JP3429265B2 - Amorphous polyester resin decorative sheet and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an amorphous polyester resin decorative sheet and a method for producing the same. More specifically, the present invention has excellent scratch resistance, has a hiding power that can withstand vacuum forming, and has a deep, highly-designed amorphous polyester resin decorative sheet, and efficiently manufactures the decorative sheet. The present invention relates to a method for producing an amorphous polyester resin decorative sheet that can be used.

[0002]

2. Description of the Related Art Conventionally, furniture, doors, door frames, wainscots,
Vinyl chloride resin films have been used in large amounts in decorative sheets used for surface materials such as skirting boards and window frames. A vinyl chloride resin decorative sheet is made by stacking a transparent vinyl chloride resin film and a printed colored vinyl chloride resin film on a heating drum of a doubling device and thermocompressing them, and then embossing the film surface with an embossing roll. It was manufactured by embossing. However, since vinyl chloride-based resins generate hydrogen chloride during combustion, a decorative sheet that replaces vinyl chloride-based resins has been demanded. Instead of the vinyl chloride resin film, it has been considered to use an amorphous polyester resin film that does not generate a harmful gas even when it is burned. However, if the vinyl chloride resin film is simply replaced with the amorphous polyester resin film, the amorphous polyester resin film is fused to the heating drum, and the decorative film cannot be stably manufactured. As a method for stably producing an amorphous polyester resin decorative sheet by preventing fusion of an amorphous polyester resin film to a heating drum, the present applicant previously described in Japanese Patent Application No. 11-61730. A method of manufacturing a decorative sheet using a transparent amorphous polyester resin film containing wax has been proposed. According to this method, without causing fusion of the film to the heating drum,
A decorative sheet can be manufactured by thermocompressing a transparent film and a colored film. However, there is a need for a step of forming a film by blending a wax with an amorphous polyester resin, and further improvement has been desired due to problems such as a large amount of wax used. Japanese Patent Application Laid-Open No. 11-34269 discloses a pattern printing layer on the surface side of an amorphous polyethylene terephthalate resin-based colored film as a decorative sheet that does not generate hydrogen chloride during combustion, has excellent solvent resistance, and can be embossed. And a decorative sheet in which a surface protective layer made of a coating film of a two-component urethane resin is provided on the pattern printing layer and an embossed pattern is formed on the surface protective layer. However, this decorative sheet has a drawback that the abrasion resistance is poor because the coating film of the two-component urethane resin on the upper surface of the pattern printing layer is as thin as about 4 μm. In addition, JP-A-11-3
Japanese Patent No. 4270 discloses a decorative sheet that does not generate hydrogen chloride during combustion, has excellent solvent resistance, and can be embossed, and has a pattern printing layer on the back side of a transparent amorphous polyethylene terephthalate resin film, A decorative sheet is proposed, in which a coating layer for coloring and hiding is formed on the pattern printing layer, a surface protective layer made of a two-component urethane resin coating film is provided on the surface side, and an embossed pattern is formed on the surface protective layer. Has been done. However, since this colored hiding layer is thin, for example, when vacuum forming is performed to impart three-dimensionality to the decorative sheet,
In the stretched portion of the decorative sheet, the fiber board serving as the base material is raised on the surface, and it is not possible to obtain complete concealment.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides an amorphous polyester resin decorative sheet which is excellent in scratch resistance, has a concealing power to withstand vacuum forming, and has a deep and high designability, and the decorative sheet. The purpose of the present invention is to provide a method for producing an amorphous polyester resin decorative sheet that can be efficiently produced.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that a two-component urethane resin containing wax on the surface of a transparent amorphous polyester resin film is used. By providing a coating film, it is possible to significantly improve the scratch resistance of the decorative sheet, by laminating a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film and thermocompression bonding, It has a concealing power that can withstand vacuum forming, and it is possible to obtain a deep decorative sheet with high designability. Furthermore, it has a coating film of a two-component urethane resin containing a transparent amorphous polyester resin film wax. Adhesion of the surface to the surface of the heating drum, stacking colored opaque amorphous polyester resin films and thermocompression bonding It found that it is possible to efficiently produce over preparative stably, and completed the present invention based on this finding. That is, the present invention relates to (1) an amorphous polyester resin decorative sheet obtained by thermocompression bonding a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film, which is a transparent amorphous polyester. An amorphous polyester resin decorative sheet, characterized in that the resin film has a coating film of a two-component urethane resin containing 0.5 to 20 parts by weight of wax per 100 parts by weight of the urethane resin on its surface, (2) The colored opaque amorphous polyester resin film has a pattern print on the thermocompression bonding surface.
(3) A pattern is printed on the surface of the amorphous polyester resin decorative sheet according to item (3) where the transparent amorphous polyester resin film and the colored opaque amorphous polyester resin film are in contact with the colored opaque amorphous polyester resin film. The amorphous polyester resin decorative sheet according to item 1, which is thermocompression-bonded through a transparent film that has been applied, and (4) a colored opaque amorphous polyester resin film, which has a back surface subjected to a primer treatment. Item 5, the amorphous polyester resin decorative sheet according to item 2 or 3, (5) the dicarboxylic acid component of the amorphous polyester resin is terephthalic acid,
The diol component is ethylene glycol 50-90 mol% and 1,4-cyclohexanedimethanol 10-50 mol%
1. The amorphous polyester resin decorative sheet according to item 1, 2, 3, or 4, and (6) a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film. In a method for producing an amorphous polyester resin decorative sheet by thermocompression bonding, a urethane resin 10 is formed on one surface of a transparent amorphous polyester resin film.
A coating film of a two-component urethane resin containing 0.5 to 20 parts by weight of wax per 0 parts by weight is provided, and the surface of the transparent amorphous polyester resin film having the coating film is adhered to the surface of the heating drum. And a method for producing an amorphous polyester resin decorative sheet, comprising laminating a colored opaque amorphous polyester resin film on a transparent amorphous polyester resin film, and thermocompressing the two films. It is a thing. Further, as a preferred embodiment of the present invention, (7) the amorphous polyester resin decorative sheet according to item 1, wherein the transparent amorphous polyester resin film has a thickness of 30 to 300 μm, (8) a colored opaque non-transparent sheet The thickness of the crystalline polyester resin film is 20-1,
000 μm, the amorphous polyester resin decorative sheet according to item 1, (9) the amorphous polyester resin decorative sheet according to item 1, wherein the two-component urethane resin coating film has a thickness of 1 to 10 μm, (10) A pattern is printed on one surface of the colored opaque amorphous polyester resin film, and the colored opaque amorphous polyester resin film is laminated so that the printed surface is in contact with the transparent amorphous polyester resin film. (11) A transparent film having a pattern printed on one side between a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film, 7. The method for producing an amorphous polyester resin decorative sheet according to claim 6, which is laminated so that the pattern printed surface is in contact with the colored opaque amorphous polyester resin film. (12) A method for producing an amorphous polyester resin decorative sheet according to item 6, wherein the back surface of the thermo-compression-bonded colored opaque amorphous polyester resin film is subjected to primer treatment, (13) Dicarboxylic acid of amorphous polyester resin 7. The method for producing an amorphous polyester resin decorative sheet according to claim 6, wherein the component is terephthalic acid and the diol component is 50 to 90 mol% of ethylene glycol and 10 to 50 mol% of 1,4-cyclohexanedimethanol. And (14) the method for producing an amorphous polyester resin decorative sheet according to item 6, wherein the temperature of the heating drum is 100 to 160 ° C.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The amorphous polyester resin decorative sheet of the present invention is an amorphous polyester resin decorative sheet obtained by thermocompression bonding a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film. In addition, the transparent amorphous polyester resin film is a decorative sheet having a coating film of a two-pack type urethane resin containing 0.5 to 20 parts by weight of wax per 100 parts by weight of the urethane resin on the surface. In the method of the present invention, in the method for producing an amorphous polyester resin decorative sheet comprising a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film laminated, Urethane resin 100 on one side
A coating film of a two-pack type urethane resin containing 0.5 to 20 parts by weight of wax per part by weight is provided, and the surface of the transparent amorphous polyester resin film having the coating film is adhered to the surface of the heating drum, By laminating a colored opaque amorphous polyester resin film on a transparent amorphous polyester resin film, both films are thermocompression bonded. The amorphous polyester resin used in the present invention is a polyester resin that does not change its physical properties due to crystallization even when subjected to heat treatment and has no crystallinity. The fact that the polyester resin does not have crystallinity is confirmed by the fact that it does not show an exothermic peak due to crystallization in a thermal analysis using a differential scanning calorimeter and that it does not appear cloudy or white in appearance when heated. can do. Examples of such an amorphous polyester resin include terephthalic acid,
Examples of the copolymer polyester resin include isophthalic acid as a dicarboxylic acid component and ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol as a glycol component. Among these,
A copolyester resin containing terephthalic acid as a dicarboxylic acid component and ethylene glycol and 1,4-cyclohexanedimethanol as a glycol component can be preferably used. As the dicarboxylic acid component, terephthalic acid can be used for an esterification reaction with a glycol component, or dimethyl terephthalate can be used for an ester exchange reaction with a glycol component. A copolymerized polyester resin having terephthalic acid as a dicarboxylic acid component and ethylene glycol and 1,4-cyclohexanedimethanol as a glycol component has a glycol component of ethylene glycol 50 to 90 mol% and 1,4-cyclohexanedimethanol 10 to 50. It is preferably mol%, and ethylene glycol 60 to 80 mol% and 1,4-
More preferably, it is 20 to 40 mol% of cyclohexanedimethanol. Such an amorphous polyester resin is commercially available from Eastman Chemical Company as KODAR PETG.
It is marketed as (brand name).

The transparent amorphous polyester resin film used in the present invention preferably has a total light transmittance of 80% or more measured on a film having a thickness of 70 μm,
It is more preferably 90% or more. The total light transmittance of the film can be measured according to JIS K 7105 5.5.2. The colored opaque amorphous polyester resin film used in the present invention has a hiding power such that the surface of the base material cannot be seen from the outside when the decorative sheet is bonded to the base material such as plywood, fiber board and particle board. It has, depending on the substrate used,
The opacity can be appropriately selected. In the present invention, the thickness of the transparent amorphous polyester resin film is preferably 30 to 300 μm, and 50 to 1
More preferably, it is 00 μm. When the thickness of the transparent amorphous polyester resin film is less than 30 μm,
The function of protecting the colored and opaque amorphous polyester resin film layer may be insufficient. The thickness of the transparent amorphous polyester resin film is 300 μm or less, which satisfies the performance required for the decorative sheet, and it is usually unnecessary to use the transparent amorphous polyester resin film having a thickness of more than 300 μm. In the present invention, the colored opaque amorphous polyester resin film has a thickness of 20 to 1,000 μm.
Is preferable, and 40 to 500 μm is more preferable. If the thickness of the colored opaque amorphous polyester resin film is less than 20 μm, the hiding power may be insufficient. If you vacuum-form a decorative sheet,
Since the way the decorative sheet is stretched differs depending on the depth of the drawing, the thickness of the colored and opaque amorphous polyester resin film can be selected according to the application. The thickness of the colored opaque amorphous polyester resin film is 1,000μ.
It is not necessary to use a colored opaque amorphous polyester resin film having a thickness of m or less to satisfy the performance required for a decorative sheet and usually having a thickness of more than 1,000 μm.

In the present invention, a two-component type containing 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight of wax per 100 parts by weight of urethane resin on one side of a transparent amorphous polyester resin film. A urethane resin coating film is provided, and the surface having this coating film is the surface of the decorative sheet.
By providing a coating film of a two-component urethane resin containing wax, the scratch resistance of the decorative sheet can be improved, and an excellent product in which the surface of the decorative sheet is not easily scratched can be obtained. Further, at the time of manufacturing the decorative sheet, a coating film of a two-pack type urethane resin containing wax is adhered to the surface of the heating drum so that the amorphous polyester resin film is adhered without causing partial floating, and It can be peeled off without difficulty. The coating film of the two-pack type urethane resin is a coating film formed by mixing a polyol component and a polyisocyanate component and then applying the mixture to cure the mixture. The thickness of the two-component urethane resin coating film is 1 to 10 μm.
Is preferable, and it is more preferable that it is 3 to 7 μm. There is no particular limitation on the polyol component used in the present invention, for example, oil-modified alkyd resin having a polyester bond in the main chain, oil-free polyester, polycaprolactone polyol, polycarbonate polyol, acrylic polyol, vinyl polymer having a hydroxyl group, hydroxyl group Examples thereof include fluororesins, polyether polyols and epoxy polyols. Among these, acrylic polyol can be preferably used. The polyol component is preferably used as a solution dissolved in an organic solvent. Examples of the solvent used include solvents having no active hydrogen, such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. There is no particular limitation on the polyisocyanate used in the present invention, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like, and burettes thereof. , Isocyanurates, and the like. Among these, non-yellowing hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate can be preferably used. The wax used in the present invention is not particularly limited, and examples thereof include hydrocarbon wax such as paraffin, polyethylene wax and polypropylene wax, fatty acid wax such as stearic acid, hydroxystearic acid, complex type stearic acid and oleic acid, and stearic acid amide. , Oxystearic acid amide, oleic acid amide, erucyl amide, ricinoleic acid amide, behenic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide and other aliphatic amide waxes, stearic acid-n-butyl and other aliphatic esters Wax, aliphatic metal soap wax,
A urea-formaldehyde wax etc. can be mentioned. The wax is preferably dispersed in advance in the solution of the polyol component.

In the present invention, a wax-containing two-component urethane resin coating film is provided by applying a two-component urethane resin coating material containing wax to one surface of a transparent amorphous polyester resin film. If the wax content is less than 0.5 parts by weight per 100 parts by weight of the urethane resin, the scratch resistance of the decorative sheet may be insufficient. Further, when the transparent amorphous polyester resin film and the colored opaque amorphous polyester resin film are thermocompression-bonded, the peelability from the heating drum may be poor. Wax content is urethane resin 1
If the amount exceeds 20 parts by weight per 00 parts by weight, the wax may bleed on the surface of the decorative sheet and the appearance of the decorative sheet may be impaired. In addition, when the transparent amorphous polyester resin film and the colored opaque amorphous polyester resin film are thermocompression-bonded, the adhesion to the heating drum may be poor. If a coating film of a two-component type urethane resin containing no wax is provided on the surface of a transparent amorphous polyester resin film, fusion with the heating drum can be prevented, but peelability from the heating drum becomes poor and peeling occurs. At that time, the film is stretched, the thickness unevenness and the pattern elongation of the printed pattern are increased, and a decorative sheet in which two films are laminated cannot be stably manufactured. Also,
The scratch resistance of the obtained decorative sheet becomes poor. By including 0.5 to 20 parts by weight of wax per 100 parts by weight of the urethane resin in the coating film of the two-component urethane resin, the entire film adheres to the heating drum and can be peeled off without difficulty when peeled off. You can Further, a two-component urethane resin coating film is generally easily scratched and has poor scratch resistance, but the inclusion of wax in the two-component urethane resin coating film improves scratch resistance.

FIG. 1 is an illustration of an embodiment of the method of the present invention. A transparent amorphous polyester resin film provided with a coating film of a two-pack type urethane resin containing wax on one surface is fed from a feeding roll 1 with the surface having the coating film being the lower surface of the film in the figure. It is fed out and brought into close contact with the surface of the heating drum 3 of the doubling device by the pressure roll 2. The temperature of the heating drum is 100 to 160
C. is preferable, and 130 to 150.degree. C. is more preferable. The colored and opaque amorphous polyester resin film is fed from the feeding roll 4 and laminated on the transparent amorphous polyester resin film on the heating drum by the pressure bonding roll 5. Both laminated films are
The film is transferred by the rotation of the heating drum, and the two films are thermocompression-bonded in the meantime to form one decorative sheet. If necessary, the infrared heater 6 can be used to heat the colored opaque amorphous polyester resin film side. The thermocompression-bonded decorative sheet can be cooled and wound as it is, or can be embossed if necessary. When embossing is performed, a decorative sheet is passed between the embossing roll 7 and the backing roll 8. The temperature of the embossing roll is preferably about 150 ° C. By embossing, for example, a wood grain pattern conduit pattern or the like can be formed. The decorative sheet is further cooled by the cooling rolls 9 and 10 and wound on the winding roll 11.

In the present invention, pattern printing can be carried out on one side of a colored and opaque amorphous polyester resin film, and the layer can be laminated so that the pattern printed surface is in contact with the transparent amorphous polyester resin film and thermocompression bonded. . In this embodiment, the pattern-printed surface of the colored opaque amorphous polyester resin film is unrolled from the unrolling roll 4 in a state of being the lower surface of the film in FIG. There is no particular limitation on the resin constituting the printing ink used for pattern printing, for example,
Examples thereof include acrylic resins, urethane resins, and vinyl chloride-based resins. A printing ink can be prepared by blending a coloring pigment with these resins. The pattern to be printed is not particularly limited, and any pattern such as a wood grain pattern, a floral pattern, an abstract pattern, and a leather grain pattern can be selected according to the application of the decorative sheet. Pattern printing on a colored opaque amorphous polyester resin film, by laminating with a transparent amorphous polyester resin film, the background color of the colored opaque amorphous polyester resin film and the pattern printing are entangled,
It is possible to obtain a decorative sheet having a deep pattern and excellent design. In addition, the transparent amorphous polyester resin film and the colored opaque amorphous polyester resin film are laminated and printed on the colored opaque amorphous polyester resin film before thermocompression bonding to complete the decorative sheet. You can do a proof to get exactly the color you want.

In the present invention, a transparent film having a pattern printed on one side is provided between a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film, and an amorphous pattern-printed surface is colored and opaque. It can be laminated so as to be in contact with the high quality polyester resin film and thermocompression bonded. FIG. 2 is an explanatory diagram of another embodiment of the present invention.
In this embodiment, the transparent film having a pattern printed on one side is unwound from the unrolling roll 12 in a state where the pattern printing surface is the upper surface of the film in the drawing, and is transparent on the heating drum of the doubling device. It is sandwiched between a crystalline polyester resin film and a colored opaque amorphous polyester resin film, and thermocompression bonded. The material of the transparent film on which the pattern is printed on one side is not particularly limited as long as it can be thermocompression-bonded with the transparent amorphous polyester resin film and the colored opaque amorphous polyester resin film. Examples thereof include an amorphous polyester resin film or an amorphous polyester resin film having the same or different composition as the colored opaque amorphous polyester resin film, a polycarbonate film, a polyolefin film subjected to corona discharge treatment, a primer treatment and the like. The thickness of the transparent film having a pattern printed on one side is not particularly limited, but is preferably 10 to 50 μm, and more preferably 15 to 30 μm. By adding a slight difference between the refractive index of a transparent amorphous polyester resin film and the refractive index of a transparent film with a pattern printed on one side, it gives a deeper pattern and enhances the design of the decorative sheet. You can Further, by pre-stocking various kinds of films having a pattern printed on one side, it is possible to quickly cope with the production of many kinds of small lots. In the present invention, the back surface of the thermo-compression-bonded colored opaque amorphous polyester resin film can be treated with a primer. By subjecting the back surface of the colored opaque amorphous polyester resin film to a primer treatment, it is possible to improve the adhesiveness when the decorative sheet is attached to a base material such as plywood, fiber board, or particle board. The primer used is not particularly limited, and examples thereof include an ethylene-vinyl acetate resin primer and a thermoplastic urethane resin primer. The amorphous polyester resin decorative sheet of the present invention has good scratch resistance, has a concealing power that can withstand vacuum forming, and is excellent in design. According to the method of the present invention, such an amorphous polyester resin decorative sheet can be easily and stably manufactured.

[0012]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, evaluation was performed by the following method. (1) Adhesion with heating drum ◯: Adhesion with heating drum is good and workability is good. X: Since it does not come into close contact with the heating drum, air bleeding marks are generated and the product cannot be commercialized. (2) Peelability from heating drum ◯: Good peelability from the heating drum and good workability. X: It is difficult to peel from the heating drum, the film is stretched, and it does not become a product. (3) Scratch resistance ○: 200 g load according to JIS K 5400 8.4
The pencil hardness measured in 2 is 2B or more. ×: According to JIS K 5400 8.4, a load of 200 g
The pencil hardness measured in 3 is 3B or less. The surface of the film is easily scratched. (4) Abrasion resistance: Passes the JAS special plywood abrasion A test. X: Those that do not pass the JAS special plywood wear A test. (5) Vacuum Forming Test A decorative sheet having a length of 250 mm, a width of 180 mm, and a depth of 8 mm is formed by vacuum forming, and is superposed on a fiber board having a recess having the dimensions, and the state of vacuum forming is visually observed. ◯: There is no protrusion of the fiber board, which is in a good state. X: The fiberboard is raised and the commercial value is reduced. (6) Design The appearance of the molded product obtained by vacuum molding is visually evaluated. ◯: The molded product has a depth and is excellent in design. X: The molded product has no depth and the design is inferior.

Example 1 Amorphous polyester resin [Eastman Chemical Company,
PETG6763] was used to form a transparent amorphous polyester resin film having a thickness of 70 μm. A colored opaque amorphous polyester resin film having a thickness of 60 μm was formed from a mixture of 100 parts by weight of the same amorphous polyester resin and 45 parts by weight of a colorant [Sumika Color Co., Ltd., EPM7A1441]. An amorphous polyester resin decorative sheet was manufactured using these transparent amorphous polyester resin film and the colored opaque amorphous polyester resin film. A solution of 100 parts by weight of acrylic polyol, 100 parts by weight of toluene and 100 parts by weight of ethyl acetate was added to polypropylene wax [CLODA Japan
Co., Ltd., WN113, 5 parts by weight was added and uniformly dispersed, and further 5 parts by weight of hexamethylene diisocyanate was added to prepare a two-component urethane resin coating material. This two-component urethane resin coating material was applied to one surface of a transparent amorphous polyester resin film to form a coating film having a thickness of 5 μm. The surface temperature of the heating drum of the doubling device [Nishimura Manufacturing Co., Ltd.] having a heating drum with a diameter of 1,000 mm is set to 1
Keep the temperature at 40 ° C. and bring the surface of the transparent amorphous polyester resin film having the coating film into close contact with the surface of the heating drum.
It was fed out at a speed of 0 m / min. Furthermore, the colored opaque amorphous polyester resin film is fed at the same speed,
A decorative sheet was manufactured by laminating a transparent amorphous polyester resin film on a heating drum and thermocompressing it. In the production of the decorative sheet, the adhesion to the heating drum and the peelability from the heating drum were good. Both the scratch resistance and the wear resistance of the obtained decorative sheet were good. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design. Example 2 As a wax to be added to the two-component urethane resin coating, polyethylene wax [WN3025, manufactured by Croda Japan Co., Ltd.] was used instead of polypropylene wax. In addition, a wood grain pattern was printed by gravure printing on one surface of the colored and opaque amorphous polyester resin film, and laminated so that the printed surface was in contact with the transparent amorphous polyester resin film. After thermocompression bonding the two films, a primer treatment was performed on the back surface of the colored and opaque film using a thermoplastic urethane resin primer. An amorphous polyester resin decorative sheet was manufactured in the same manner as in Example 1 except for this. In the production of the decorative sheet, the adhesion to the heating drum and the peelability from the heating drum were good. Both the scratch resistance and the wear resistance of the obtained decorative sheet were good. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design. When this decorative sheet was bonded to plywood using a rubber adhesive, it was firmly bonded and a good bonding state was obtained. Example 3 A decorative sheet was produced in the same manner as in Example 1 except that ethylenebisstearic acid amide was used instead of polypropylene wax as the wax added to the two-component urethane resin coating material. In the production of the decorative sheet, the adhesion to the heating drum and the peelability from the heating drum were good. Both the scratch resistance and the wear resistance of the obtained decorative sheet were good. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design.

Comparative Example 1 A decorative sheet was produced in the same manner as in Example 1 except that no wax was added to the two-pack type urethane resin coating material.
In the production of the decorative sheet, the adhesiveness with the heating drum was good, the peelability from the heating drum was poor, and the film was stretched during peeling, resulting in uneven thickness. The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design. Comparative Example 2 A decorative sheet was produced in the same manner as in Example 2 except that the amount of polyethylene wax added was 23 parts by weight. In the production of the decorative sheet, the adhesion to the heating drum was poor and the peelability from the heating drum was good. Both the scratch resistance and the wear resistance of the obtained decorative sheet were good. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design. However, the wax bleeded onto the surface of the decorative sheet. Comparative Example 3 A decorative sheet was produced in the same manner as in Example 2 except that the amount of polyethylene wax added was 0.1 part by weight.
In the production of the decorative sheet, the adhesiveness with the heating drum was good, the peelability from the heating drum was poor, and the film was stretched during peeling, resulting in uneven thickness. The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design. Comparative Example 4 A decorative sheet was produced in the same manner as in Example 1 except that the amount of polypropylene wax added was 23 parts by weight.
In the production of the decorative sheet, the adhesion to the heating drum was poor and the peelability from the heating drum was good. Both the scratch resistance and the wear resistance of the obtained decorative sheet were good. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design. However, the wax bleeded onto the surface of the decorative sheet. Comparative Example 5 A decorative sheet was produced in the same manner as in Example 1 except that the amount of polypropylene wax added was 0.1 part by weight. In the production of the decorative sheet, the adhesion with the heating drum is good, and the peelability from the heating drum is poor,
During peeling, the film was stretched and uneven thickness occurred.
The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, no embossing of the fiber board was observed, and the molded product had a depth and was excellent in design.

Comparative Example 6 Amorphous polyester resin [Eastman Chemical Company,
100 parts by weight of PETG6763] and a coloring agent [Sumika Color
Co., EPM7A1441] 45 parts by weight of the mixture,
A 130 μm thick colored opaque amorphous polyester resin film was formed. Acrylic polyol 100 is provided on one side of the colored opaque amorphous polyester resin film.
A two-part urethane resin coating material prepared by adding 5 parts by weight of hexamethylene diisocyanate to a solution consisting of 100 parts by weight of toluene, 100 parts by weight of ethyl acetate, and 5 parts by weight of hexamethylene diisocyanate to form a coating film having a thickness of 5 μm. , Manufactured a decorative sheet. The scratch resistance and abrasion resistance of the obtained decorative sheet were both poor. In the vacuum forming test,
Although no rise of the fiber board was observed, the molded product had no depth and was inferior in design. Comparative Example 7 On one side of the colored opaque amorphous polyester resin film used in Comparative Example 6, a wood grain pattern was printed by gravure printing, and the same two-component urethane resin coating material as in Comparative Example 6 was applied to make a thick film. A 5 μm thick coating film was formed to manufacture a decorative sheet. The scratch resistance and abrasion resistance of the obtained decorative sheet were both poor. In the vacuum forming test, no protrusion of the fiber board was observed, but the molded product had no depth and was inferior in design. Comparative Example 8 On one side of the colored opaque amorphous polyester resin film used in Comparative Example 6, a wood grain pattern was printed by gravure printing, and the same two-component urethane resin coating material as in Comparative Example 6 was applied on the surface to form a thick film. A coating film having a thickness of 5 μm was formed, and a thin film layer of a two-component urethane resin was further formed on the other surface to manufacture a decorative sheet. The scratch resistance and abrasion resistance of the obtained decorative sheet were both poor. In the vacuum forming test,
Although no rise of the fiber board was observed, the molded product had no depth and was inferior in design. Comparative Example 9 On one side of the colored and opaque amorphous polyester resin film used in Comparative Example 6, a wood grain pattern was printed by gravure printing, and the same two-component urethane resin coating material as in Comparative Example 6 was applied to thicken the same. A coating film having a thickness of 5 μm was formed. A wood grain pattern conduit pattern was formed on this coating film by embossing, and wiping printing was performed using a two-component urethane resin-based matte ink, and the concave portion of the embossed pattern was filled with ink to produce a decorative sheet. . The scratch resistance and abrasion resistance of the obtained decorative sheet were both poor. In the vacuum forming test, no protrusion of the fiber board was observed, but the molded product had no depth and was inferior in design.

Comparative Example 10 Amorphous polyester resin [Eastman Chemical Company,
PETG6763] was used to form a transparent amorphous polyester resin film having a thickness of 130 μm. A grain pattern is printed on one side of this transparent amorphous polyester resin film by gravure printing, and on the other side, a solution of 100 parts by weight of acrylic polyol, 100 parts by weight of toluene and 100 parts by weight of ethyl acetate is added to 5 parts of hexamethylene diisocyanate. A two-component urethane resin coating material prepared by adding 1 part by weight was applied to form a coating film having a thickness of 5 μm to manufacture a decorative sheet. The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, the fiber board was found to be raised, but the formed product had depth and was excellent in design. Comparative Example 11 On one surface of the transparent amorphous polyester resin film used in Comparative Example 10, a wood grain pattern was printed by gravure printing,
A coating layer for coloring and hiding was formed thereon, and Comparative Example 1 was formed on the other surface.
The same two-component urethane resin paint as 0 is applied and the thickness is 5 μm
The coating film was formed to produce a decorative sheet. The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, the fiber board was found to be raised, but the formed product had depth and was excellent in design. Comparative Example 12 The transparent amorphous polyester resin film used in Comparative Example 10 was formed with a coating layer for coloring and concealing on one surface, and the other surface was printed with a grain pattern by gravure printing, and Comparative Example 10 was formed thereon.
The same two-component urethane resin coating material was applied to form a coating film having a thickness of 5 μm, and a decorative sheet was manufactured. The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, the fiber board was found to be raised, but the formed product had depth and was excellent in design. Comparative Example 13 A coating layer for coloring and concealing was formed on one side of the transparent amorphous polyester resin film used in Comparative Example 10, and a wood grain pattern was printed on the coating layer by gravure printing, and further thereon. The same two-component urethane resin coating material as in Comparative Example 10 was applied to form a coating film having a thickness of 5 μm, and a decorative sheet was manufactured.
The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, the fiber board was found to be raised, but the formed product had depth and was excellent in design. Comparative Example 14 A thin film layer of a two-component urethane resin was formed on one side of the transparent amorphous polyester resin film used in Comparative Example 10, and a coating layer for coloring and hiding was formed on the other side. A woodgrain pattern was printed on the above by gravure printing, and the same two-component urethane resin coating material as in Comparative Example 10 was further applied thereon to form a coating film having a thickness of 5 μm, and a decorative sheet was manufactured. The obtained decorative sheet had poor scratch resistance and good abrasion resistance. In the vacuum forming test, the fiber board was found to be raised, but the formed product had depth and was excellent in design. The results of Examples 1 to 3 and Comparative Examples 1 to 14 are
It is shown in Table 1.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

The amorphous polyester resin decorative sheet produced by the method of the present invention has a concealing power capable of withstanding vacuum forming by providing a concealing effect by using a colored opaque film, and has a depth. Since the surface coating film contains wax, the decorative sheet has good scratch resistance.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of an embodiment of the method of the present invention.

FIG. 2 is an explanatory diagram of another mode for carrying out the method of the present invention.

[Explanation of symbols] 1 Feeding roll 2 Crimping roll 3 heating drum 4 Feeding roll 5 Crimping roll 6 infrared heater 7 Embossing roll 8 backing rolls 9 cooling rolls 10 cooling rolls 11 winding roll 12 Roll out

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuo Kobayashi 3-11-5 Nihonbashihonmachi, Chuo-ku, Tokyo Riken Vinyl Industry Co., Ltd. (56) Reference JP-A-10-166536 (JP, A) JP Hei 5-278171 (JP, A) JP-A-11-262984 (JP, A) International Publication 99/40154 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00 -35/00

Claims (6)

(57) [Claims] 1. A non-crystalline polyester resin decorative sheet obtained by thermocompression bonding a transparent non-crystalline polyester resin film and a colored opaque non-crystalline polyester resin film,
Amorphous polyester resin characterized in that 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 urethane resin on the surface. Makeup sheet. 2. The amorphous polyester resin decorative sheet according to claim 1, wherein the colored and opaque amorphous polyester resin film has a pattern print on the thermocompression bonding surface. 3. A transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film are thermocompression bonded via a transparent film having a pattern printed on the surface in contact with the colored opaque amorphous polyester resin film. The amorphous polyester resin decorative sheet according to claim 1, which is 4. The amorphous polyester resin decorative sheet according to claim 1, 2 or 3, wherein the colored opaque amorphous polyester resin film has a back surface subjected to a primer treatment. 5. The dicarboxylic acid component of the amorphous polyester resin is terephthalic acid, and the diol component is 50 to 90 mol% of ethylene glycol and 10 to 50 mol% of 1,4-cyclohexanedimethanol. , Claim 2,
The amorphous polyester resin decorative sheet according to claim 3 or 4. 6. A method for producing an amorphous polyester resin decorative sheet comprising thermocompression-bonding a transparent amorphous polyester resin film and a colored opaque amorphous polyester resin film, the method comprising: A coating film of a two-component urethane resin containing 0.5 to 20 parts by weight of wax per 100 parts by weight of the urethane resin is provided on one surface, and the surface of the transparent amorphous polyester resin film having the coating film is a heating drum. Manufacture of an amorphous polyester resin decorative sheet, characterized in that the two films are thermocompressed by laminating a colored and opaque amorphous polyester resin film on a transparent amorphous polyester resin film Method.