JP4803441B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet that is used as a decorative sheet by being bonded to the surface of, for example, wooden boards, inorganic boards, and metal plates with an adhesive.

  Conventionally, as a decorative sheet used for a decorative board, a sheet made of a polyvinyl chloride resin has been most common. In recent years, however, polyvinyl chloride resin has become a cause of the generation of hydrogen chloride gas and dioxin, a highly toxic substance, which causes acid rain during incineration, and further due to the bleed-out of plasticizer added to the sheet made of polyvinyl chloride resin. There are also problems such as deterioration in designability, and it has been regarded as a problem from the viewpoint of environmental protection. From the background as described above, a decorative sheet using a non-vinyl chloride resin such as polypropylene, polyethylene, and acrylic has been demanded.

  Under such circumstances, decorative sheets using resins such as polyethylene, polypropylene, polyethylene terephthalate, ethylene vinyl alcohol, and acrylic as a resin replacing vinyl chloride resin have been proposed and marketed.

  Among them, the decorative sheet using polypropylene, which has the appropriate flexibility, abrasion resistance, scratch resistance, heat resistance, chemical resistance, post-processability, etc. required for decorative sheets and is provided at low cost, is the most. Many proposals have been made, and some of them have only been provided with a pattern layer using a known printing method, but from the viewpoint of design and durability, the base layer provided with a pattern layer Most of them are laminated with polypropylene on the pattern side.

  However, since polypropylene resin is generally nonpolar, it has poor adhesion to the same or different types of resins. When a polypropylene resin layer is laminated on another resin layer, for example, polar groups such as maleic acid-modified resin A method of laminating via a resin layer having a selenium or a method of introducing a functional group by ozone treatment or corona treatment is used. Furthermore, in order to improve lamination adhesiveness, an anchor coat layer, a urethane adhesive layer, or the like is also provided.

In recent years, there has been a great demand not only for a decorative sheet using a resin other than a vinyl chloride resin but also for further improvement of required physical properties. Among the required physical properties, one is to further improve the strength of the laminated part after the heat resistance test, and the other is to improve the post-processability of the decorative sheet. For improving the heat resistance, a method of laminating a polypropylene resin via a maleic acid-modified polypropylene resin has already been proposed as an effective method (see Patent Document 1). The decorative sheet is often subjected to a tensile load, such as the production of decorative members by the lapping method, vacuum forming method, etc., and the manufacture of steel sheet decorative members by pressing or bending the steel sheet member to which the decorative sheet is bonded. There is a need to develop decorative sheets that can be used for post-processing.
JP 2001-353828 A

  The present invention has been made in order to solve the above-mentioned problems, and the problem is that a material other than vinyl chloride resin is used, and moderate scratch resistance, chemical resistance, and heat resistance. An object of the present invention is to provide a decorative sheet that has weather resistance and suppresses changes in design such as whitening and cracking during post-processing as much as possible.

The invention according to claim 1 of the present invention for achieving the above object is a decorative sheet obtained by laminating at least a pattern layer and a transparent polypropylene resin layer in this order on a base sheet, the transparent polypropylene resin layer comprising: Random polypropylene having a two-layer structure of a polypropylene protective layer and a polypropylene adhesive resin layer having adhesiveness to the pattern layer in order from the surface layer side, wherein the polypropylene adhesive resin layer contains ethylene the resin as a main component, wherein Ri Na contain ethylene-propylene copolymer elastomer and an ethylene-butene copolymer elastomer, and a maleic acid-modified polypropylene in a weight ratio of random polypropylene: the maleated polypropylene = 45: 5 ratio of It is a decorative sheet characterized by containing .

The invention according to claim 2 is characterized in that 10 to 80 parts by weight of an ethylene / propylene copolymer elastomer is added to 100 parts by weight of the random polypropylene resin in the polypropylene adhesive resin layer. The decorative sheet according to claim 1.

  The invention according to claim 3 is characterized in that the ethylene / butene copolymer elastomer is added in an amount of 0.5 to 1.5 times by weight with respect to the ethylene / propylene copolymer elastomer. Item 3. A decorative sheet according to Item 1 or 2.

The invention according to claim 4 is the decorative sheet according to any one of claims 1 to 3, wherein the polypropylene adhesive resin layer has an elastic modulus of 700 MPa or less.

The invention of claim 5, wherein the lamination of the two layers of the polypropylene protective layer and a polypropylene adhesive resin layer, characterized in that it is made by co-extrusion, in any one of claims 1 to 4 It is a decorative sheet of description.
The invention according to claim 6 is the decorative sheet according to any one of claims 1 to 5, wherein the ethylene content of the random polypropylene resin is 6 to 9% by weight.
The invention according to claim 7 is the decorative sheet according to any one of claims 1 to 5, wherein the ethylene content of the random polypropylene resin is 7% by weight.

  According to the invention of claim 1, the transparent polypropylene resin layer is made into two layers, that is, the polypropylene protective layer having performance such as weather resistance, chemical resistance, and scratch resistance, and adhesiveness to the pattern layer, By dividing into two layers, a polypropylene adhesive resin layer that does not impair the adhesion to the pattern layer even after various durability tests, it becomes possible to select a grade resin having a characteristic function for each. . Especially for the polypropylene adhesive resin layer, by adding ethylene / propylene copolymer elastomer with polypropylene as the main component, the stress relaxation ability as a layer is improved, and the stress of peeling is prevented from concentrating on the sheet lamination interface, As a result, a suppressing effect is obtained with respect to a decrease in the adhesion strength of the transparent polypropylene resin layer after the weather resistance test and other durability tests.

  Further, by adding an ethylene / butene copolymer elastomer, compatibility between, for example, a random polypropylene resin and an ethylene / propylene copolymer elastomer is increased. As a result, since the cohesive force of the polypropylene adhesive resin layer is improved, the peel strength after the heat resistance test and the effect of suppressing whitening during bending of the decorative sheet can be obtained.

  In the first place, since a propylene resin and an ethylene resin are not compatible, for example, a decorative sheet using a resin obtained by alloying a random polypropylene resin with an ethylene / propylene copolymer elastomer for a polypropylene adhesive resin layer is used for bending or pressing. Depending on the processing conditions, a dissociation part called “craze” is generated at the interface between the random polypropylene and the ethylene / propylene copolymer elastomer. This causes a decrease in cohesive force, resulting in a decrease in peel strength, and whitening due to irregular reflection of light.

  However, when an ethylene / butene copolymer elastomer is added thereto, the ethylene part of the ethylene / butene copolymer elastomer and the ethylene / propylene copolymer elastomer are well compatible, and the butene part is also well compatible with polypropylene. The ethylene / butene copolymer elastomer functions as a compatibilizer between polypropylene and ethylene / propylene copolymer elastomer. As a result, generation of craze is suppressed, and as a result, phenomena such as a decrease in peel strength and whitening of the polypropylene adhesive resin layer are suppressed in the processed portion.

  Further, according to the invention of claim 2, by adding 10 to 80 parts by weight of ethylene / propylene copolymer elastomer to 100 parts by weight of polypropylene in the polypropylene adhesive resin layer, the peel strength between the sheet layers is maximized. can do. By adding 10 parts by weight or more, the stress relaxation ability can be sufficiently expressed, and by adding 80 parts by weight or less, the cohesive force of the polypropylene adhesive resin layer is maintained, and the peel strength is not lowered.

  Further, according to the invention described in claim 3, whitening of the polypropylene adhesive resin layer in the processed portion during bending and pressing can be minimized. By adding the ethylene / butene copolymer elastomer 0.5 times or more with respect to the ethylene / propylene copolymer elastomer, whitening during processing can be sufficiently suppressed. In addition, when added exceeding 1.5 times, compatibility will become high too much and the stress relaxation capability will be reduced, and as a result, the peeling strength after various durability tests will be reduced.

In addition, since the polypropylene resin in the polypropylene adhesive resin layer is a random polypropylene resin having an ethylene content of 5% or more , the random polypropylene itself can be softened, so that the stress relaxation of the polypropylene adhesive resin layer is achieved. Ability can be improved. Further, since random polypropylene is soft, it is difficult to cause a deviation from the ethylene / propylene copolymer elastomer, which is also a soft component, and an effect of suppressing whitening of the polypropylene adhesive resin layer during bending can be obtained.

According to the invention of claim 4 , whitening and cracking suppression effects can be imparted to the polypropylene resin of the polypropylene adhesive resin layer. Moreover, the effect which suppresses the stress concentration to the lamination | stacking part at the time of peel strength measurement is also acquired by restraining an elasticity modulus in the range of this invention. Moreover, the effect of increasing transparency can be expected by making the polypropylene resin of the polypropylene adhesive resin layer a homopolypropylene or a random polypropylene with a large amount of amorphous.

In addition, the invention according to claim 5 makes it possible to adhere polypropylenes that are inherently nonpolar and difficult to adhere to each other by entanglement of physical materials, and suppress swelling at the interface of the laminate in the durability test of the decorative sheet. Effect is obtained.

  Embodiments of the present invention will be described below with reference to the drawings.

  In FIG. 1, the structure of the cross section is shown about one Example of the decorative sheet of this invention. A base sheet 1 for a decorative sheet made of a non-vinyl chloride material is laminated with a pattern layer 2 by using, for example, a gravure printing method, and a random polypropylene resin as a main component and ethylene via an anchor coat layer 3. A polypropylene adhesive resin layer 4 to which a propylene copolymer elastomer and an ethylene / butene copolymer elastomer are added, and a polypropylene protective layer 5 made of homopolypropylene to which an ultraviolet absorber and a radical scavenger are added are laminated in this order, and The decorative sheet of the present invention can be obtained by laminating an acrylic surface protective layer 6 to which an ultraviolet absorber and a radical scavenger are added on the outermost layer.

  The greatest point in the present invention lies in the polypropylene adhesive resin layer 4, and since polypropylene has a melting point of 130 to 170 ° C., it has an advantage of being resistant to a heat load that may occur in an actual environment. In addition, the main purpose in the functional part using the polypropylene adhesive resin layer 4 is to improve the adhesion between the pattern layer 2 and the polypropylene protective layer 5. Therefore, in addition to introducing a functional group into the polypropylene adhesive resin layer 4 by graft polymerization of maleic anhydride, the resin layer may be provided with a function of absorbing stress. In this form, the introduction ratio of maleic anhydride is preferably 0.1 to 1.0 mol% with respect to polypropylene.

  Polypropylene resin has an elastic modulus of about 700 to 2000 MPa and high rigidity, and therefore has a poor ability to absorb stress due to peeling or the like in the entire resin layer. Therefore, by adding various thermoplastic elastomer components, the rigidity is reduced, and since the elastomer components exhibit spring-like performance, it is possible to impart stress absorption capability. There are various types of thermoplastic elastomers, but by using an ethylene / propylene copolymer elastomer and an ethylene / butene copolymer elastomer at the same time as in the present invention, of course, the above-mentioned stress absorption capability can be imparted. The effect of suppressing whitening in bending can be imparted. Here, the elastic modulus is a tensile elastic modulus and is a value measured based on JIS Z1702. The polypropylene adhesive resin layer 4 in the present invention desirably has an elastic modulus of 700 MPa or less. By controlling the elastic modulus to 700 MPa or less, it is possible to impart whitening and cracking suppression effects. Moreover, the effect which suppresses the stress concentration to the laminated part at the time of peel strength measurement is also acquired. The elastic modulus of the preferable polypropylene adhesive resin layer 4 is 100 to 500 MPa.

  The ethylene content in the ethylene / propylene copolymer elastomer is preferably 60 to 80% by weight, and the ethylene content in the ethylene / butene copolymer elastomer is preferably 10 to 40% by weight.

As described above, it is preferable that 10 to 80 parts by weight of the ethylene / propylene copolymer elastomer is added to 100 parts by weight of the polypropylene resin in the polypropylene adhesive resin layer 4. More preferably, it is 15-40 weight part.
The ethylene / butene copolymer elastomer is preferably added in an amount of 0.5 to 1.5 times by weight with respect to the ethylene / propylene copolymer elastomer. More preferably, the addition is 1.0 to 1.2 times. The polypropylene adhesive resin layer 4 is preferably a single layer of polypropylene or a layer in which the matrix part of the matrix-domain structure becomes polypropylene when the polypropylene and other resins are laminated by lamination.

In the present invention, the polypropylene resin of polypropylene adhesive resin layer 4, random polypropylene resins of more than 5% of ethylene content is preferred. When using a random polypropylene resin, it is possible to improve the stress relaxation ability of the polypropylene adhesive resin layer 4, also, bending whitening effect of suppressing polypropylene adhesive resin layer 4 at the time of processing can be obtained. A more preferable ethylene content is 6 to 9% by weight .

  As for the thickness of the polypropylene adhesive resin layer 4, 5-30 micrometers is preferable.

  Hereinafter, other layers will be described.

  As the material of the base sheet 1 in the present invention, there is nothing specially defined as long as it is other than the polyvinyl chloride resin, but a polypropylene-based material is preferably used in view of printability and economy. However, this is not always the case. For example, polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polystyrene, ABS, polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, poly Examples include vinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, polyamide, nylon 6, and nylon 66.

  Further, in the resin used for the base sheet 1, one or more additives such as inorganic pigments, antioxidants, light stabilizers and antiblocking agents can be added in appropriate amounts. is there.

  In the decorative sheet of the present invention, a base sheet made of a non-vinyl chloride material that is concealed can be used as the base sheet 1. The reason for concealing is to prevent a base material such as a wooden board, an inorganic board, or a metal plate to be bonded from being visible from the surface of the decorative sheet.

  In order to prevent the base material such as a wooden board, an inorganic board, and a metal plate to be bonded to the base sheet 1 of the decorative sheet of the present invention from being visible from the surface of the decorative sheet, Thus, it is desirable to provide concealability to the base sheet 1 of the decorative sheet and its intermediate layer by means such as addition of a pigment or formation of a pigment coating layer (concealment layer). However, this is not the case when it is desired to make use of the texture of the base material.

  As a method for forming the concealability (the concealing layer) and the pattern layer 2 on the base sheet 1, gravure printing, intaglio printing, flexographic printing on the front surface or the back surface of the base sheet 1 or both, Printing is generally performed by a known printing method such as silk printing, electrostatic printing, and ink jet printing, but this is not necessarily the case. Ink used is also known, that is, a colorant such as a dye or pigment or an extender pigment is added to the vehicle, and further, a plasticizer, a stabilizer, a wax, a grease, a desiccant, a curing agent, a thickener, and a dispersant. The ink may be obtained by arbitrarily adding a filler or the like and sufficiently kneading with a solvent, a diluent or the like.

  Further, the concealing layer or the pattern layer 2 or both of them are formed on an arbitrary transfer base sheet different from the base sheet 1 for the decorative sheet by the above forming method or the like, and the above heat laminate The substrate sheet for transfer is peeled off after being bonded to the substrate sheet 1 by the method, dry lamination method, wet lamination method, extrusion lamination method, etc., and the concealing layer or the pattern layer 2 or both are removed. A method of transferring to the base sheet 1 can also be used.

  Further, when the T-die extrusion method is used as the method for producing the base sheet 1, the synthetic resin material for forming the base sheet 1 is directly colored with a concealing colorant such as a dye or pigment. By extruding from a T-die in a heated and melted state to form the base sheet 1, it is possible to have a concealing effect.

  As a coloring method of the base sheet 1 in the T-die extrusion method in this case, a dry color method, a master batch method, and the like are known, but are not particularly limited. In the dry color method, a fine powdery colorant obtained by treating a pigment with a dispersion aid or a surfactant is directly mixed into an ordinary uncolored synthetic resin material for forming the base sheet 1. This is a method of coloring. On the other hand, in the master batch method, a master batch pellet in which a normal synthetic resin material that is not colored for forming the base sheet 1 and a high concentration pigment is melt-kneaded and pre-dispersed is prepared in advance. In the extrusion hopper, this master batch pellet is dry blended with an ordinary uncolored synthetic resin material for forming the base sheet 1 into a film.

  The types of pigments may be those usually used, but inorganic pigments such as titanium oxide, ultramarine blue, cadmium pigment, iron oxide and the like are particularly desirable in consideration of heat resistance and weather resistance. Also, organic pigments such as phthalocyanine pigments and quinacridone pigments can be used. The pigment-to-resin ratio and color are appropriately determined in view of the degree of concealment and design properties, and are not particularly limited.

  As a method of applying the pattern layer 2 to the base sheet 1, there is a method of applying to the base sheet 1 itself (in the layer of the sheet 1) in addition to the method of applying the pattern layer 2 to the surface of the base sheet 1 as described above. As a method for applying to the base sheet 1 itself, a master batch pellet in which a high concentration pigment is melt-kneaded into a resin having different flow characteristics from the resin of the base sheet 1 and pre-dispersed, or wood powder, glass powder, etc. It is added to the synthetic resin material provided with the concealability for forming the base sheet 1 and heated and melted, extruded, and formed into a film, and master batch pellets and wood powder are formed on the concealable base sheet 1 itself. There is also a method of forming a pattern with glass powder or the like. Of course, it can be used in combination with these methods of forming a color hiding property or pattern on the substrate sheet 1 itself.

  In addition, when the calendar method is used as a method for manufacturing the base material sheet 1 having concealability, the same method, that is, while the base material sheet 1 is manufactured by the calender method, the base material sheet 1 itself is colored and concealed simultaneously. The concealability and the pattern can also be formed on the base sheet 1 by a method of forming a pattern or a method using these methods in combination with the above-described printing method, transfer method or the like.

  When the resin is extruded and laminated on the surface layer on the pattern layer side of the base material sheet 1 provided with the pattern layer 2, the lamination of the anchor coat layer 3 is preferably used. If a non-chlorine material is used for the anchor coat layer 3, the material is not limited, but a two-component curable urethane resin that forms a urethane bond by reaction of polyol and isocyanate is desirable. As the isocyanate, those containing at least one of hexamethylene diisocyanate and isophorone diisocyanate are suitable. The formation method of the anchor coat layer 3 is preferably a gravure method (gravure printing method, gravure coating method), but is not limited thereto.

  The polypropylene protective layer 5 in the present invention is mainly used for protecting the decorative layer of the decorative sheet and improving the design, and exhibiting scratch resistance, abrasion resistance, chemical resistance, etc. In principle, the printed pattern layer must be transparent. In addition, a heat stabilizer, a flame retardant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a catalyst supplement, and the like are appropriately added to the resin layer as necessary to improve the functionality of the decorative sheet.

  In selecting a polypropylene resin to be used for the polypropylene protective layer 5, for example, if importance is attached to scratch resistance, a high crystalline homopolypropylene with a high pentad fraction may be used, and if importance is attached to V-cut suitability, Random polypropylene having a high ethylene content or low crystal polypropylene containing a lot of amorphous components may be used.

  As for the thickness of the polypropylene protective layer 5, 30-200 micrometers is preferable.

  As a method for laminating the polypropylene adhesive resin layer 4 and the transparent polypropylene resin layer 5, a known method may be used, but in order to carry out lamination more simply, a heat-melt coextrusion method using a T die is desirable.

  In the decorative sheet of the present invention, as a method for laminating the base material sheet 1 provided with the pattern layer 2 and the laminate of the polypropylene adhesive resin layer 4 and the polypropylene protective layer 5, a known method may be used. The coextrusion laminating method is preferably used because of its good productivity.

  Further, in the decorative sheet of the present invention, depending on the case, in order to obtain a touch feeling on the surface of the decorative sheet and a further design feeling, a concave pattern is given to an arbitrary resin layer, or in the concave part as necessary. The filling ink is preferably embedded (not shown).

  The method for applying the concave pattern may be a normal hot-pressure embossing method and is not limited at all. In addition, when the T-die extrusion method is used as a method for producing a decorative sheet, a protrusion pattern in which a concave pattern is reversed is applied to the surface of a chill roll for cooling and solidifying a molten resin, and the extruded resin is used as a chill roll and a press roll. In general, a method of embossing between the layers and forming a concave pattern on the surface of the transparent resin layer or the transparent polypropylene resin layer is generally used.

  EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.

  As a base sheet, 6% by weight of an inorganic pigment, 0.2% by weight of a phenolic antioxidant, 0.3% by weight of a hindered amine light stabilizer, and 0.2% by weight of an antiblocking agent are added to a random polypropylene resin. Using a sheet obtained by melt-extruding the resulting resin, corona treatment is applied to the surface of the sheet, and then a gravure printing method is used to apply a wood grain pattern using pattern ink (manufactured by Toyo Ink Manufacturing Co., Ltd .; Lamister). Formed. Furthermore, a two-component curable urethane anchor coating agent (Mitsui Chemical Polyurethanes Co., Ltd .; Takelac (main agent), Takenate (hardener)) is applied to the wood grain pattern layer with a thickness of about 1 μm by gravure printing. Thus, the anchor coat layer 3 was formed.

On the other hand, biaxial extrusion of (1) polypropylene, (2) ethylene / propylene copolymer elastomer, (3) ethylene / butene copolymer elastomer, and (4) maleic acid modified polyolefin resin based on the recipes in Tables 1 and 2 The polypropylene adhesive resins of Examples and Comparative Examples were obtained by kneading using a machine. In addition, Example 2 is a reference example.

Random PP: Random polypropylene resin (ethylene content 7% by weight) manufactured by Sun Allomer Co., Ltd.
Homo PP: Homo polypropylene manufactured by Prime Polymer Co., Ltd. (crystallinity 70%)
EP912: Ethylene / propylene copolymer elastomer Dynalon 6200P manufactured by JSR Corporation Ethylene / butene copolymer elastomer Umex 1001 manufactured by JSR Corporation Maleic acid-modified polypropylene manufactured by Sanyo Chemical Industries

Next, 10 μm of the polypropylene adhesive resin layer and 70 μm of homopolypropylene (Prime Polymer Co., Ltd .; Prime TPO) are applied to the anchor coat coated surface side of the base sheet on which the pattern layer has been applied, by a coextrusion laminating method. The layers were laminated in this order at an extrusion resin temperature of 230 ° C. At that time, an ozone concentration of 10 g / m ³ (numerical value at 0 ° C. and 1 atm) and an ozone flow rate of 3 m ³ / h (numerical value at 0 ° C. and 1 atm) are provided at the laminated interface between the anchor coat coated surface and the polypropylene adhesive resin layer. The substrate was laminated with an embossed pattern of recesses on the surface at the same time as the ozone treatment.

  Isocyanate-curing type, in which 3% by weight of a hindered amine-based light stabilizer and 5% by weight of a benzotriazole-based UV absorber are added to the outermost surface of a transparent polypropylene resin layer having a concave and recessed pattern of the laminated laminate. A coating (made by Dainippon Ink & Chemicals, Inc .: UC Clear) was laminated with a thickness of 6 μm to provide a surface protective layer to obtain a decorative sheet.

<Comparison result>
For each decorative sheet thus obtained, a peel test under an atmosphere of 23 ° C., a peel test after heating at 90 ° C. for 72 hours, and a 2000-hour ultraviolet irradiation test using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) The peeling test after (black panel 63 ° C., shower spraying for 12 minutes in 60 minutes) was performed. In addition, each decorative sheet obtained this time was bonded to a steel sheet substrate having a thickness of 0.5 mm, and 1R bending was performed in a 5 ° C. environment, and whitening of the bent portion was observed.

  As can be seen from Table 3, in the decorative sheets of Examples 1 and 2 of the present invention, relatively high physical property values are obtained in all the evaluated items. In Example 3, the cohesive force of the polypropylene adhesive resin layer was lowered due to excessive elastomer component, and the relative strength was lowered. In Example 4, the compatibility between the polypropylene and the ethylene / propylene copolymer elastomer was lowered due to the insufficient blending amount of the ethylene / butene copolymer elastomer, and in the polypropylene adhesive resin layer at 5 ° C. and 1R bending. Craze was generated at the interface between polypropylene and the ethylene / propylene copolymer elastomer, and whitening occurred. However, for the other items, physical property values equivalent to those in Example 1 were obtained.

  On the other hand, in Comparative Example 1, since ethylene / propylene copolymer elastomer or ethylene / butene copolymer elastomer is not blended, stress concentrates on the lamination interface, and as a result, the adhesion strength is that of other conditions. Compared to a large drop.

  Since the decorative sheet of the present invention does not use any vinyl chloride, there is no concern about environmental problems, and the adhesiveness between the polypropylene protective layer and the pattern layer is less affected by stress such as heating and ultraviolet irradiation. Furthermore, even if the decorative sheet of the present invention is bonded to various substrates and subjected to bending processing, a decorative sheet that does not deteriorate in design properties such as whitening can be provided.

It is explanatory drawing which shows the structure of the cross section of one Example of the decorative sheet of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Base material sheet, 2 ... Pattern layer, 3 ... Anchor coat layer, 4 ... Polypropylene adhesive resin layer, 5 ... Polypropylene protective layer, 6 ... Surface protective layer.

Claims (7)

In a decorative sheet formed by laminating a pattern layer and a transparent polypropylene resin layer at least in this order on a base sheet, the transparent polypropylene resin layer has an adhesive property to the polypropylene protective layer and the pattern layer in order from the surface layer side. The polypropylene adhesive resin layer has a two-layer structure, and the polypropylene adhesive resin layer is composed mainly of a random polypropylene resin containing ethylene, and an ethylene / propylene copolymer elastomer and an ethylene / butene copolymer. elastomer Ri Na contain, and the random polypropylene maleic acid-modified polypropylene in a weight ratio: the maleated polypropylene = 45: decorative sheet characterized by containing in a ratio of 5. The decorative sheet according to claim 1, wherein 10 to 80 parts by weight of an ethylene / propylene copolymer elastomer is added to 100 parts by weight of the random polypropylene resin in the polypropylene adhesive resin layer.   The decorative sheet according to claim 1 or 2, wherein the ethylene / butene copolymer elastomer is added in an amount of 0.5 to 1.5 times by weight with respect to the ethylene / propylene copolymer elastomer.   The decorative sheet according to claim 1, wherein the polypropylene adhesive resin layer has an elastic modulus of 700 MPa or less. The decorative sheet according to any one of claims 1 to 4 , wherein two layers of the polypropylene protective layer and the polypropylene adhesive resin layer are laminated by a coextrusion method. The decorative sheet according to any one of claims 1 to 5, wherein the random polypropylene resin has an ethylene content of 6 to 9% by weight. The decorative sheet according to any one of claims 1 to 5, wherein the random polypropylene resin has an ethylene content of 7% by weight.

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