JP2005297377A - Decorative laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative laminated sheet which shows the restrained deterioration of lamination part strength after a weatherability test by irradiation with an ultraviolet light or the like while keeping performance such as proper pliability, wear resistance, flaw resistance, chemical resistance, after-processability or heat resistance with the use of materials other than polyvinyl chloride, and further, excellent designability. <P>SOLUTION: In the decorative laminated sheet consisting of a pattern layer 2 and a transparent resin layer 4 formed at least in that order on a base material sheet 1, the base material sheet 1 is made of a non-vinyl chloride material and the transparent resin layer 4 is made of polypropylene resin containing not less than 10 mol% of ethylene. In addition, the polypropylene resin containing not less than 10 mol% of the ethylene is a block polypropylene and the average particle diameter of the ethylene block of the block poplypropylene resin is not more than 3 μm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a decorative sheet that is used as a decorative sheet by being bonded to the surface of a wooden board, an inorganic board, a metal plate or the like with an adhesive.

  Conventionally, a vinyl chloride resin sheet has been most common as a decorative sheet used for the decorative board. In recent years, however, vinyl chloride resin has become a cause of the generation of hydrogen chloride gas and dioxin, which is a highly toxic substance, which causes acid rain during incineration, and also the problem of bleeding out of plasticizers added to vinyl chloride resin sheets As a result, it is becoming a problem from the viewpoint of environmental protection. Decorative sheets using non-vinyl chloride resins such as polypropylene, polyethylene, and acrylic have been demanded.

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

  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 a single layer, but from the viewpoint of design, most are made of a laminate of two or more layers.

  However, since polypropylene resins are generally nonpolar, they have poor adhesion to the same or different types of resins. When a polypropylene resin layer is laminated on another resin layer, for example, maleic acid-modified polyethylene resin or ethylene -The method of laminating | stacking through the resin layer which has polarity, such as (meth) acrylic acid copolymer resin, is used.

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 further improve the strength of the laminated part after the weather resistance test. Regarding the improvement of the heat resistance performance, a method of laminating a polypropylene resin via a maleic acid-modified polypropylene resin has already been proposed as an effective technique (see Patent Document 1), but as a measure for further improving the weather resistance performance. Is only prescribed to adjust the type and amount of UV absorbers and light stabilizers added to the surface protective layer of the polypropylene resin or decorative sheet, and even in that case, for polypropylene applications currently on the market As long as the various weathering agents are prescribed, even if compared with the current decorative sheet, a significant improvement effect cannot be obtained.
JP 2001-353828 A

  The present invention has been made in order to solve the above-mentioned problems, and the object of the present invention is to use materials other than vinyl chloride resin to provide appropriate flexibility, wear resistance, and scratch resistance. An object of the present invention is to provide a decorative sheet that has chemical resistance, post-workability, and heat resistance, and that suppresses a decrease in the strength of the laminated portion after a weather resistance test due to irradiation with ultraviolet rays and the like, and is excellent in design.

  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 resin layer in this order on a base sheet, wherein the base sheet is a non-vinyl chloride type. A decorative sheet made of a material, wherein the transparent resin layer is made of a polypropylene resin containing 10 mol% or more of ethylene.

  The invention according to claim 2 is the decorative sheet according to claim 1, wherein the polypropylene resin containing 10 mol% or more of ethylene is block polypropylene.

  The invention according to claim 3 is the decorative sheet according to claim 2, wherein the average particle diameter of the ethylene block of the block polypropylene resin is 3 μm or less.

  The invention according to claim 4 is a decorative sheet formed by laminating at least a pattern layer and a transparent resin layer in this order on a base sheet, and the base sheet is made of a non-vinyl chloride material, and the transparent resin layer Is a decorative sheet comprising a polymer alloy of a polypropylene resin and a thermoplastic elastomer containing at least an ethylene component, and the ethylene component in the polymer alloy is 10 mol% or more.

  The invention according to claim 5 is characterized in that the transparent resin layer is laminated on the pattern layer side of the base sheet provided with the pattern layer by hot melt extrusion. A decorative sheet according to any one of the above.

  The invention according to claim 6 is the decorative sheet according to any one of claims 1 to 5, wherein a transparent polypropylene resin layer is further laminated on the transparent resin layer.

  The invention according to claim 7 is that the transparent resin layer and the transparent polypropylene resin layer are laminated by heating and melt coextrusion on the pattern layer side of the base sheet provided with the pattern layer. The decorative sheet according to claim 6, characterized in that it is a decorative sheet.

  The invention according to claim 8 is characterized in that the polypropylene resin containing 10 mol% or more of ethylene is modified with an unsaturated carboxylic acid or an anhydride thereof. This is a decorative sheet.

  According to the invention described in claim 1, by using a transparent polypropylene resin having an ethylene content of 10 mol% or more, the resin layer surface is subjected to corona treatment, ozone treatment, plasma treatment, etc., which are usually performed immediately before lamination. The amount of polar groups introduced increases, and it becomes possible to strengthen the adhesion of the laminate interface with the pattern layer side of the substrate sheet provided with the pattern layer.

  According to a second aspect of the present invention, the transparent polypropylene resin having an ethylene content of 10 mol% or more is a block polypropylene, so that a sea-island structure is formed by a propylene matrix and an ethylene domain. The stress at the time of peeling is relaxed, and the effect of improving the laminate strength is obtained.

  According to the invention described in claim 3, when the average particle size of the ethylene block of the block polypropylene resin is 3 μm or less, it is possible to ensure transparency with no practical problem.

  According to a fourth aspect of the invention, a resin is used which is a polymer alloy of a polypropylene resin and a thermoplastic elastomer containing at least an ethylene component, and the ethylene component in the polymer alloy is 10 mol% or more. Therefore, since the sea-island structure is formed by the polypropylene matrix and the thermoplastic elastomer domain, the stress relaxation action works in the same way as in the case of the block polypropylene, and it is possible to obtain almost the same physical properties as in the case of using the block polypropylene. It becomes possible.

  Further, according to the invention of claim 5, the transparent resin layer is laminated by heating and melt extrusion on the pattern layer side of the base sheet provided with the pattern layer, thereby strengthening the adhesion at the lamination interface, In addition, productivity can be improved.

  According to the invention of claim 6, by further laminating a transparent polypropylene resin layer on the transparent resin layer, the transparent resin layer gives interlayer adhesive strength to the decorative sheet, and further by the transparent polypropylene resin layer. It is possible to impart surface scratch resistance and V-cut suitability.

  Further, according to the invention of claim 7, the transparent resin layer and the transparent polypropylene resin layer are further laminated by heating and melt coextrusion on the pattern layer side of the base sheet provided with the pattern layer. It becomes possible to strengthen the adhesion at the interface and improve the productivity.

  According to the invention of claim 8, the polypropylene resin containing 10 mol% or more of ethylene is modified with an unsaturated carboxylic acid or its anhydride, so that the resin itself has a polar group. It is possible to omit steps such as corona treatment, ozone treatment, and plasma treatment.

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

  In FIG. 1, the structure of the cross section of one Example of the decorative sheet of this invention is shown. A pattern sheet 2 and a transparent resin layer 4 made of a transparent polypropylene resin having an ethylene content of 10 mol% or more are laminated in this order on a base sheet 1 for a decorative sheet made of a non-vinyl chloride material.

  In FIG. 2, the structure of the cross section of the other Example of the decorative sheet of this invention is shown. A base sheet 1 for a decorative sheet made of a non-vinyl chloride material, a pattern layer 2, an anchor coat layer 3, a transparent resin layer 4 made of a transparent polypropylene resin having an ethylene content of 10 mol% or more, and a transparent polypropylene resin layer 5. A top coat layer is laminated in this order.

  The transparent resin layer 4 in the present invention is mainly used to protect the pattern layer of the decorative sheet and improve the design, and to exhibit scratch resistance, abrasion resistance, chemical resistance, etc. In order to improve the property, a heat stabilizer, a flame retardant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a catalyst supplement, and the like are appropriately added as necessary. Moreover, the transparent resin layer 4 in FIG. 2 mainly functions as an adhesive resin layer between the base sheet 1 and the transparent transparent polypropylene resin layer 5.

  Since the polypropylene resin used for the transparent resin layer 4 of the present invention generally does not have a polar group, it has poor adhesion with different materials. In order to compensate for this, the transparent resin layer 4 is coated with a non-vinyl chloride resin-based substrate sheet 1 provided with the pattern layer 2 on the side of the laminated surface by a known technique such as corona treatment, ozone treatment, or plasma treatment. Application of polar groups is preferably used.

  Moreover, as shown in FIG. 2, lamination | stacking of the anchor coat layer 3 is used suitably between the base material sheet 1 which provided the transparent resin layer 4 and the pattern layer 2. As shown in FIG. 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.

  In the decorative sheet of the present invention, by using a transparent polypropylene resin having an ethylene content of 10 mol% or more for the transparent resin layer 4, the adhesive force at the lamination interface with the substrate sheet 1 provided with the pattern layer 2, It becomes possible to further strengthen.

  When the ethylene content of the transparent polypropylene resin is in the range of 10 mol% or less, the amount of polar groups introduced into the resin layer surface by the corona treatment, ozone treatment, plasma treatment, etc. is reduced, Sufficient strength is not developed. This is because the introduction of polar groups in the various surface treatments described above is performed more in the ethylene part than in the propylene part. In order to ensure a sufficient number of polar groups at the lamination interface, the ethylene content is at least 10 mol%. The above is necessary.

  Even if the ethylene content is 10 mol% or less, it is possible to introduce a large number of polar groups at the lamination interface by increasing the treatment degree of various surface treatments. By the surface treatment, the molecular chain of the propylene portion at the laminated interface on the transparent polypropylene side is cut and the molecular weight is lowered, and the weather resistance performance of the laminated interface strength of the decorative sheet is lowered.

  In addition, when the transparent polypropylene resin having an ethylene content of 10 mol% or more is a block polypropylene, since a sea island structure is formed by a propylene matrix and an ethylene domain, the stress at the time of peeling the laminate interface is relieved. The effect of improving the laminate strength can be obtained. In addition, this effect appears more healthy in the laminate strength evaluation after the weather resistance test assuming a long-term actual use environment by a sunshine weather meter or the like, rather than in a normal environment.

  In general, block polypropylene containing ethylene at a high concentration is inferior in transparency compared to general homopolypropylene and random polypropylene, and is therefore often not suitable for use as a laminate for printing patterns on decorative sheets. However, by setting the average particle size of the ethylene block to 3 μm or less, it is possible to ensure transparency with no practical problem.

  In place of block polypropylene, even if an alloy resin in which an ethylene-based thermoplastic elastomer such as ethylene-propylene rubber is added to polypropylene is used, a sea-island structure is formed by the polypropylene matrix and the thermoplastic elastomer domain. As in the case, the stress relaxation action works, and it is possible to obtain almost the same physical properties as when block polypropylene is used. However, also in this case, it is necessary to determine the addition amount of the ethylene-based thermoplastic elastomer so that the ethylene content of the alloy resin does not fall below 10 mol%.

  As an example of the polypropylene resin used for the transparent polypropylene resin layer 5 in FIG. 2, if importance is attached to scratch resistance, a high crystalline homopolypropylene having a high pentad fraction may be used, and if V-cut suitability is important. Random polypropylene having a high ethylene content or low crystal homopolypropylene having a low pentad fraction may be used. However, on the other hand, since it is necessary to give the transparent polypropylene resin layer sufficient performance to maintain the strength of the lamination interface with the printed pattern layer, when it is impossible to obtain these simultaneously with one type of polypropylene, As shown in FIG. 2, the two-layer structure of the transparent resin layer 4 and the transparent polypropylene resin layer 5 is selected so that the strength of the laminated interface between the transparent resin layer 4 and the pattern layer can be obtained. For the transparent polypropylene resin layer 5, a resin having scratch resistance and V-cut suitability may be selected.

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

  Further, here, if a transparent polypropylene resin having an ethylene content of 10 mol% or more is modified with an unsaturated carboxylic acid or its anhydride, the resin itself has a polar group, and the corona treatment or ozone treatment described above. It is also possible to omit steps such as plasma treatment. However, the strength between the laminated layers instead tends to be inferior to that obtained by performing corona treatment, ozone treatment, or plasma treatment. Further, if the amount of modification is increased excessively in order to increase the polar group, there arises a problem that the polypropylene resin is changed to brown. Therefore, even when the transparent resin layer 4 of FIG. 1 or FIG. 2 is modified, it is preferable to perform various surface treatments such as corona treatment, ozone treatment, and plasma treatment of the resin. When the polar group is given by modification of the resin and various surface treatments are combined, if the surface treatment amount is the same, if the polar group is given by modification of the resin, the interlayer strength tends to increase. It is in.

  Examples of the unsaturated carboxylic acid or anhydride thereof include acrylic acid, methacrylic acid, maleic acid, phthalic acid, citraconic acid, itaconic acid, and anhydrides thereof, among which maleic anhydride is Particularly preferred.

  In the decorative sheet of the present invention, the base sheet 1 provided with the pattern layer 2 and the transparent resin layer 4 or the laminate of the transparent resin layer 4 and the transparent polypropylene resin layer 4 is subjected to heat and pressure. Bonding thermal laminating method, dry laminating method and wet laminating method to bond via an adhesive, extrusion laminating method in which polypropylene resin is heated and extruded from a T-die on a base sheet, and two or more resins from a T-die at the same time There is a co-extrusion laminating method that performs heat-melt extrusion. Of these, the extrusion lamination method or the coextrusion lamination method is preferably used because of its high productivity.

In the decorative sheet of the present invention, the resin used for the base sheet 1 is preferably a polypropylene resin as a non-vinyl chloride resin material, but is not necessarily limited thereto. For example, polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polystyrene, ABS, polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral , Polyvinyl acetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, polyamide, nylon 6, nylon 66, and the like.
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, 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 (concealing 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 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.

  The method of applying the pattern layer 2 to the base sheet 1 includes the method of applying to the surface of the base sheet 1 and the method of applying to the base sheet 1 itself (in the layer of the sheet 1). The printing method and the transfer method as described above can be used. 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, these methods of forming the color concealing property and pattern on the base sheet 1 itself can be used in combination with the printing method and the transfer method described above.

  Further, when the calendar method is used as a method for producing the concealable base sheet 1, the same method, that is, while the base sheet 1 is produced by the calender method, the base sheet 1 itself is simultaneously colored and concealed. The concealability and the pattern can be formed on the base sheet 1 by a method of forming a pattern, or a method using these methods in combination with the printing method, the transfer method and the like described above.

In the decorative sheet of the present invention, in some cases, in order to obtain a touch feeling on the surface of the decorative sheet and a further design feeling, a concave pattern is formed on the transparent resin layer 4 in FIG. 1 or the transparent polypropylene resin layer 5 in FIG. It is also preferable to fill (wiping) the filling ink in the recessed portion and to provide a topcoat layer on the outermost surface. (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 recessed pattern is inverted is applied to the surface of a chill roll for cooling and solidifying a molten resin, and the extruded resin is 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. In addition, it is also preferable to embed ink in the recessed portion of the recessed pattern applied and to provide a topcoat layer on the outermost surface, but these methods are performed with conventional decorative sheets made of vinyl chloride resin It can be performed by the same method as the wiping process and the top coat process.

  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 give a wood grain pattern using pattern ink (Toyo Ink Manufacturing Co., Ltd .; Lamister). Formed. Furthermore, a two-component curable urethane anchor coating agent (manufactured by Mitsui Takeda Chemical Co., Ltd .; Takelac (main agent), Takenate (curing agent)) is applied to the grain pattern layer 2 with a thickness of about 1 μm by gravure printing. Thus, an anchor coat layer was formed.

Next, on the surface of the anchor coat layer on the substrate sheet on which the pattern layer has been applied, a phenolic antioxidant is added to a transparent block polypropylene (Idemitsu Petrochemical Co., Ltd .; Idemitsu TPO) having an ethylene content of 27 mol%. 2% by weight, 0.3% by weight of hindered amine light stabilizer, 0.5% by weight of benzotriazole UV absorber, 0.2% by weight of anti-blocking agent, embossed transparent with concave pattern on the surface A polypropylene resin layer is heated and extruded through a T-die through the base sheet between a cooling roll subjected to conduit embossing and a pressure roll, and an ozone concentration of 20 g / m ³ ( (Numerical value at 0 ° C under 1 atm) While performing ozone treatment under the condition of ozone flow rate 3m ³ / h (numerical value at 0 ° C under 1 atm), at the same time, the surface is embossed with a concave pattern. Laminate while.

  On the outermost surface of the transparent polypropylene resin layer on which the concave laminate pattern of this laminated laminate was applied, 1.5% by weight of a hindered amine-based light stabilizer and 2.5% by weight of a benzotriazole-based ultraviolet absorber were added, A topcoat layer was applied using a urethane topcoat agent to obtain a decorative sheet.

  Other than using transparent block polypropylene with an ethylene content of 27 mol%, an alloy of random polypropylene with an ethylene content of 4 mol% and ethylene / propylene copolymer rubber (Mitsui Chemicals, Inc .; Mitsui EPT) was used. Used the manufacturing method similar to Example 1 to obtain a decorative sheet.

  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. In addition, a two-component curable urethane anchor coat agent (Mitsui Takeda Chemical Co., Ltd .; Takelac (main agent), Takenate (hardener)) is applied to the wood grain pattern layer to a thickness of about 1 μm by gravure printing. Thus, an anchor coat layer was formed.

Separately, 0.2% by weight of a phenolic antioxidant, 0.5% by weight of a hindered amine light stabilizer, and 0.5% by weight of a benzotriazole UV absorber in a homopolypropylene resin as a transparent polypropylene resin layer , And a polypropylene resin to which 0.2% by weight of an antiblocking agent is added and a transparent block polypropylene (Idemitsu Petrochemical Co., Ltd .; Idemitsu TPO) having an ethylene content of 27 mol% as a transparent resin layer are subjected to conduit embossing. Between the cooling roll and the pressure roll, heat melting and co-extrusion is performed from the T die through the base sheet, and the ozone concentration is 20 g / m ³ (numerical value at 0 ° C. under 1 atm) ozone flow rate at the laminate interface. While performing ozone treatment under the condition of 3 m ³ / h (0 ° C. and 1 atm), at the same time applying a concave embossed pattern to the surface Laminated.

  1.5% by weight of a hindered amine light stabilizer and 2.5% by weight of a benzotriazole-based UV absorber were added to the outermost surface of the transparent polypropylene resin layer 5 on which the concave pattern of the laminated laminate was applied. The topcoat layer 6 was applied using a urethane topcoat agent to obtain a decorative sheet.

Transparent block polypropylene (Idemitsu Petrochemical Co., Ltd .; Idemitsu TPO) resin having an ethylene content of 27 mol% used as a transparent resin layer is graft-polymerized with maleic anhydride (the carbonyl group content in 1 g of the modified random polypropylene is 0.02 mmol) The decorative sheet was obtained in the same manner as in Example 3 except that
<Comparative Example 1>
A decorative sheet was obtained in the same manner as in Example 3 except that the ethylene content of the block polypropylene in Example 3 was changed to 8 mol%.
<Comparison result>
Thus, about each decorative sheet obtained in Examples 1-4 and Comparative Example 1, the peeling test in 23 degreeC atmosphere, and 2000-hour ultraviolet irradiation by a sunshine weather meter (made by Suga Test Instruments Co., Ltd.) A peel test after the test was performed, and the laminate strength under each condition was measured. The results are shown in Table 1 below.

表から見て明らかなように、本発明の実施例１〜４の化粧シートは、比較例１の化粧シートと比べてサンシャインウェザーメーターでの２０００時間の紫外線照射試験後の剥離試験結果に優位性が見受けられる。

As can be seen from the table, the decorative sheets of Examples 1 to 4 of the present invention are superior to the decorative sheet of Comparative Example 1 in the peel test results after a 2000-hour ultraviolet irradiation test with a sunshine weather meter. Can be seen.

  Since the decorative sheet of the present invention does not use any vinyl chloride, there is no concern about environmental problems, and in addition to moderate flexibility, abrasion resistance, scratch resistance, chemical resistance, post-processing properties, and heat resistance, it is practical. A decorative sheet exhibiting excellent effects such as having sufficient weather resistance and excellent design 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. It is explanatory drawing which shows the structure of the cross section of the other 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 ... Transparent resin layer 5 ... Transparent polypropylene resin layer

Claims (8)

  A decorative sheet formed by laminating at least a pattern layer and a transparent resin layer in this order on a base sheet, wherein the base sheet is made of a non-vinyl chloride material, and the transparent resin layer contains 10 mol% or more of ethylene. A decorative sheet comprising a resin.   The decorative sheet according to claim 1, wherein the polypropylene resin containing 10 mol% or more of ethylene is block polypropylene.   The decorative sheet according to claim 2, wherein an average particle size of the ethylene block of the block polypropylene resin is 3 µm or less.   In a decorative sheet formed by laminating at least a pattern layer and a transparent resin layer in this order on a base sheet, the base sheet is made of a non-vinyl chloride material, and the transparent resin layer contains at least a polypropylene resin and an ethylene component. A decorative sheet comprising a polymer alloy with a thermoplastic elastomer and containing 10 mol% or more of an ethylene component in the polymer alloy.   The decorative sheet according to any one of claims 1 to 4, wherein the transparent resin layer is laminated by heat melting extrusion on the pattern layer side of the base sheet provided with the pattern layer.   The decorative sheet according to any one of claims 1 to 5, wherein a transparent polypropylene resin layer is further laminated on the transparent resin layer.   The decorative sheet according to claim 6, wherein the transparent resin layer and the transparent polypropylene resin layer are laminated on the pattern layer side of the base sheet provided with the pattern layer by heat-melt coextrusion. .   The decorative sheet according to any one of claims 1 to 7, wherein the polypropylene resin containing 10 mol% or more of ethylene is modified with an unsaturated carboxylic acid or an anhydride thereof.

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