JP4834457B2 - Laminated decorative sheet - Google Patents

Description

  The present invention relates to a laminated decorative sheet. More specifically, the present invention has good embossability, excellent abrasion resistance and scratch resistance on the sheet surface, high dynamic friction coefficient, and is not slippery, excellent solvent resistance and interlayer adhesion at high temperature, The present invention relates to a laminated decorative sheet having good three-dimensional formability.

Conventionally, a lot of vinyl chloride resin films have been used in decorative sheets used for furniture, doors, door frames, waistboards, skirting boards, window frames, and other surface materials. The vinyl chloride resin decorative sheet is laminated on a heating drum of a doubling machine, with a transparent vinyl chloride resin film and a printed colored vinyl chloride resin film superimposed on each other, and thermocompression bonded. Manufactured by embossing. However, since the vinyl chloride resin generates hydrogen chloride during combustion, development of a laminated decorative sheet using a material that replaces the vinyl chloride resin has been underway.
Currently, the base layer is a colored opaque amorphous polyester resin film having a printing layer on the surface, the surface layer is a transparent olefin resin film, and a top coat of a two-component curable urethane resin thereon However, there are problems in that it is inferior in wear resistance and it is difficult to achieve both slip prevention and scratch resistance. Furthermore, the three-dimensional formability is not good.
A transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film that have excellent scratch resistance, have a concealing power that can withstand vacuum forming, and have a deep, highly designed amorphous polyester resin film. Is a thermo-compression bonding, and the surface of the transparent amorphous polyester resin film has a two-component urethane resin coating film containing 0.5 to 20 parts by weight of wax per 100 parts by weight of the urethane resin A decorative sheet has been proposed (Patent Document 1). However, the coating film of this two-pack type urethane resin does not sufficiently satisfy the abrasion resistance, and the solvent is volatilized as a volatile organic compound (VOC) when forming the coating film, and a part of the solvent Remains in the coating film and easily causes environmental pollution. Furthermore, there is a problem that it is difficult to achieve both slip prevention and scratch resistance.
Also, as a coating sheet that can obtain a molded product with excellent appearance, the surface does not whiten even when molded by applying a large pressure at room temperature, such as a stamping molding method. The surface layer mainly composed of elastomer, the adhesive layer mainly composed of polyolefin resin, and the base material layer mainly composed of polyolefin resin are laminated and integrated in this order, and the stress at break of the adhesive layer is 25 MPa or more. A laminated sheet is proposed (Patent Document 2). However, this laminated sheet is inferior in three-dimensional formability, and has a problem that interlayer adhesion is weak when used at high temperatures.
JP 2002-103544 A JP 2002-86618 A

  The present invention has good embossability, excellent abrasion resistance and scratch resistance on the sheet surface, high dynamic friction coefficient, non-slip, excellent solvent resistance and interlayer adhesion at high temperature, and three-dimensional formability It was made for the purpose of providing a laminated decorative sheet that is also good.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a transparent thermoplastic urethane elastomer or a laminate of a transparent thermoplastic urethane elastomer and a transparent amorphous polyester resin as an upper layer, Using an amorphous polyethylene terephthalate-based resin having a printing layer as the above, by laminating the upper layer and the lower layer, the embossability is good, the sheet surface is excellent in abrasion resistance and scratch resistance, and the dynamic friction coefficient is It was found that a laminated decorative sheet that is difficult to slip due to its large size, excellent in solvent resistance and interlaminar adhesion at high temperature, and also excellent in three-dimensional formability was obtained, and the present invention was completed based on this finding. .
That is, the present invention
(1) As upper layer (A), (A) thermoplastic urethane elastomer layer, as lower layer (A), (E) amorphous polyethylene terephthalate resin layer, (F) polyvinyl chloride resin layer or (G) ABS A laminated decorative sheet characterized in that a resin layer is laminated and (A) a matte unstretched polypropylene resin layer is provided as a protective transfer layer on the upper side of the thermoplastic urethane elastomer layer ;
(2) As the upper layer (a), (A) a thermoplastic urethane elastomer layer, (B) an amorphous polyester resin layer, (C) an acrylic resin layer or (D) a polycarbonate resin layer are laminated in this order. And (E) an amorphous polyethylene terephthalate resin layer, (F) a polyvinyl chloride resin layer, or (G) an ABS resin layer , and (A) an upper layer of a thermoplastic urethane elastomer layer. And (H) a laminated decorative sheet characterized by having a mat unstretched polypropylene resin layer as a protective transfer layer ,
(3) Laminated product of (A) thermoplastic urethane elastomer layer of upper layer (a) and (B) amorphous polyester resin layer, (C) acrylic resin layer or (D) polycarbonate resin layer is coextruded. The laminated decorative sheet according to (2), which is obtained by molding,
( 4 ) The laminated decorative sheet according to any one of (1) to ( 3 ), wherein the upper surface is embossed.
( 5 ) (1) or (2) having a primer layer under the (E) amorphous polyester resin layer, (F) polyvinyl chloride resin layer or (G) ABS resin layer of the lower layer (a) The laminated decorative sheet,
( 6 ) (E) Amorphous polyethylene terephthalate resin is a cyclohexanedimethanol copolymer in which the dicarboxylic acid component is terephthalic acid, and the glycol components are ethylene glycol 60 to 90 mol% and cyclohexanedimethanol 10 to 40 mol%. The laminated decorative sheet according to (1) or (2), which is an amorphous polyethylene terephthalate resin,
( 7 ) (B) Amorphous polyester-based resin, in which the dicarboxylic acid component is terephthalic acid, the glycol component is ethylene glycol 60 to 90 mol% and cyclohexane dimethanol 10 to 40 mol%. A laminated decorative sheet according to (2), which is a crystalline polyethylene terephthalate resin, and
( 8 ) The laminated decorative sheet according to (1) or (2), wherein (A) the thermoplastic urethane elastomer is a non-yellowing polycarbonate urethane elastomer, a non-yellowing ether urethane elastomer or a non-yellowing ester urethane elastomer,
Is to provide.
As another aspect of the present invention,
(1) As upper layer (A), (A) transparent thermoplastic urethane elastomer layer, as lower layer (A), (E) amorphous polyethylene terephthalate resin layer, (F) polyvinyl chloride resin layer or (G) A laminated decorative sheet comprising an ABS resin layer laminated, and having a printing layer between an upper layer (a) and a lower layer (a),
(2) As the upper layer (a), (A) a transparent thermoplastic urethane elastomer layer, (B) a transparent amorphous polyester resin layer, (C) a transparent acrylic resin layer or (D) a transparent polycarbonate resin layer Laminated in order, (E) Amorphous polyethylene terephthalate resin layer, (F) polyvinyl chloride resin layer or (G) ABS resin layer are laminated as the lower layer (A), and the upper layer (A) A laminated decorative sheet characterized by having a printed layer between the lower layers (A),
(3) Laminated product of (A) transparent thermoplastic urethane elastomer layer of upper layer (a) and (B) transparent amorphous polyester resin layer, (C) transparent acrylic resin layer or (D) transparent polycarbonate resin layer Is a laminated decorative sheet according to (2), which is obtained by coextrusion molding,
(4) The laminated decorative sheet according to (1), (2) or (3), which has (H) an unstretched polypropylene resin layer as a protective transfer layer on the upper side of the (A) transparent thermoplastic urethane elastomer layer,
(5) The laminated decorative sheet according to any one of (1) to (4), wherein the upper surface is embossed.
(6) A primer layer is provided under the (E) amorphous polyester resin layer, (F) polyvinyl chloride resin layer, or (G) ABS resin layer of the lower layer (A) (1) or (2) The laminated decorative sheet,
(7) (E) Amorphous polyethylene terephthalate resin is a cyclohexanedimethanol copolymer in which the dicarboxylic acid component is terephthalic acid, and the glycol components are ethylene glycol 60 to 90 mol% and cyclohexanedimethanol 10 to 40 mol%. The laminated decorative sheet according to (1) or (2), which is an amorphous polyethylene terephthalate resin,
(8) (B) Transparent amorphous polyester-based resin is a cyclohexanedimethanol copolymer in which the dicarboxylic acid component is terephthalic acid, and the glycol components are ethylene glycol 60 to 90 mol% and cyclohexanedimethanol 10 to 40 mol%. The laminated decorative sheet according to (2), which is an amorphous polyethylene terephthalate resin, and
(9) The laminated decorative sheet according to (1) or (2), wherein (A) the transparent thermoplastic urethane elastomer is a non-yellowing polycarbonate urethane elastomer, a non-yellowing ether urethane elastomer or a non-yellowing ester urethane elastomer. ,
Is to provide.

  The laminated decorative sheet of the present invention uses a transparent thermoplastic urethane elastomer layer or a laminate of a transparent thermoplastic urethane elastomer layer and a transparent amorphous polyester resin layer as an upper layer, and an amorphous polyethylene having a printed layer as a lower layer Since a terephthalate-based resin layer is used, when a mat unstretched polypropylene film is laminated on the upper layer as a protective transfer layer, good embossing properties can be obtained, and it has excellent wear resistance and scratch resistance. The impact strength is high even at low temperatures and the solvent resistance is good, the delamination strength is high even at high temperatures, the appearance of the plywood laminate is good, and the three-dimensional formability is also excellent. The laminated decorative sheet of the present invention can be suitably used as a surface material for furniture, doors, door frames, waistboards, skirting boards, window frames and the like by being bonded to plywood and steel plates.

The first aspect of the laminated decorative sheet of the present invention comprises: (A) a transparent thermoplastic urethane elastomer layer as the upper layer (a); (E) an amorphous polyethylene terephthalate resin layer as the lower layer (a); A laminated decorative sheet comprising a polyvinyl chloride resin layer or (G) ABS resin layer laminated and having a printing layer between an upper layer (A) and a lower layer (A).
In the second aspect of the laminated decorative sheet of the present invention, as the upper layer (a), (A) a transparent thermoplastic urethane elastomer layer, (B) a transparent amorphous polyester resin layer, (C) a transparent acrylic resin layer, or (D) A transparent polycarbonate resin layer is laminated in this order, and (E) an amorphous polyethylene terephthalate resin layer, (F) a polyvinyl chloride resin layer, or (G) an ABS resin layer as a lower layer (A). A laminated decorative sheet that is laminated and has a printed layer between an upper layer (a) and a lower layer (a).
In the first aspect of the laminated decorative sheet of the present invention, the thickness of the (A) transparent thermoplastic urethane elastomer layer of the upper layer (a) is preferably 30 to 200 μm, more preferably 50 to 120 μm. preferable. If the thickness of the transparent thermoplastic urethane elastomer layer is less than 30 μm, the abrasion resistance of the laminated decorative sheet may be insufficient. The thickness of the transparent thermoplastic urethane elastomer layer is 200 μm or less and has sufficient performance as a laminated decorative sheet, and usually a transparent thermoplastic urethane elastomer layer having a thickness exceeding 200 μm is not necessary.
In the first aspect of the laminated decorative sheet of the present invention, the thickness of the lower layer (A) (E) amorphous polyethylene terephthalate resin layer, (F) polyvinyl chloride resin layer or (G) ABS resin layer is It is preferable that it is 50-300 micrometers, and it is more preferable that it is 80-250 micrometers. When the thickness of the lower layer (a) amorphous polyethylene terephthalate resin layer, polyvinyl chloride resin layer or ABS resin layer is less than 50 μm, the laminated decorative sheet may have insufficient strength. The lower layer (a) amorphous polyethylene terephthalate resin layer, polyvinyl chloride resin layer or ABS resin layer has a thickness of 300 μm or less and has sufficient performance as a laminated decorative sheet, and usually has a thickness exceeding 300 μm. A crystalline polyethylene terephthalate resin layer, a polyvinyl chloride resin layer or an ABS resin layer is not required.

In the second aspect of the laminated decorative sheet of the present invention, the thickness of the thermoplastic urethane elastomer layer (A) above the upper layer (a) is preferably 10 to 100 μm, more preferably 15 to 70 μm. preferable. Moreover, it is preferable that the thickness of (B) transparent amorphous polyester-based resin layer, (C) transparent acrylic resin layer or (D) transparent polycarbonate resin layer on the lower side of the upper layer (a) is 10 to 100 μm, More preferably, it is 20-70 micrometers. If the thickness of the thermoplastic urethane elastomer layer on the upper side of the upper layer (a) is less than 10 μm, the abrasion resistance of the laminated decorative sheet may be insufficient. The thermoplastic urethane elastomer layer on the upper side of the upper layer (a) has a thickness of 100 μm or less and has sufficient performance as a laminated decorative sheet. Usually, a transparent thermoplastic urethane elastomer layer having a thickness exceeding 100 μm is not necessary. If the thickness of the transparent amorphous polyester resin layer, transparent acrylic resin layer or transparent polycarbonate resin layer on the lower side of the upper layer (a) is less than 10 μm, the mechanical strength of the laminated decorative sheet is lowered, and the plywood is laminated. There is a risk that the appearance of the time will deteriorate. The thickness of the transparent amorphous polyester-based resin layer, transparent acrylic resin layer or transparent polycarbonate resin layer on the lower side of the upper layer (a) is 100 μm or less and has sufficient performance as a laminated decorative sheet, and usually has a thickness of 100 μm. A transparent amorphous polyester-based resin layer, a transparent acrylic resin layer or a transparent polycarbonate resin layer is not required.
In the second aspect of the laminated decorative sheet of the present invention, the thickness of the lower layer (A) (E) amorphous polyethylene terephthalate resin layer, (F) polyvinyl chloride resin layer or (G) ABS resin layer Is preferably 40 to 250 μm, more preferably 60 to 200 μm. If the thickness of the lower layer (a) amorphous polyethylene terephthalate resin layer, polyvinyl chloride resin layer or ABS resin layer is less than 40 μm, the laminated decorative sheet may have insufficient strength. The lower layer (a) amorphous polyethylene terephthalate resin layer, polyvinyl chloride resin layer or ABS resin layer has a thickness of 250 μm or less and has sufficient performance as a laminated decorative sheet, and usually has a thickness exceeding 250 μm. A crystalline polyethylene terephthalate resin layer, a polyvinyl chloride resin layer or an ABS resin layer is not required.

The transparent thermoplastic urethane elastomer used in the present invention is not particularly limited, and examples of the diisocyanate component include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, cyclohexane diisocyanate, and xylylene diene. Examples thereof include isocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Among these, a transparent thermoplastic urethane elastomer having a diisocyanate component of hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate can be preferably used because it is difficult to yellow. A transparent thermoplastic urethane elastomer having diisocyanate as a diisocyanate component can be particularly preferably used.
Examples of the polyol component of the transparent thermoplastic urethane elastomer used in the present invention include polyether polyol, polycarbonate polyol, condensed polyester polyol, and lactone polyester polyol. Among these, a transparent thermoplastic urethane elastomer having a polyether polyol or polycarbonate polyol as a polyol component has good moisture resistance and weather resistance, and can be suitably used.

In the laminated decorative sheet of the present invention, there is no particular limitation on the location where the printing layer is provided between the upper layer (a) and the lower layer (b) .For example, back printing can be performed on the upper layer (a), or the lower layer (b) ) Can also be top printed. In many cases, amorphous polyethylene terephthalate resin, polyvinyl chloride resin or ABS resin has better printing workability than transparent thermoplastic urethane elastomer or a laminate thereof, so amorphous polyethylene terephthalate resin, It is preferable to print on a polyvinyl chloride resin or ABS resin. There is no restriction | limiting in particular in the pattern of a printing layer, For example, a fine grain pattern, an abstract pattern, a geometric pattern etc. can be mentioned. In the present invention, the printing method is not particularly limited, and examples thereof include gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing. Among these, gravure printing can be suitably used.
In the present invention, as the (E) amorphous polyethylene terephthalate resin used as the lower layer (a), for example, the dicarboxylic acid component is terephthalic acid, the glycol component is ethylene glycol 60 to 90 mol%, and cyclohexanedimethanol 10 40 mol% cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin, dicarboxylic acid component is terephthalic acid, glycol component is 60-90 mol% ethylene glycol and neopentyl glycol is 10-40 mol% neopentyl Glycopolymerized amorphous polyethylene terephthalate resin, isophthalic acid copolymerized amorphous polyethylene terephthalate having dicarboxylic acid components of 60 to 98 mol% and phthalic acid of 2 to 40 mol%, and glycol component of ethylene glycol. Examples include phthalate resins. Among these, a cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin in which the dicarboxylic acid component is terephthalic acid and the glycol components are 60 to 90 mol% of ethylene glycol and 10 to 40 mol% of cyclohexanedimethanol is preferably used. Can be used.

In the present invention, examples of the (F) polyvinyl chloride resin used as the lower layer (a) include a vinyl chloride homopolymer and a vinyl chloride / vinyl acetate copolymer. In the present invention, the (G) ABS resin used as the lower layer (a) includes, for example, a mixture of a copolymer of styrene and acrylonitrile and polybutadiene, a resin obtained by graft polymerization of styrene and acrylonitrile on polybutadiene, and a copolymer of styrene and acrylonitrile. Examples thereof include a mixture of a polymer and a resin obtained by graft polymerization of styrene and acrylonitrile on polybutadiene, and a mixture of a copolymer of styrene and acrylonitrile and a copolymer of butadiene and acrylonitrile.
In the second embodiment of the present invention, as the upper layer (a), (A) a transparent amorphous urethane-based resin laminated with a transparent thermoplastic urethane elastomer includes, for example, an amorphous polyethylene terephthalate-based resin, Examples thereof include crystalline polybutylene terephthalate resins and polytrimethylene terephthalate resins.
As an amorphous polyethylene terephthalate-based resin, for example, a dicarboxylic acid component is terephthalic acid, and a glycol component is ethylene glycol 60 to 90 mol% and cyclohexane dimethanol 10 to 40 mol%. Polyethylene terephthalate resin, dicarboxylic acid component is terephthalic acid, glycol component is 60-90 mol% ethylene glycol and neopentyl glycol 10-40 mol% neopentyl glycol copolymerized amorphous polyethylene terephthalate resin, dicarboxylic acid Examples thereof include isophthalic acid copolymerized amorphous polyethylene terephthalate resin in which the components are 60 to 98 mol% terephthalic acid and 2 to 40 mol% isophthalic acid, and the glycol component is ethylene glycol. That.
Examples of the amorphous polybutylene terephthalate resin include, for example, a polytetramethylene glycol copolymer polybutylene terephthalate resin containing 10 to 30% by mass of polytetramethylene glycol as a copolymer component, and a dicarboxylic acid component of 70 to 95 mol of terephthalic acid. And isophthalic acid copolymerized polybutylene terephthalate-based resin in which the glycol component is 1,4-butanediol.
Particularly preferred amorphous polyethylene terephthalate resin and amorphous polybutylene terephthalate resin are amorphous polyethylene terephthalate resin and amorphous half-time from crystallization for at least 5 minutes, preferably at least 12 minutes. Polybutylene terephthalate resin. Crystallization half time can be measured using a Perkin-Elmer model DSC-2 differential scanning calorimeter. Specifically, 15.0 mg of sample is sealed in an aluminum pan and heated at 290 ° C. for 2 minutes at a rate of about 320 ° C./min. The sample is then immediately cooled in the presence of helium to a predetermined isothermal crystallization temperature at a rate of about 320 ° C./min (20 ° C./min if the apparatus is not possible). The crystallization half time is a numerical value measured by determining the time interval from reaching the isothermal crystallization temperature to the point of the crystallization peak on the DSC curve.

In the second embodiment of the present invention, as the upper layer (A), (A) the transparent acrylic resin laminated with the transparent thermoplastic urethane elastomer includes, for example, polyacrylic acid ester, polymethacrylic acid ester and the like. Can do. Among these, polymethyl methacrylate can be suitably used. In the second embodiment of the present invention, as the upper layer (A), (A) the polycarbonate resin laminated with the transparent thermoplastic urethane elastomer is, for example, 2,2-bis (4-hydroxyphenyl) propane as pyridine. Examples thereof include resins obtained by reacting with phosgene in the presence of.
In the second aspect of the laminated decorative sheet of the present invention, (A) a transparent thermoplastic urethane elastomer layer, (B) a transparent amorphous polyester resin layer, (C) a transparent acrylic resin layer, or (D) a transparent polycarbonate resin. There is no particular limitation on the method for producing the upper layer (a) in which the layers are laminated. For example, a laminating method in which a single-layer film is bonded and composited, and two or more extruders are used to laminate in a molten state. Extrusion molding etc. can be mentioned. Among these, coextrusion molding can be suitably used because it is easy to expand the functional properties to meet quality requirements and is excellent in economic efficiency. There are no particular restrictions on the coextrusion molding method, for example, the multi-manifold method where the molten resin joins the die in the die, the two types of molten resin are combined in the feed block before the die, and then widened with a single manifold die The feed block method can be mentioned.

In the laminated decorative sheet of the present invention, (A) it is preferable to have (H) an unstretched polypropylene resin layer as a protective transfer layer on the upper side of the transparent thermoplastic urethane elastomer layer, and to have a mat unstretched polypropylene resin layer. Is more preferable. There is no particular limitation on the method for producing a mat unstretched polypropylene film as a mat unstretched polypropylene resin layer. For example, a mixed resin of 70 to 90% by mass of polypropylene and 10 to 30% by mass of hydrogenated SBR is formed using a T-die. It can be manufactured by mat processing using a 150-250 mesh grain roll.
In the present invention, there is no particular limitation on the method of providing the mat non-stretched polypropylene resin layer on the upper side of the transparent thermoplastic urethane elastomer layer. For example, the transparent thermoplastic urethane elastomer or the transparent thermoplastic on the mat non-stretched polypropylene resin film. An upper film having a matte unstretched polypropylene resin layer on the upper side of the transparent thermoplastic urethane elastomer layer by extrusion laminating a coextruded laminate of urethane elastomer and transparent amorphous polyester resin, transparent acrylic resin or transparent polycarbonate resin; can do. A laminated decorative sheet with high design, by matting the surface of the unstretched polypropylene resin film on the transparent thermoplastic urethane elastomer by extrusion laminating a transparent thermoplastic urethane elastomer on the unstretched polypropylene resin film. Can be obtained.

In the present invention, the matte unstretched polypropylene resin layer covers the transparent thermoplastic urethane elastomer layer until the laminated decorative sheet is processed into a final product, thereby protecting the surface of the laminated decorative sheet and preventing contamination. The mat unstretched polypropylene resin layer is preferably removed at the final stage of product processing.
In the laminated decorative sheet of the present invention, it is preferable to emboss from the top of the (H) mat unstretched polypropylene resin layer. For example, by printing a fine woodgrain pattern on the print layer and further embossing the fine woodgrain pattern, the laminated decorative sheet can be given a real feeling as a woody material, and the design can be enhanced. The mat unstretched polypropylene resin film has better embossability than the mat biaxially stretched polyethylene terephthalate film and the mat biaxially stretched polypropylene film, and can accurately transfer the pattern of the metal emboss roll.

The laminated decorative sheet of the present invention has a primer layer under the (E) amorphous polyethylene terephthalate resin layer, (F) polyvinyl chloride resin layer or (G) ABS resin layer of the lower layer (A). It is preferable. There is no particular limitation on the method of providing the primer layer below the amorphous polyethylene terephthalate resin layer, the polyvinyl chloride resin layer or the ABS resin layer. For example, the amorphous polyethylene terephthalate resin layer, the polyvinyl chloride resin The primer layer can be formed by applying an oily primer to the lower side of the layer or the ABS resin layer and drying. Adhesion when laminating a laminated decorative sheet to plywood, steel plate, etc. by providing a primer layer below the lower layer (a) amorphous polyethylene terephthalate resin layer, polyvinyl chloride resin layer or ABS resin layer You can increase your power. Examples of the primer to be used include a polyurethane primer and a polyester primer.
In the laminated decorative sheet of the present invention, it is preferable that (A) the transparent thermoplastic urethane elastomer is a non-yellowing polycarbonate urethane elastomer, a non-yellowing ether urethane elastomer or a non-yellowing ester urethane elastomer. (A) By using a non-yellowing urethane elastomer as a transparent thermoplastic urethane elastomer, a decorative material prepared by laminating a laminated decorative sheet to a plywood or a steel plate can be used for a long time in a state where it is exposed to sunlight. It can keep its beauty for a long time without yellowing over time. Non-yellowing polycarbonate-based urethane elastomer, non-yellowing ether-based urethane elastomer or non-yellowing ester-based urethane elastomer are aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, It can be produced by reacting an alicyclic diisocyanate with a polycarbonate diol, polyether diol or polyester diol.

FIG. 1 is a process flow diagram of one embodiment of the method for producing a laminated decorative sheet of the present invention. From the first raw material roll 1, an upper layer (a) composed of (A) a transparent thermoplastic urethane elastomer layer and (H) a matt unstretched polypropylene resin layer is arranged so that the matt unstretched polypropylene resin layer is in contact with the heating drum. After being unwound and preheated by the preheating roll 2, it is pressure-bonded to the heating drum 4 by the press roll 3. From the second raw material roll 5, the lower layer (A) film comprising the (E) amorphous polyethylene terephthalate resin layer having the printed layer is unwound so that the printed layer is in contact with the upper layer film, and is preheated by the preheating roll 6. After that, the press roll 7 is pressed against the upper film on the heating drum. The surface temperature of the heating drum is preferably 120 to 160 ° C, and more preferably 130 to 150 ° C.
The laminate composed of two layers of the upper layer film and the lower layer laminate laminated on the heating drum is then applied to a roll comprising a pair of an embossing roll 8 and a rubber pressure roll 9 and embossed. There is no particular limitation on the pattern of the embossing roll, and examples thereof include grain, grain, satin, and abstract pattern formed by hand carving or photographic engraving. The surface temperature of the embossing roll is preferably 120 to 140 ° C, and more preferably 125 to 135 ° C. The embossed laminated sheet is cooled by the cooling roll 11 via the guide roll 10 and then taken up by a take-up roll (not shown) as a laminated decorative sheet of the product. The mat unstretched polypropylene resin layer can be wound together with the laminated decorative sheet of the product, or can be removed before winding up the laminated decorative sheet of the product.

FIG. 2 is a schematic cross-sectional view of one embodiment of the laminated decorative sheet of the present invention. In the laminated decorative sheet of this embodiment, the upper layer film 12 and the lower layer film 13 are laminated by thermal lamination. The laminated decorative sheet according to this embodiment includes (F) a mat unstretched polypropylene resin layer 14, (A) a transparent thermoplastic urethane elastomer layer 15, a printing layer 16, and (E) an amorphous polyethylene terephthalate resin layer 17 in order from the surface side. The primer layer 18 is laminated.
FIG. 3 is a schematic cross-sectional view of another embodiment of the laminated decorative sheet of the present invention. In the laminated decorative sheet of this embodiment, the upper layer film 19 and the lower layer film 20 are laminated by thermal lamination. The laminated decorative sheet of this embodiment comprises (F) a mat unstretched polypropylene resin layer 21, (A) a transparent thermoplastic urethane elastomer layer 22, (B) a transparent amorphous polyester resin layer 23, and a printing layer 24 in order from the surface side. (E) Amorphous polyethylene terephthalate resin layer 25 and primer layer 26 are laminated.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In Examples and Comparative Examples, the evaluation was performed by the following method after removing the mat film and the like.
(1) Embossing process An embossing machine consisting of a metal engraving roll with a temperature of 130 ° C and a pressure roll coated with semi-hard rubber is installed between the doubling device with a heating drum temperature of 140 ° C and the cooling drum, and the fine graining. The embossing of the pattern is performed, and the surface properties of the laminated decorative sheet obtained by the embossing are visually observed and determined according to the following criteria.
○: Good
Δ: Somewhat bad
X: Defect (2) Abrasion resistance According to JIS K 7204, a decrease in mass after 2,000 rotations with a total load of 9.8 N is measured using an H18 wear wheel.
○: Mass reduction less than 1,200 mg
Δ: Mass reduction of 1,200 mg or more and less than 2,000 mg
×: Mass reduction of 2,000 mg or more (3) Scratch resistance According to JIS L 0849, with a load of 2N, No. 3 (cotton) specified in JIS L 0803 was used for 200 round-trips of Gakushin test and surface condition Are visually observed and determined according to the following criteria.
○: No change is observed at all.
(Triangle | delta): Although change is slight, it is recognized clearly.
X: Change is remarkable.
(4) Coefficient of dynamic friction According to JIS K 7125, a sliding piece with a contact area of 40 cm 2 and a total mass of 700 g wrapped in No. 3 (cotton) specified in JIS L 0803 is placed on the surface of the test piece and tested at a speed of 50 mm / min. To determine the coefficient of dynamic friction.
○: Dynamic friction coefficient 0.4 or more
Δ: Dynamic friction coefficient 0.2 or more and less than 0.4
×: Dynamic friction coefficient less than 0.2 (5) Low-temperature impact resistance According to JIS K 5600-5-3, a shooting die with a radius of 6.35 mm and a cradle are attached to a DuPont impact tester, and the upper layer of the test piece faces upward And put in between. A weight of 500 g is started from a height of 10 cm and is dropped by 10 cm on the shooting mold, and the lowest height that causes damage to the specimen is recorded. The test is performed at -20 ° C.
A: No damage occurs even at 50 cm.
○: Damage occurs at 40 cm or 50 cm.
Δ: Damage occurs at 20 cm or 30 cm.
X: Damage occurs at 10 cm.
(6) Solvent resistance The surface of the laminated decorative sheet is rubbed 5 times with a cloth containing lacquer thinner, and the subsequent surface property is visually determined based on the following criteria.
○: Not attacked.
Δ: Slightly affected.
X: Attacked.
(7) Interlayer adhesion A test piece having a width of 25 mm and a length of 400 mm was cut out in the longitudinal direction of the laminated decorative sheet, and in accordance with JIS K 6854-2, the gripping movement speed was 50 mm / min on the upper layer and the lower layer, 180 Perform a peel test. The test is performed at 80 ° C.
A: Peel strength 6.0 N / 25 mm or more
○: Peel strength 4.0 N / 25 mm or more and less than 6.0 N / 25 mm
Δ: Peel strength 2.0 N / 25 mm or more and less than 4.0 N / 25 mm
×: Peel strength less than 2.0 N / 25 mm (8) Appearance of plywood laminate After applying 10 g / 30 cm × 30 cm of the emulsion adhesive to the MDF (medium density fiber material) with a roll coater, the decorative sheet is roll-bonded. Clamping was performed at a pressure of 5 kg / 30 cm × 30 cm. The appearance of the produced sample is determined based on the following criteria.
A: Smoothness is very high.
○: Although smoothness is high, some undulation is observed.
Δ: Yuzu skin is conspicuous.
X: Concavity and convexity are conspicuous.
(9) Three-dimensional formability A laminate of release paper and an adhesive layer is attached to the lower surface of the laminated decorative sheet, and the release paper is peeled off to form an adhesive layer. A laminated decorative sheet 28 is stretched and applied to a corner portion of a test plate 27 having a shape shown in FIG. About the finish after construction, it judges visually based on the following reference | standard.
○: No whitening is observed.
Δ: Some whitening is observed.
X: Significant whitening is observed.

Moreover, the resin material used for the laminated decorative sheet is shown below.
(1) TPU (1): Non-yellowing polycarbonate-based transparent thermoplastic urethane elastomer, DIC Bayer Polymer Co., Ltd., Pandex (registered trademark) T-7895N, Shore A hardness 95.
(2) TPU (2): polycarbonate-based transparent thermoplastic urethane elastomer, DIC Bayer Polymer Ltd., Pandex (registered trademark) T-9280N, Shore A hardness 80.
(3) TPU (3): Non-yellowing polyether-based transparent thermoplastic urethane elastomer, DIC Bayer Polymer Ltd., Texin (registered trademark) DP7-3041, Shore D hardness 55.
(4) Matt CPP: mat unstretched polypropylene film, Riken Technos Co., Ltd., TPP092, XZ025, mat (mixed resin of 80% by mass of polypropylene and 20% by mass of hydrogenated SBR is formed using a T-die, and 200 mesh shivo roll ), Thickness 70 μm.
(5) Gloss CPP: Gloss unstretched polypropylene film, Riken Technos Co., Ltd., TPP092, XZ025, Gloss (Mixed resin of 80% by mass of polypropylene and 20% by mass of hydrogenated SBR is formed into a film using a T-die, and a mirror-surfaced scallop is used. And a mirror-finished film), thickness 70 μm.
(6) Matt PET: Matt biaxially stretched polyethylene terephthalate film, Teijin DuPont Films, Teijin Tetron (registered trademark) U4, thickness 23 μm.
(7) Matt OPP: Matt biaxially stretched polypropylene film, Tosero Co., Ltd., WH-OP FM-0, thickness 25 μm.
(8) PETG: cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin, Eastman Chemical Co., PETG6763, crystallization half time 12 minutes or more.
(9) PETN: Neopentyl glycol copolymerized amorphous polyethylene terephthalate resin, Toyobo Co., Ltd., SR173CA, crystallization half time 12 minutes or more.
(10) Acrylic: Acrylic resin, Mitsubishi Rayon Co., Ltd., Acrypet (registered trademark) MD.
(11) PC: Polycarbonate resin, Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000R.
(12) PP: polypropylene resin film, Riken Technos Co., Ltd., TPP061, XZ025.
(13) PVC: vinyl chloride resin film, Riken Technos, S12027, FC93522.
(14) ABS: ABS resin film, Riken Technos Co., Ltd., SST087, FZ91834.

Example 1
Matt unstretched polypropylene resin film [RIKEN TECHNOS CORPORATION, TPP092, XZ025, thickness 70 μm], non-yellowing polycarbonate transparent thermoplastic urethane elastomer [DIC Bayer Polymer Co., Ltd., Pandex T-7895N, Shore A hardness 95] was extrusion laminated to a thickness of 70 μm to produce an upper layer film.
Colored film with a thickness of 100 μm [Riken Technos Co., Ltd., SET588, FZ92963] by calendering a material obtained by adding a brown pigment to cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin [Eastman Chemical Co., PETG6763] A fine woodgrain pattern was printed on the surface by gravure printing using a vinegar vinyl-acrylic ink [The Inktec Co., Ltd., VTP-NT] to produce a lower layer film.
The upper film was attached to the first raw material roll of the apparatus shown in FIG. 1 so that the mat unstretched polypropylene resin film was in contact with the heating drum, and the lower film was attached to the second raw material roll so that the printing surface was in contact with the upper film. . From each raw material roll, the upper layer film and the lower layer film are unwound at a speed of 4 m / min, preheated by a preheating roll, and then pressed and laminated to a heating drum having a surface temperature of 140 ° C by a press roll, and embossing having a surface temperature of 130 ° C. The roll was embossed with a fine grain pattern, cooled with a cooling roll via a guide roll, and wound up.
Primer [Tokushiki, AD265] was applied to the back side of the obtained sheet, dried, and wound up as a laminated decorative sheet.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,030 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.72. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.5 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Example 2
A laminated decorative sheet was produced in the same manner as in Example 1 except that a polycarbonate-based transparent thermoplastic urethane elastomer [DIC Bayer Polymer Co., Ltd., Pandex T-9280N, Shore A hardness 80] was used for the upper layer film. .
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 960 mg. In the scratch resistance test, a slight change was clearly observed. The dynamic friction coefficient was 1.02. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.3 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Example 3
A non-yellowing polyether-based transparent thermoplastic urethane elastomer [DIC Bayer Polymer Co., Ltd., Texin DP7-3041, Shore D hardness 55] is used for the upper layer film, and neopentyl glycol copolymerized amorphous polyethylene terephthalate resin is used for the lower layer. A laminated decorative sheet was produced in the same manner as in Example 1 except that [Toyobo Co., Ltd., SR173CA] was used.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,260 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.31. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.4 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.

Example 4
Example 1 except that the thickness of the non-yellowing polycarbonate-based transparent thermoplastic urethane elastomer layer of the upper layer film is 90 μm, and a vinyl chloride resin film [RIKEN TECHNOS, S12027, FC93522] thickness of 150 μm is used for the lower layer. Similarly, a laminated decorative sheet was produced.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,010 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.86. In the low-temperature impact resistance test, damage was caused at a height of 20 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.0 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Example 5
A non-glossy polypropylene film [Riken Technos Co., Ltd., TPP092, XZ025, gloss, thickness 70 μm] is used for the upper film, the non-yellowing polycarbonate-based transparent thermoplastic urethane elastomer layer is 100 μm in thickness, and the ABS resin film is used for the lower layer [Riken Technos Co., Ltd., SST087, FZ91834] A laminated decorative sheet was produced in the same manner as in Example 1 except that a thickness of 200 µm was used.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,000 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.90. In the low temperature impact resistance test, damage occurred at a weight height of 30 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 4.9 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. Some whitening was observed in the three-dimensional formability test.
Example 6
A laminated decorative sheet was produced in the same manner as in Example 1 except that a mat biaxially stretched polyethylene terephthalate film having a thickness of 23 μm was used as the upper layer film.
Embossed surface properties of the resulting laminated decorative sheet are heavy peeling from the transparent thermoplastic urethane elastomer, insufficient adhesion of the mat biaxially stretched polyethylene terephthalate film to the heating drum, poor appearance, and slightly poor Met. In the abrasion resistance test, the mass loss was 1,020 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.75. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.3 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Example 7
A laminated decorative sheet was produced in the same manner as in Example 1 except that a matte biaxially stretched polypropylene film having a thickness of 25 μm was used as the upper layer film.
The resulting embossed surface properties of the laminated decorative sheet were slightly poor due to light peeling from the transparent thermoplastic urethane elastomer and floating due to peeling. In the abrasion resistance test, the mass loss was 1,010 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.73. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.2 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.

Example 8
For the production of the upper layer film, a multi-layer extruder [Ikegai Co., Ltd.] in which a T-die type feed block was attached to a 40 mm extruder for the main layer and a 30 mm extruder for the sublayer was attached to the side. Matt unstretched polypropylene resin film [RIKEN TECHNOS CORPORATION, TPP092, XZ025, thickness 70 μm], non-yellowing polycarbonate transparent thermoplastic urethane elastomer [DIC Bayer Polymer Co., Ltd., Pandex T-7895N, Shore A hardness 95] Thickness 30 μm and cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin [Eastman Chemical Co., PETG6763] 30 μm thick, two-layer coextrusion laminate so that the thermoplastic urethane elastomer is in contact with the polypropylene resin film Thus, an upper layer film was produced.
Colored film of 80 μm thickness [Riken Technos Co., Ltd., SET588, FZ92963] by calendering of a material obtained by adding a brown pigment to cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin [Eastman Chemical Co., PETG6763] A fine woodgrain pattern was printed on the surface by gravure printing using a vinegar vinyl-acrylic ink [The Inktec Co., Ltd., VTP-NT] to produce a lower layer film.
The upper film was attached to the first raw material roll of the apparatus shown in FIG. 1 so that the mat unstretched polypropylene resin film was in contact with the heating drum, and the lower film was attached to the second raw material roll so that the printing surface was in contact with the upper film. . From each raw material roll, the upper layer film and the lower layer film are unwound at a speed of 4 m / min, preheated by a preheating roll, and then pressed and laminated to a heating drum having a surface temperature of 140 ° C by a press roll, and embossing having a surface temperature of 130 ° C. The roll was embossed with a fine grain pattern, cooled with a cooling roll via a guide roll, and wound up as a laminated decorative sheet.
Primer [Tokushiki, AD265] was applied to the back side of the obtained sheet, dried, and wound up as a laminated decorative sheet.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,050 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.63. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 7.5 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Example 9
In the upper film, the thickness of the non-yellowing polycarbonate-based transparent thermoplastic urethane elastomer layer is 20 μm, and the thickness of the cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin is 40 μm. A laminated decorative sheet was produced in the same manner as in Example 8 except that the thickness of the crystalline polyethylene terephthalate resin was 100 μm.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,060 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.59. In the low-temperature impact resistance test, no damage occurred even at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 7.6 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.

Example 10
In the upper layer film, a non-yellowing polyether-based transparent thermoplastic urethane elastomer [DIC Bayer Polymer Co., Ltd., Texin DP7-3041, Shore D hardness 55] thickness 50 μm, neopentyl glycol copolymer amorphous polyethylene terephthalate system Resin [Toyobo Co., Ltd., SR173CA] with a thickness of 50 μm was co-extruded and used as a lower layer film, except that a vinyl chloride resin film [RIKEN TECHNOS, S12027, FC93522] with a thickness of 150 μm was used. A laminated decorative sheet was produced in the same manner as in Example 8.
The surface property of embossing of the obtained laminated decorative sheet was good. In the wear resistance test, the mass loss was 1,320 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.27. In the low temperature impact resistance test, damage occurred at a weight height of 30 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 5.3 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Example 11
A laminated decorative sheet in the same manner as in Example 8 except that an acrylic resin [Mitsubishi Rayon Co., Ltd., Acrypet MD] was used in place of the cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin in the upper film. Was made.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,040 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.62. In the low-temperature impact resistance test, damage was caused at a height of 20 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 4.9 N / 25 mm. The appearance of the laminated plywood was very smooth. In the three-dimensional formability test, no whitening was observed.
Example 12
In the upper layer film, in the same manner as in Example 8, except that a polycarbonate resin [Mitsubishi Engineering Plastics Co., Ltd., Iupilon E-2000R] was used instead of the cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin, A laminated decorative sheet was produced.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,050 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.61. In the low-temperature impact resistance test, damage occurred at a height of 50 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 4.8 N / 25 mm. The appearance of the laminated plywood was very smooth. In the three-dimensional formability test, no whitening was observed.

Comparative Example 1
An upper film [RIKEN TECHNOS, SET248, FZ025] having a thickness of 60 μm was prepared by calendering of cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin [Eastman Chemical Co., PETG6763].
Colored film of 90 μm thickness [Riken Technos Co., Ltd., SET588, FZ92963] by calendering a material obtained by adding tea pigment to cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin [Eastman Chemical Co., PETG6763] A fine woodgrain pattern was printed on the surface by gravure printing using a vinegar vinyl-acrylic ink [The Inktec Co., Ltd., VTP-NT] to produce a lower layer film.
The upper layer film was attached to the first raw material roll of the apparatus shown in FIG. 1, and the lower layer film was attached to the second raw material roll so that the printing surface was in contact with the upper layer film. From each raw material roll, the upper layer film and the lower layer film are unwound at a speed of 4 m / min, preheated by a preheating roll, and then pressed and laminated to a heating drum having a surface temperature of 140 ° C by a press roll, and embossing having a surface temperature of 130 ° C. The roll was embossed with a fine grain pattern, cooled with a cooling roll via a guide roll, and wound up.
Polyurethane [The Inktec Co., Ltd., XEL curing agent, solid content concentration 75% by weight on 100 parts by weight of urethane two-component curable paint [The Inktec Co., Ltd., NHWP Clear] containing wax on the surface of the upper layer film %] A topcoat layer having a thickness of 3 μm was formed using a paint added with 10 parts by weight and wound up.
Primer [Tokushiki, AD265] was applied to the back side of the obtained sheet, dried, and wound up as a laminated decorative sheet.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 2,700 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.32. In the low-temperature impact resistance test, damage occurred at a weight height of 40 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 7.8 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Comparative Example 2
Comparative Example 1 except that a top coat layer was formed on the surface of the upper layer film using a urethane two-component curable coating material [The Inktec Co., Ltd., paint obtained by removing the wax from NHWP clear] without wax. Similarly, a laminated decorative sheet was produced.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 2,800 mg. Changes were noticeable in the scratch resistance test. The dynamic friction coefficient was 0.45. In the low-temperature impact resistance test, damage occurred at a weight height of 40 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 7.9 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Comparative Example 3
On the surface of the upper film, hexafunctional acrylate ester [Nippon Kayaku Co., Ltd., DPHA] 80 parts by weight, bifunctional acrylate ester [Nippon Kayaku Co., Ltd., HDDA] 20 parts by weight, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., Darocur (registered trademark) 1173] except that a topcoat layer was formed by irradiating with ultraviolet rays using a paint consisting of 5 parts by weight, 50 parts by weight of isopropyl alcohol and 50 parts by weight of methyl ethyl ketone. A laminated decorative sheet was produced in the same manner as in Comparative Example 1.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 1,020 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.44. In the low-temperature impact resistance test, damage occurred at a height of 10 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 8.0 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, significant whitening was observed.

Comparative Example 4
Using a transfer foil [Reiko Co., Ltd., MC-66] coated with an acrylic one-component paint on the surface of the upper film, the thickness of the upper film is 150 μm. A laminated decorative sheet was produced in the same manner as in Comparative Example 1 except that the thickness of the lower layer film was 120 μm.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 2,900 mg. In the scratch resistance test, a slight change was clearly observed. The dynamic friction coefficient was 0.43. In the low-temperature impact resistance test, damage occurred at a weight height of 40 cm. In the solvent resistance test, the surface was attacked. The delamination strength was 7.8 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Comparative Example 5
A laminated decorative sheet was produced in the same manner as in Comparative Example 1 except that the topcoat layer using the urethane two-component curable coating was not formed.
The surface property of embossing of the obtained laminated decorative sheet was good. In the abrasion resistance test, the mass loss was 3,200 mg. Changes were noticeable in the scratch resistance test. The dynamic friction coefficient was 0.36. In the low-temperature impact resistance test, damage occurred at a weight height of 40 cm. In the solvent resistance test, the surface was attacked. The delamination strength was 7.7 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, no whitening was observed.
Comparative Example 6
Matt unstretched polypropylene resin film [RIKEN TECHNOS CORPORATION, TPP092, XZ025, thickness 70 μm], non-yellowing polycarbonate transparent thermoplastic urethane elastomer [DIC Bayer Polymer Co., Ltd., Pandex T-7895N, Shore A hardness 95] was extrusion laminated to a thickness of 70 μm to produce an upper layer film.
Colored polypropylene resin film [Riken Technos Co., Ltd., TPP061, LP9080] Fine-grained by gravure printing using urethane-vinyl acetate two-component ink [Daiichi Seika Kogyo Co., Ltd., LAP] on a 100 μm thick surface A printed pattern is printed thereon, and a paint comprising 100 parts by mass of a polyester resin [Toyobo Co., Ltd., Byron 24SS] and 3 parts by mass of hexamethylene diisocyanate [Nippon Polyurethane Industry Co., Ltd.] is applied as an anchor coating agent. It dried and produced the lower layer film.
The upper film was attached to the first raw material roll of the apparatus shown in FIG. 1 so that the mat unstretched polypropylene resin film was in contact with the heating drum, and the lower film was attached to the second raw material roll so that the printing surface was in contact with the upper film. . From each raw material roll, the upper layer film and the lower layer film are unwound at a speed of 4 m / min, preheated by a preheating roll, and then pressed and laminated to a heating drum having a surface temperature of 140 ° C by a press roll, and embossing having a surface temperature of 130 ° C. The roll was embossed with a fine grain pattern, cooled with a cooling roll via a guide roll, and wound up.
Primer [Tokushiki, AD265] was applied to the back side of the obtained sheet, dried, and wound up as a laminated decorative sheet.
The surface property of embossing of the obtained laminated decorative sheet was somewhat poor. In the abrasion resistance test, the mass loss was 1,050 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.73. In the low temperature impact resistance test, damage occurred at a weight height of 30 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 1.8 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, significant whitening was observed.
Comparative Example 7
A laminated decorative sheet was produced in the same manner as in Comparative Example 1 except that a polypropylene resin film [RIKEN TECHNOS CORPORATION, TPP061, XZ025] film having a thickness of 60 μm was used as the upper layer film and the thickness of the lower layer film was set to 100 μm. did.
The surface property of embossing of the obtained laminated decorative sheet was somewhat poor. In the abrasion resistance test, the mass loss was 2,400 mg. In the scratch resistance test, no change was observed. The dynamic friction coefficient was 0.22. In the low-temperature impact resistance test, damage occurred at a height of 10 cm. In the solvent resistance test, the surface was not attacked. The delamination strength was 2.3 N / 25 mm. Although the appearance of the plywood laminate was high in smoothness, some undulation was observed. In the three-dimensional formability test, significant whitening was observed.
Table 1 shows the configurations of the laminated decorative sheets of Examples 1 to 12, Table 2 shows the performance evaluation results, Table 3 shows the configurations of the laminated decorative sheets of Comparative Examples 1 to 7, and Table 4 shows the performance evaluation results. Shown in

As can be seen in Tables 1 and 2, the laminated decorative sheets of Examples 1 to 4 and Examples 8 to 12 and a gloss unstretched polypropylene film using a mat unstretched polypropylene film as the protective transfer layer of the upper film were used. The laminated decorative sheet of Example 5 has good embossability. The laminated decorative sheets of Examples 6 to 7 using a mat biaxially stretched polyethylene terephthalate film or a mat biaxially stretched polypropylene film as the protective transfer layer are slightly inferior in embossability.
The laminated decorative sheets of Examples 1-2, Examples 4-9, and Examples 11-12 using a transparent thermoplastic urethane elastomer having a Shore A hardness of 95 or a Shore A hardness of 80 as the resin layer of the upper film are wear resistant. Excellent in properties. The laminated decorative sheets of Example 3 and Example 10 using a hard transparent thermoplastic urethane elastomer having a Shore D hardness of 55 are slightly inferior in wear resistance.
The laminated decorative sheets of Examples 1 and 3 to 12 using a transparent thermoplastic urethane elastomer having a Shore A hardness of 95 or a Shore D hardness of 55 as the resin layer of the upper film have good scratch resistance. The laminated decorative sheet of Example 2 using a soft transparent thermoplastic urethane elastomer having a Shore A hardness of 80 is slightly inferior in scratch resistance.
The laminated decorative sheets of Examples 1-2, Examples 4-9, and Examples 11-12 using a transparent thermoplastic urethane elastomer having a Shore A hardness of 95 or a Shore A hardness of 80 are used as the resin layer of the upper film. Because it is large, it is hard to slip. The laminated decorative sheets of Example 3 and Example 10 using a hard transparent thermoplastic urethane elastomer having a Shore D hardness of 55 have a slightly low dynamic friction coefficient and are slightly slippery.
Laminated decorative sheets of Examples 1-2 and Examples 6-9 using cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin as the resin layer of the lower film, and neopentyl glycol copolymerized amorphous polyethylene terephthalate system The laminated decorative sheet of Example 3 using a resin is excellent in low-temperature impact resistance.
The laminated decorative sheets of Examples 8-9, in which the lower film of the upper film and the lower film are both cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin, have high delamination strength, and particularly excellent interlayer adhesion at high temperatures. Suitable for applications requiring heat resistance, such as range hoods.
In Examples 11-12 using a laminate of a transparent thermoplastic urethane elastomer layer and an acrylic resin layer or a laminate of a transparent thermoplastic urethane elastomer layer and a polycarbonate resin layer as the upper layer, the appearance of the plywood laminate was very good. is there. Since both the acrylic resin and the polycarbonate resin have high heat resistance and rigidity, they can be heated to 90 to 100 ° C. by pressing and wrapping when bonded to the plywood, and the smoothness is improved.
The laminated decorative sheets of Examples 1 to 4 and Examples 6 to 12 all have good three-dimensional formability, but the laminated decorative sheet of Example 5 using an ABS resin for the lower layer film has three-dimensional formability. Slightly inferior.

The laminated decorative sheet of Comparative Example 6 in which the lower layer film is a polypropylene resin and the upper layer film is a polypropylene resin even when a matte unstretched polypropylene film is used as the protective transfer layer of the upper layer film and a thermoplastic urethane elastomer is used as the resin The laminated decorative sheet of Example 7 is slightly inferior in embossability.
The laminated decorative sheet in which the upper film is a cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin or polypropylene resin has poor wear resistance except for the laminated decorative sheet of Comparative Example 3 having an ultraviolet curable topcoat layer. It is.
A laminated decorative sheet of Comparative Example 2 in which the upper film is a cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin and the topcoat layer contains a urethane two-component paint without wax, and Comparative Example 5 without the topcoat layer The laminated decorative sheet has poor scratch resistance.
The laminated decorative sheet of Comparative Example 1 in which the upper film is a cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin, and the urethane two-component paint containing wax is used for the topcoat layer, and the laminated film of Comparative Example 5 without the topcoat layer The laminated decorative sheet of Comparative Example 7 using the decorative sheet and the urethane two-component paint whose upper layer film is a polypropylene resin and the top coat layer contains wax has a slightly small dynamic friction coefficient and is slightly slippery.
The laminated decorative sheet of Comparative Example 3 having an ultraviolet curable top coat layer and the laminated decorative sheet of Comparative Example 7 using a polypropylene resin for the upper film have poor low temperature impact resistance.
The upper layer film is a cyclohexanedimethanol copolymerized amorphous polyethylene terephthalate resin, and the laminated decorative sheet of Comparative Example 4 is provided with an acrylic one-component topcoat layer using a transfer foil, and the upper layer film is a cyclohexanedimethanol copolymer. The laminated decorative sheet of Comparative Example 5 which is an amorphous polyethylene terephthalate resin and does not have a top coat layer has poor solvent resistance.
The laminated decorative sheet of Comparative Example 6 in which the upper layer film is a thermoplastic urethane elastomer and the lower layer film is a polypropylene resin has low delamination strength and poor interlayer adhesion.
The laminated decorative sheet of Comparative Example 3 using an ultraviolet curable paint for the top coat layer and the laminated decorative sheets of Comparative Examples 6 to 7 using polypropylene resin for the upper film or the lower film have poor three-dimensional formability.

  The laminated decorative sheet of the present invention uses an amorphous polyethylene terephthalate resin having a printed layer as a lower layer, using a transparent thermoplastic urethane elastomer or a laminate of a transparent thermoplastic urethane elastomer and a transparent amorphous polyester resin as an upper layer. Therefore, when mat unstretched polypropylene film is used as a protective transfer layer, good embossability can be obtained, it has excellent wear resistance and scratch resistance, it has a high coefficient of dynamic friction, is difficult to slip, and has low impact strength even at low temperatures. Large, good solvent resistance, high delamination strength even at high temperatures, good plywood laminate appearance, and excellent three-dimensional formability. The laminated decorative sheet of the present invention can be suitably used as a surface material for furniture, doors, door frames, waistboards, skirting boards, window frames and the like by being bonded to plywood and steel plates.

It is a process flow diagram of one mode of a manufacturing method of a lamination decorative sheet of the present invention. It is a typical sectional view of one mode of a lamination decorative sheet of the present invention. It is typical sectional drawing of the other aspect of the lamination | stacking decorative sheet of this invention. It is explanatory drawing of the evaluation method of three-dimensional moldability.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st raw material roll 2 Preheating roll 3 Press roll 4 Heating drum 5 2nd raw material roll 6 Preheating roll 7 Press roll 8 Embossing roll 9 Rubber pressure roll 10 Guide roll 11 Cooling roll 12 Upper layer film 13 Lower layer film 14 (F) Matt unstretched polypropylene resin layer 15 (A) Transparent thermoplastic urethane elastomer layer 16 Printing layer 17 (E) Amorphous polyethylene terephthalate resin layer 18 Primer layer 19 Upper layer film 20 Lower layer film 21 (F) Matt unstretched polypropylene resin layer 22 (A) Transparent thermoplastic urethane elastomer layer 23 (B) Transparent amorphous polyester resin layer 24 Printing layer 25 (E) Amorphous polyethylene terephthalate resin layer 26 Primer layer 27 Test plate 28 Laminated decorative sheet

Claims (8)

As the upper layer (A), (A) a thermoplastic urethane elastomer layer, and as the lower layer (A), (E) an amorphous polyethylene terephthalate resin layer, (F) a polyvinyl chloride resin layer, or (G) an ABS resin layer. A laminated decorative sheet, which is laminated and has (H) a matt unstretched polypropylene resin layer as a protective transfer layer on the upper side of the (A) thermoplastic urethane elastomer layer . As the upper layer (a), (A) a thermoplastic urethane elastomer layer, (B) an amorphous polyester resin layer, (C) an acrylic resin layer or (D) a polycarbonate resin layer are laminated in this order, and the lower layer ( A), (E) an amorphous polyethylene terephthalate resin layer, (F) a polyvinyl chloride resin layer, or (G) an ABS resin layer , and (A) a protective transfer layer on the upper side of the thermoplastic urethane elastomer layer. A laminated decorative sheet comprising (H) a matt unstretched polypropylene resin layer as a layer .   A laminate of the upper layer (A) (A) thermoplastic urethane elastomer layer and (B) amorphous polyester resin layer, (C) acrylic resin layer or (D) polycarbonate resin layer is obtained by coextrusion molding. The laminated decorative sheet according to claim 2, which is obtained. The laminated decorative sheet according to any one of claims 1 to 3 , wherein the upper surface is embossed.   The laminate according to claim 1 or 2, further comprising a primer layer under the (E) amorphous polyester resin layer, (F) polyvinyl chloride resin layer, or (G) ABS resin layer of the lower layer (A). Makeup sheet.   (E) Amorphous polyethylene terephthalate resin is a cyclohexanedimethanol copolymerized amorphous material in which the dicarboxylic acid component is terephthalic acid, and the glycol component is ethylene glycol 60 to 90 mol% and cyclohexanedimethanol 10 to 40 mol%. The laminated decorative sheet according to claim 1 or 2, which is a polyethylene terephthalate resin.   (B) Cyclohexanedimethanol copolymerized amorphous polyethylene in which the non-crystalline polyester resin is a dicarboxylic acid component is terephthalic acid, and a glycol component is 60 to 90 mol% of ethylene glycol and 10 to 40 mol% of cyclohexanedimethanol. The laminated decorative sheet according to claim 2, which is a terephthalate resin. The laminated decorative sheet according to claim 1 or 2, wherein the thermoplastic urethane elastomer is a non-yellowing polycarbonate urethane elastomer, a non-yellowing ether urethane elastomer or a non-yellowing ester urethane elastomer.

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