a film, and the intermediate layer 30 is formed. In this example, at this time, the molten resin is discharged toward the pressure-bonding roll 50b.
The melting temperature in the extruder 40 is preferably set in the range of 150 to 280 ° C.
The discharge amount is appropriately set so as to be the thickness of the intermediate layer 30 described above.

  In the press bonding between the intermediate layer 30 and the surface layer 10 and the design layer 20, the design layer 20 supplied from the design layer sending means 52 to the press roll 50b is applied to the second surface 30b of the intermediate layer 30 by the press roll 50b. At approximately the same time, the surface layer 10 supplied from the surface layer delivery means 51 to the pressure roll 50a is pressure-bonded to the first surface 30a of the intermediate layer 30 by the pressure roll 50a.

Here, the surface layer 10 and the design layer 20 may be bonded to the intermediate layer 30 simultaneously or substantially simultaneously, and the pressing order of the surface layer 10 and the design layer 20 to the intermediate layer 30 may be reversed.
The direction in which the surface layer 10 or the design layer 20 is pressure-bonded may be from the top or the bottom toward the intermediate layer 30 and can be set as appropriate. The intermediate layer 30 is discharged from the T-die 41 of the extruder 40 toward the space between the pressure roll 50a and the pressure roll 50b, and the intermediate layer 30 is pressure-bonded so as to be sandwiched between the surface layer 10 and the design layer 20 from the side. Good (Figure 3).

  After pressure bonding of the intermediate layer 30, the surface layer 10, and the design layer 20, a film in which the surface layer 10, the intermediate layer 30, and the design layer 20 are laminated is discharged from the manufacturing apparatus 60, and the decorative sheet 1 is obtained.

E. Effect The decorative sheet 1 produced by the production method of the present invention is superior in appearance as compared with a decorative sheet attached by a dry laminating method. Further, if an adhesive containing a polyester-polyurethane resin is used, higher adhesion strength can be obtained. That is, according to the production method of the present invention, it is possible to produce a high-quality decorative sheet 1 having excellent appearance and high adhesion strength.
Moreover, according to the manufacturing method of the present invention, since the intermediate layer 30 is formed, the surface layer 10 and the design layer 20 can be attached to the intermediate layer 30 simultaneously or substantially simultaneously in the same process. Simplification and further reduction in manufacturing time can be achieved.

F. Other Embodiments The production method of the present invention comprises a surface layer 10 mainly composed of a polyethylene terephthalate resin, which is provided with an adhesive, and a molten or semi-solidified polyethylene formed in a film form from an extruder 40. There is an essential technical significance in that a terephthalate-based resin is used and stuck by an extrusion laminating method.
Therefore, in the surface layer 10 of FIG. 1, the hard coat layer 13 located on the surface side of the decorative sheet 1 can be omitted because it does not directly relate to the bonding with the intermediate layer 30 (FIG. 4). In this case, after producing the decorative sheet 1 by the manufacturing method of the present invention using the surface layer 10 that does not have the hard coat layer 13, the hard coat layer 13 may be adhered.

In the design layer 20 used in the manufacturing method of the present invention, the print layer 22 may be omitted if the design properties of the decorative sheet 1 can be satisfied only by the design base material layer 21 (FIG. 4).
Further, a coating layer may be provided instead of the printing layer 22. The coating in the coating layer is to apply the same ink as the ink used for the printing layer 22 to the surface of the design base material layer 21 to uniformly color the surface of the design base material layer 21.
Examples of the coating method include a gravure coating method (including a micro gravure coating method), a roll knife coating method, a die coating method, a reverse roll coating method, a roll coating method, and a cast coating method.

In addition, since the present invention has the above technical significance, the design layer 20 may be a molten or semi-solidified polyethylene terephthalate resin formed into a film form from the extruder 40 described above. (FIG. 5). That is, it may be a manufacturing method including an extrusion laminating step in which the surface layer 10 is pressure-bonded to the design layer 20 formed by melt-extruding a polyethylene terephthalate resin into a film shape. In this case, in order to obtain the effect according to the present invention, the design layer 20 is not provided with a printing layer, and consists only of the design base material layer 21 (FIG. 6).
The design substrate layer 21 in this case may be transparent or colored. Moreover, the thickness of the design base material layer 21 in this case is preferably 100 to 600 μm, for example, when transparent PETG is used. When using colored PETG, 100-700 micrometers is preferable and 200-550 micrometers is more preferable.

Hereinafter, specific examples of the present invention will be described by way of examples.
In Reference Examples 1 to 3 described later, the decorative sheet 1 was produced by an extrusion laminating method using the manufacturing apparatus 60 shown in FIG.

(Reference Example 1)
An adhesive was applied to stretched polyethylene terephthalate film A-4100 (Toyobo Co., Ltd.) so as to be 4 g (dry mass) per 1 m ² . Adhesive used is Dick Seal A970 / Dick Seal A970FP-8 / W-AH (80/20/3) (manufactured by DIC Graphics Corp.) containing polyester-urethane resin as the main agent and isocyanate as the curing agent. did. After coating, curing was performed at 35 ° C. for 2 days to obtain a surface layer 10. The surface layer 10 was wound up into a wound body, and the wound body was attached to the surface layer sending means 51 when the decorative sheet 1 was produced.
Further, a design film 20 was obtained by printing on a resin film containing transparent PETG (GN071 (Eastman Chemical Co., Ltd.)) as a main component with SX ink (Showa Ink Industry Co., Ltd.).
The design layer 20 was wound into a wound body, and the wound body was attached to the design layer sending means 52 when the decorative sheet 1 was produced.

In producing the decorative sheet 1, first, transparent PETG (GN071) was melted in the extruder 40. The melting temperature of the extruder was set to 240 ° C. The melted resin was discharged from the T die 41 of the extruder 40 in the form of a film, and the intermediate layer 30 was formed. Further, the surface layer 10 was sent from the surface layer sending means 51 toward the pressure roll 50a, and the design layer 20 was sent from the design layer sending means 52 toward the pressure roll 50b.
Next, the design layer 20 wound on the pressure roll 50b from the design layer sending means 52 is pressure-bonded to the second surface 30b of the intermediate layer 30, and at the same time, the surface temperature is set to 160 ° C. from the surface layer sending means 51. The surface layer 10 wound around the crimping roll 50 a was crimped to the first surface 30 a of the intermediate layer 30.
After the pressure bonding, the laminated film was discharged from the manufacturing apparatus 60, and the decorative sheet 1 was obtained.

(Reference Example 2)
In place of the adhesive used in Reference Example 1, a urethane-vinyl chloride / vinyl acetate copolymer resin as a main agent and an adhesive containing isocyanate as a curing agent, a THF primer (S) / XEL curing agent (D) ( 100/5) (manufactured by Inktec Co., Ltd.) was used to produce a decorative sheet 1 in the same manner as in Reference Example 1.

(Reference Example 3)
In place of the adhesive used in Reference Example 1, except that TM-A1HS (K) (manufactured by Dainichi Seika Co., Ltd.), which is an adhesive containing urethane-vinyl chloride / vinyl acetate copolymer resin, is used as the main agent. A decorative sheet 1 was produced in the same manner as in Reference Example 1.

(Comparative example)
In the same manner as in Reference Example 1, an intermediate layer was formed. The same design layer as that used in Reference Examples 1 to 3 was thermally attached to this intermediate layer from below.
Next, Hibon YA790-1 / Coronate L (100/10) (Hitachi Chemical Polymer), which is an adhesive containing a polyester resin as a main agent and an isocyanate as a curing agent, on a stretched polyethylene terephthalate film A-4100 (Toyobo Co., Ltd.) Co., Ltd.) was applied so as to be 10 g (dry mass) per m ² and dried at 80 ° C.
Finally, the stretched polyethylene terephthalate film coated with an adhesive was pasted on the intermediate layer on which the design layer was heat pasted by the dry laminating method, and then aged at 50 ° C. for 2 days to obtain a decorative sheet.

(Evaluation test of decorative sheet)
An evaluation test of the decorative sheets prepared in the above Reference Examples 1 to 3 and Comparative Example was performed.
Appearance was evaluated by visual observation of whether or not the skin of the decorative sheet was damaged.
The adhesion strength was evaluated by a 180 ° peel test according to JISK6854-2 and a T-shaped peel test according to JISK6854-3. In the evaluation, Autograph AG-500D (Shimadzu Corporation) was used as a measuring device under the conditions of a test temperature of 23 ° C. and a tensile speed of 300 mm / min.
The results of these evaluation tests are shown in Table 1.

These results show that the decorative sheets of Reference Examples 1 to 3 produced by the above production method are superior in appearance compared to the decorative sheet of the comparative example in which the surface layer is pasted by the dry laminating method. .
In particular, Reference Example 1 using a polyester-urethane resin as the main agent and an adhesive containing isocyanate as the curing agent indicates a decorative sheet having excellent appearance and sufficient adhesion strength.

DESCRIPTION OF SYMBOLS 1 ... Cosmetic sheet 10 ... Surface layer 11 ... Surface base material layer 12 ... Adhesive layer 13 ... Hard-coat layer 20 ... Design layer 21 ... Design base material layer 22 ... Print layer 30 ... Intermediate | middle layer 30a ... 1st surface 30b ... 2nd Surface 40 ... Extruder 41 ... T-die 50a, 50b ... Pressure roll 51 ... Surface layer sending means 52 ... Design layer sending means 60 ... Manufacturing apparatus

Claims (3)

A method for producing a decorative sheet in which a design layer mainly comprising a polyethylene terephthalate resin and a surface layer mainly comprising a polyethylene terephthalate resin are laminated,
Including an extrusion laminating step for pressure-bonding the surface layer to the design layer formed by melt-extruding a polyethylene terephthalate-based resin into a film,
The surface layer includes a surface base material layer made of a stretched polyethylene terephthalate film, and an adhesive layer provided in advance on the side of the surface base material layer on which the design layer is pressure-bonded.
A method for producing a decorative sheet.   The adhesive layer includes at least one heat-sealable resin selected from the group consisting of a polyester resin, a polyurethane resin, a polyester-polyurethane resin, an acrylic resin, and an ethylene-vinyl acetate copolymer. The manufacturing method of the decorative sheet of description.   The manufacturing method of the decorative sheet of Claim 1 or 2 which provides a hard-coat layer previously in the opposite side to the side which crimps | bonds the said design layer of the said surface base material layer.

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