JP4322084B2 - Decorative multilayer sheet and molded product thereof - Google Patents

Description

  The present invention relates to a decorative multilayer sheet used for forming a surface layer instead of painting in order to improve the design of various molded articles, and a molded article having the decorative multilayer sheet as a surface layer. More specifically, it is possible to form a surface layer having various colors and excellent gloss and scratch resistance, and a decorative multilayer sheet having excellent vacuum formability and adhesion to a substrate, and the surface layer as a surface layer. It relates to the molded product used.

  Plastic injection molded products are used in various fields such as vehicle parts, home appliances, office supplies, sports equipment, building supplies, and decorative articles. These injection-molded products are often painted to enhance the surface scratch resistance and aesthetics, but are omitted to avoid production and cost penalties and environmental problems associated with the painting process. Alternatives are being sought. One such alternative is a composite film in which a transparent layer, a colored layer, an adhesive layer, and a base material layer are sequentially laminated, and an ethylene copolymer obtained by polymerizing with a metallocene catalyst as the base material layer. The use of a paint substitute film using a blend of propylene and a propylene copolymer has been proposed (see Patent Document 1). In this proposal, a mixture of fluororesin and acrylic resin is used in the transparent layer and the colored layer, and chlorinated polyethylene is used in the adhesive layer. In these laminations, specifically, since these are obtained by recoating them by dissolving them in an organic solvent, the disadvantages and problems associated with the painting process are sufficiently eliminated. Has not reached. Furthermore, since the composite film as described above is based on a non-polyolefin resin, it is difficult to apply it to recyclability.

Japanese Patent Laid-Open No. 11-207899

  Therefore, the object of the present invention is to easily mold without using an organic solvent or the like, and when used as a surface material for an injection molded product as described above, it has a surface appearance excellent in scratch resistance, gloss, design and the like. An object of the present invention is to provide a decorative multilayer sheet capable of forming a surface layer having the same. Another object of the present invention is a decorative multilayer sheet that can form an excellent surface layer even when used as a surface material for an injection-molded article having a complicated shape, and that is excellent in vacuum formability or pressure formability. Is to provide. Still another object of the present invention is to provide a decorated multilayer sheet having excellent interlayer adhesion. In the present invention, the term “sheet” is used to include a film.

That is, the present invention is a decorative multilayer sheet having at least three layers composed of a surface layer / decorative layer / adhesive layer, wherein the surface layer is made of an ionomer of an ethylene / unsaturated carboxylic acid copolymer. It is a clear layer, and the decorative layer is composed of 0.3 to 5% by weight of aluminum powder having an average particle diameter of 0.1 to 50 μm, or ethylene / unsaturated carboxylic acid blended with 0.1 to 20% by weight of a colorant It is an ionomer layer of a polymer, and the adhesive layer is selected from an ethylene copolymer layer polymerized by a metallocene catalyst and having a density of 880 to 920 kg / m ³ or polypropylene, polyethylene and an ethylene copolymer having a polar group. Olefin polymer (A) 20 to 85% by weight, amorphous or low crystalline ethylene / α-olefin copolymer (B) 10 to 50% by weight, tackifying resin (C) 5 to 30 About decorative multilayer sheet, characterized in that the quantity% and hydrogenated diene-based elastomer (D) a resin composition layer consisting of 0-30 wt%.

  The present invention also relates to a decorative molded product obtained by laminating the decorative multilayer sheet on the substrate surface.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in glossiness, scratch resistance, and vacuum moldability, and can provide the decorative multilayer sheet which has a metallic tone and various color tones. Such a decorative multilayer sheet is excellent in interlayer adhesion and substrate adhesion, and can be used as a coating substitute sheet as a surface material for various substrates, for example, injection molded products. Decorative molded products obtained by laminating the above decorative multilayer sheet on the base material surface are used as vehicle parts such as automobiles, motorcycles, trucks, home appliances, building equipment, office supplies, sports equipment, decorative goods, miscellaneous goods, etc. can do.

  The decorative multilayer sheet of the present invention has a layer structure of at least three layers comprising a surface layer / decorative layer / adhesive layer, and each layer may be composed of one layer or two layers or more. It may also have other layers, such as a backing layer, adjacent to the adhesive layer. The surface layer is a clear layer (transparent layer), and the decorative layer includes a layer containing aluminum powder and / or a colorant such as a color pigment or dye, but both layers are co-polymerized with ethylene / unsaturated carboxylic acid. It consists of a combined ionomer.

  The ethylene / unsaturated carboxylic acid copolymer which is the base polymer of the ionomer used for the surface layer and the decorative layer is not only a binary copolymer of ethylene and unsaturated carboxylic acid, but also ethylene, unsaturated carboxylic acid and further It may be a multi-component copolymer in which other monomers are copolymerized. Examples of the unsaturated carboxylic acid in the copolymer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, monomethyl maleate, monoethyl maleate, etc., and particularly acrylic acid or methacrylic acid. Is preferred. Examples of the other monomer that can be a polymerization component of the copolymer include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate. , Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, dimethyl maleate, diethyl maleate and other unsaturated carboxylic acid esters, vinyl acetate such as vinyl acetate, carbon monoxide and the like. it can.

  Examples of the cationic species in the ionomer include monovalent metals such as lithium, sodium, and potassium, and polyvalent metals such as calcium, magnesium, and zinc. Such metal ions do not need to be one kind, and may be two kinds or more, and two or more ionomers may be used in combination. Particularly preferred ionic species are sodium and zinc.

  As an ionomer used for the surface layer of the decorative multilayer sheet of the present invention, in consideration of gloss, transparency, scratch resistance, vacuum formability, etc., the unsaturated polymer base in the ethylene / unsaturated carboxylic acid copolymer is unsaturated. The carboxylic acid content is 5 to 30% by weight, preferably 10 to 25% by weight, the other monomer content is 0 to 20% by weight, preferably 0 to 10% by weight, and the degree of neutralization is 10 to 90%. %, Preferably in the range of 20 to 80%.

  In addition, the ionomer used in the decorative layer is an ethylene / unsaturated base polymer, considering the affinity and dispersibility with aluminum powder and colorant, interlayer adhesion with the surface layer and adhesive layer, and workability. The unsaturated carboxylic acid content in the carboxylic acid copolymer is 2 to 30% by weight, preferably 5 to 25% by weight, the other monomer content is 0 to 40% by weight, preferably 0 to 30% by weight, Further, those having a degree of neutralization in the range of 5 to 90%, preferably 10 to 80% are suitable.

  The ionomers used in these two layers also have a melt flow rate of 0.01 to 200 g / 10 min, particularly 0.1 to 100 g / 10 at 190 ° C. and a load of 2160 g in consideration of processability and mechanical strength. Minutes are preferred.

  Various additives can be blended in the ionomer used for the surface layer as long as the above properties are not substantially impaired. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents and the like.

  The ionomer used for the decorative layer is blended with aluminum powder having an average particle size of 0.1 to 50 μm, preferably 0.1 to 20 μm, or a coloring agent. That is, when the particle size of the aluminum powder becomes too large, the shielding property is not sufficient, and the effect of improving the design property becomes insufficient. By blending aluminum powder having a predetermined particle size, a glossy metallic decorative multilayer sheet can be obtained. Moreover, when mix | blending a coloring agent, the decorating multilayer sheet excellent in the designability which has various color tones can be obtained by selection of a coloring agent. In addition, a decorative metallic multi-layer sheet with a colored metallic tone by making it a layer containing aluminum powder and a colorant as a decorative layer, or by forming a multilayer structure of a layer containing aluminum powder and a layer containing a colorant. Is obtained. In consideration of the design properties, it is preferable to provide a layer in which aluminum powder or a colorant is blended as the decorative layer. The blending amount of the aluminum powder in the blending layer of the aluminum powder is preferably 0.3 to 5% by weight, particularly preferably 0.5 to 3% by weight. That is, if the amount is too small, the shielding property is inferior. On the other hand, if the amount is too large, the effect of increasing the amount is not recognized and it is not economical.

In the case of blending aluminum powder, it is preferable to use a master batch having an aluminum powder concentration of about 5 to 25% by weight in order to uniformly disperse it in the ionomer. In that case, in order to uniformly disperse the aluminum powder, it is preferable to use, as the carrier resin, an ionomer or linear low-density polyethylene as described above as used as a decorative layer. The linear low density polyethylene is a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, preferably 4 to 10 carbon atoms, and has a density of about 900 to 930 kg / m ^3. Suitable are those having a melt flow rate of 0.1 to 200 g / 10 min, particularly 0.5 to 50 g / 10 min at a load of 2160 g at ° C. Examples of the α-olefin having 3 or more carbon atoms in the linear low density polyethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 4-methyl. Examples thereof include -1-pentene.

When a colorant is used as the decorative layer, a pigment or a dye is used as the colorant. As the pigment, both inorganic pigments and organic pigments can be used. More specifically, as inorganic pigments, white pigments such as titanium oxide and zinc oxide, extender pigments such as calcium carbonate and barium sulfate, black pigments such as carbon black, brown rice, red lead, molybdenum red, cadmium red and the like Examples thereof include red pigments, yellow pigments such as risurge, yellow lead and yellow iron oxide, and blue pigments such as bitumen and ultramarine blue. Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, isoindolinone pigments, dioxazine pigments, and selenium pigments. The dye has a sulfonic acid group or a carboxyl group and does not contain an amino group (—NH ₂ ) or an imino group (—NH—), and an azo group, a phthalocyanine group, a triarylmethane group, a nitro group, and Preference is given to using organic acid dyes having a chromophore selected from nitroso groups.

  When the colorant is blended in the decorative layer, the blending amount of the colorant is preferably 0.1 to 20% by weight, particularly preferably 0.1 to 5% by weight.

  When providing both a layer containing aluminum powder and a layer containing colorant as a decorative layer, a layer containing aluminum powder is provided as a layer adjacent to the surface layer, and a colorant is provided adjacent to the layer. It is preferable to provide a blended layer.

In the decorative multilayer sheet of the present invention, an adhesive layer is provided in addition to the surface layer and the decorative layer. This adhesive layer preferably has good adhesion to the decorative layer, and is a polyethylene that is widely used as a base material for injection-molded products because it becomes an adhesive layer when a decorative multilayer sheet is laminated on various base materials. It is desirable to have good adhesion to polyolefins such as polypropylene. Furthermore, it is desired that the decorative multilayer sheet has excellent vacuum formability. As a result of examination from this viewpoint, the density obtained by copolymerization of ethylene and an α-olefin having 3 or more carbon atoms, preferably an α-olefin having 4 to 10 carbon atoms, using a metallocene catalyst is 880 to 930 kg / m ^3. It is most preferable to use an ethylene copolymer of 890 to 925 kg / m ³ . Specific examples of the α-olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 4-methyl-1 -A pentene etc. can be illustrated. A typical metallocene catalyst is a catalyst composed of a zirconium compound coordinated with a cyclopentadienyl group and an aluminoxane, and may be used by being supported on an inorganic substance. As the ethylene copolymer polymerized by the metallocene catalyst, those having a melt flow rate of 0.1 to 200 g / 10 min, particularly 0.5 to 50 g / 10 min at 190 ° C. and a load of 2160 g are suitable.

  As the adhesive layer, instead of the ethylene copolymer polymerized by the metallocene catalyst, olefin polymer (A) selected from polypropylene, polyethylene and an ethylene copolymer having a polar group, 20 to 85% by weight, amorphous Composition comprising 10 to 50% by weight of a crystalline or low crystalline ethylene / α-olefin copolymer (B), 5 to 30% by weight of a tackifier resin (C) and optionally a hydrogenated diene elastomer (D) Similar effects can also be achieved when a physical layer is used.

  The olefin polymer (A) used for the resin composition layer as the adhesive layer is selected from polypropylene, polyethylene and an ethylene copolymer having a polar group. Here, polyethylene is an ethylene homopolymer or an ethylene / α-olefin copolymer having ethylene as a main component and one or more α-olefins having about 3 to 20 carbon atoms as subcomponents. The ethylene copolymer having a polar group is, for example, an ethylene / polar monomer copolymer containing ethylene as a main component and a polar monomer as a subcomponent, and polypropylene is a propylene homopolymer or propylene mainly containing propylene. And other α-olefin copolymers.

As the polyethylene, those generally referred to as high density polyethylene, medium density polyethylene, high pressure method low density polyethylene, linear low density polyethylene, etc. can be used. Ethylene alone or ethylene and α-olefin can be used as a Ziegler type catalyst. , By using a Kaminsky type catalyst, a radical polymerization catalyst or the like, and polymerizing or copolymerizing by a medium / low pressure method or a high pressure method. Examples of the α-olefin copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, and the like. An α-olefin having about 3 to 20 carbon atoms can be exemplified. For example, the linear low density polyethylene may be produced by any catalyst system, for example, in the presence of a single site catalyst represented by a Kaminsky catalyst or a multisite catalyst represented by a Ziegler catalyst. What copolymerized ethylene and the alpha olefin can be used. As these ethylene homopolymers and ethylene / α-olefin copolymers, those having a density of 900 kg / m ³ or more, preferably 910 to 970 kg / m ³ , more preferably 915 to 960 kg / m ³ are used. desirable.

  The polar monomer in the ethylene-polar monomer copolymer of the ethylene copolymer having the above polar group may be vinyl acetate or methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic An unsaturated carboxylic acid ester such as 2-ethylhexyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, dimethyl maleate and diethyl maleate is preferable, and vinyl acetate is particularly preferable. As these ethylene / polar monomer copolymers, those having a polar monomer content of 45% by weight or less, particularly 0.1 to 30% by weight are suitable.

  Polypropylene is a homopolymer of propylene, a random copolymer of propylene and another α-olefin, a block copolymer of propylene and another α-olefin, or the like. Other α-olefins in the random copolymer and block copolymer of propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, etc. An α-olefin having about 2 to 20 carbon atoms can be exemplified. Such other α-olefins may be copolymerized singly or in combination of two or more.

  Particularly suitable polypropylene is a propylene homopolymer or a random copolymer of propylene and an α-olefin having 2 to 4 carbon atoms, such as propylene and ethylene having an α-olefin content of 20 mol% or less, particularly 10 mol% or less. Or a random copolymer of propylene, ethylene and 1-butene. . Such polypropylene can be obtained by polymerizing propylene or copolymerizing propylene and one or more other α-olefins in the presence of a stereospecific catalyst.

  When the olefin polymer (A) is polyethylene or an ethylene copolymer having a polar group, the melt flow rate at 190 ° C. and 2160 g load is 0.1 to 200 g / 10 minutes, particularly 1 to 150 g / 10 minutes. In the case of polypropylene, the one having a melt flow rate at 230 ° C. and a load of 2160 g of 0.1 to 200 g / 10 min, particularly about 0.5 to 100 g / 10 min is used. Is preferred. These olefin polymers (A) can be used in combination of two or more.

The amorphous or low-crystalline ethylene / α-olefin copolymer (B) in the resin composition that can constitute the adhesive layer of the present invention is an α having 3 or more carbon atoms mainly composed of ethylene. A copolymer with an olefin having a crystallinity based on X-ray diffraction of 40% or less, preferably 1 to 30%. The copolymer (B) preferably has a density of 895 kg / m ³ or less, particularly 860 to 890 kg / m ³ . Examples of the α-olefin having 3 or more carbon atoms in the copolymer (B) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4 An α-olefin having about 3 to 20 carbon atoms such as methyl-1-pentene can be exemplified, and an α-olefin having about 3 to 8 carbon atoms is particularly preferable. In view of processability and adhesiveness, the copolymer (B) has a melt flow rate at 190 ° C. and a load of 2160 g of 0.1 to 200 g / 10 minutes, particularly 1 to 150 g / 10 minutes. It is preferred to use. Such a copolymer uses, for example, a transition metal catalyst component, for example, a catalyst comprising a vanadium compound or a zirconium compound and an organoaluminum compound catalyst component, and the ethylene content in the copolymer is preferably 50 to 95 mol%, preferably Can be obtained by copolymerizing ethylene and an α-olefin so as to be 70 to 94 mol%, more preferably about 82 to 93 mol%. Two or more of these amorphous or low crystalline ethylene / α-olefin copolymers may be used in combination.

The tackifying resin (C) in the resin composition that can constitute the adhesive layer of the present invention is an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, an aromatic hydrocarbon resin, or a polyterpene resin. Rosins, styrene resins, coumarone-indene resins, and the like. Examples of the aliphatic hydrocarbon resin include polymerization of a fraction containing at least one mono- or diolefin having 4 to 5 carbon atoms such as 1-butene, isobutene, butadiene, 1,3-pentadiene, isoprene, and the like. The resulting resin can be mentioned. Examples of alicyclic hydrocarbon resins include resins obtained by polymerizing diene components in spent C _{4 to} C ₅ fractions after cyclization and dimerization, resins obtained by polymerizing cyclic monomers such as cyclopentadiene, aromatics Examples thereof include a resin obtained by hydrogenating a hydrocarbon-based hydrocarbon resin.

Examples of aromatic hydrocarbon resins include resins obtained by polymerizing a fraction containing at least one C _{8 to} C ₁₀ vinyl aromatic hydrocarbon such as vinyl toluene, indene, α-methylstyrene, or the like Examples thereof include a resin obtained by copolymerizing a fraction and the above aliphatic hydrocarbon fraction. Examples of polyterpene resins include α-pinene polymers, β-pinene polymers, dipentene polymers, terpene / phenol copolymers, α-pinene / phenol copolymers, and hydrogenated products thereof. it can.

Examples of rosins include rosins such as gum rosin, wood rosin and tall oil, and modified products thereof. Examples of modified products include those subjected to modification such as hydrogenation, disproportionation, dimerization, and esterification. it can. As the styrenic hydrocarbon resin, a low molecular weight resinous polymer obtained by polymerizing one or more of styrene monomers such as high-purity styrene, vinyltoluene, α-methylstyrene, and isopropyltoluene. Can be mentioned.
Among these, in consideration of odorlessness, miscibility with other components, adhesion, and the like, it is preferable to use a resin obtained by hydrogenating an aromatic hydrocarbon resin or a polyterpene resin.

  The resin composition that can constitute the adhesive layer is composed of an olefin polymer (A), an amorphous or low crystalline ethylene / α-olefin copolymer (B), and a tackifying resin (C). However, a hydrogenated diene elastomer (D) can be optionally blended.

The hydrogenated diene elastomer (D) is obtained by hydrogenating at least a part of conjugated diene polymer units such as a conjugated diene homopolymer, a copolymer of conjugated dienes, and a copolymer of conjugated diene and other monomers. Specific examples of the elastomeric polymer include a hydrogenated product of a diene block polymer or a hydrogenated product of a block copolymer of a styrene monomer and a diene monomer. As an example of the former, for example, a block copolymer obtained by hydrogenating a butadiene polymer unit of a block copolymer comprising a polybutadiene segment having a small 1,2-vinyl structure and a polybutadiene segment having a large 1,2-vinyl bond is used. can do. Such a block copolymer has, for example, a polybutadiene segment (X) having a 1,2-vinyl bond content of 20% or less, preferably 15% or less, and a 1,2-vinyl bond content of 25 to 95%, preferably The polybutadiene segment (Y) is 25 to 75%, more preferably 25 to 55%, and the block structure is X— (Y—X) _n or (X—Y) _m (where n is 1 or more, m is 2) Examples thereof include those obtained by hydrogenating 90% or more, preferably 95 to 100%, of a butadiene polymer unit of a linear or branched block copolymer represented by the above integer). As such a hydrogenated butadiene block copolymer, one having a melt flow rate at 230 ° C. and a load of 2160 g of 0.1 to 100 g / 10 min, particularly about 0.5 to 50 g / 10 min is desirable.

  Further, as the latter example, a hydrogenated conjugated diene polymer unit of a block copolymer of a polymer block (S) mainly composed of a styrene monomer and a block (T) mainly composed of a conjugated diene compound is exemplified. be able to. Examples of the styrene monomer include styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, chloroprene, and 2,3-dimethylbutadiene, but butadiene or isoprene is particularly preferable.

As a block copolymer of a polymer block (S) mainly composed of a styrene-based monomer and a polymer block (T) mainly composed of a conjugated diene compound, for example, (ST) _n or (ST) _n Examples thereof include linear, branched, and radial block copolymers represented by -S (wherein n is an integer of 1 or more). The hydrogenated product is preferably a product obtained by hydrogenating 70% or more, preferably 90% or more, of the conjugated diene polymer unit of the block copolymer. More specifically, the vinyl block such as 1,2- or 3,4-in the polymer block mainly composed of a conjugated diene compound is 10% or more, preferably 20 to 80%, more preferably 30 to 60%. A hydrogenated block copolymer having a styrenic compound content of hydrogenated block copolymer of 8 to 50% by weight, preferably 10 to 40% by weight, for example, a ST′-S type block copolymer Is the best. Here, S is a styrene polymer block, and T ′ is a hydrogenated conjugated diene polymer block, that is, an alkylene copolymer block, specifically an ethylene / butene copolymer block or an ethylene / propylene copolymer block. is there. Such a block copolymer hydrogenated product is referred to as SEBS obtained by hydrogenating a butadiene polymer block of a styrene-butadiene-styrene block copolymer generally referred to as SBS, or SIS. And a so-called SEPS obtained by hydrogenating an isoprene polymer block of a styrene-isoprene-styrene block copolymer. Those having a melt flow rate at 230 ° C. and a load of 2160 g of 0.1 to 100 g / 10 min, particularly about 0.5 to 50 g / 10 min are preferred.

  In the above resin composition usable as the adhesive layer, the olefin polymer (A) is 20 to 85% by weight, preferably 30 to 70% by weight, amorphous or low crystalline ethylene / α-olefin copolymer. (B) is 10 to 50% by weight, preferably 20 to 40% by weight, tackifying resin (C) is 5 to 30% by weight, preferably 10 to 25% by weight, and hydrogenated diene elastomer (D) is 0. Those blended in a proportion of ˜30% by weight, preferably 0 to 25% by weight are preferred. When such a resin composition layer is used as an adhesive layer, good adhesiveness can be obtained even when using not only polyolefin but also a styrene polymer as a backing layer or a backing layer described later. There are advantages.

  In the decorative multilayer sheet of the present invention, a backing layer can be optionally provided adjacent to the adhesive layer in order to improve the strength of the decorative sheet. In this case, since it is laminated on various base materials via a backing layer, it is necessary to use the same type as polyolefins such as polyethylene and polypropylene or styrene polymers which are frequently used as base materials for injection molded products. preferable. This makes it possible to obtain a sufficient interlayer adhesive force with the adhesive layer, and excellent adhesion when laminated on the substrate. Examples of polyolefins useful as a backing layer material include polyethylenes of various densities obtained by various production methods, propylene homopolymers, propylene and other α-olefins, preferably ethylene or random copolymers of ethylene and 1-butene, propylene and In addition, what is generally referred to as polypropylene, such as a block copolymer with an α-olefin, preferably ethylene, can be exemplified as a suitable example.

  When the backing layer material is polyethylene, specifically, high-pressure polyethylene, linear low-density polyethylene, medium / high-density polyethylene, etc., and the melt flow rate at 190 ° C. under a load of 2160 g is 0.1 to 200 g. / 10 minutes, particularly 0.2 to 100 g / 10 minutes can be preferably used. When the backing material is polypropylene, a material having a melt flow rate at 230 ° C. and a load of 2160 g of 0.1 to 200 g / 10 minutes, particularly 0.2 to 100 g / 10 minutes can be preferably used.

  Examples of the styrenic polymer that can be used as the backing layer material include polystyrene, AS resin, rubber-reinforced polystyrene, such as impact-resistant polystyrene obtained by graft-polymerizing styrene to a rubber component such as polybutadiene, styrene-butadiene rubber, EPR, EPDM, Examples of the rubber component include ABS type resins obtained by grafting styrene and other monomers such as acrylonitrile, methyl methacrylate, α-methylstyrene, ethylene bismaleimide, and maleimide.

  In the decorative layer, the adhesive layer, or the backing layer, additives such as those exemplified above as those that can be arbitrarily mixed in the surface layer can be arbitrarily mixed.

  The thickness of each layer in the decorative multilayer sheet of the present invention is 30 to 1000 μm, preferably 50 to 500 μm, and the surface layer is 30 to 1000 μm, considering gloss, appearance, design, scratch resistance, vacuum formability, interlayer adhesion, and the like. The decoration layer is 30 to 1000 μm, preferably 50 to 500 μm, the adhesive layer is 30 to 500 μm, preferably 40 to 400 μm, and the backing layer is 0 to 1000 μm, preferably 0 to 500 μm. When providing both the layer which mix | blended the aluminum powder and the layer which mix | blended the coloring agent as a decoration layer, both layers are 10-500 micrometers, Preferably it is set to 30-300 micrometers, and 30-1000 micrometers is the layer thickness of the whole decoration layer The thickness is preferably in the range of 50 to 500 μm.

  Since the decorative multilayer sheet of the present invention can be produced by a multilayer casting method, a multilayer inflation method, an extrusion lamination method, or the like, it does not require the use of an organic solvent. In the multilayer casting method or the multilayer inflation method, a decorative multilayer sheet can be obtained by combining and molding the layer components extruded from a plurality of extruders in a flat die or a cylindrical die. Further, in the extrusion lamination method, a single layer or a multilayer sheet constituting the decorative multilayer sheet is prepared in advance, and a method of extruding and laminating one layer or a multilayer of other constituent layers is performed a plurality of times. The intended decorative multilayer sheet can be obtained by the method.

  The decorated multilayer sheet of the present invention can be used as a surface layer of various molded articles (base materials). In particular, since it is excellent in secondary workability such as vacuum forming and pressure forming, a good surface layer can be formed even in a molded product having a complicated shape. In particular, it is suitable as a surface layer of a molded article (base material) made of polyolefin such as polyethylene and polypropylene. In order to form the decorative multilayer sheet layer of the present invention on the surface of the molded article (base material), various methods can be employed. For example, a molded product that matches part or all of the external shape of the target injection-molded product is produced from the decorative multilayer sheet by vacuum molding, and this is placed in an injection mold to add part or all of the molded product. A method (such as a film insert molding method) for producing a decorated decorative molded product can be employed. In this case, if it is an injection molding method (thermoject molding method) that uses both a vacuum mold and an injection mold, it is easier to remove from the vacuum mold and insert into the injection mold. A decorative molded product can be obtained. In any case, by using a molding method known as vacuum molding, pressure molding, film insert molding, in-mold molding, thermoject molding, etc., the decorative multilayer sheet as a surface layer and the molded body body A decorative molded product excellent in adhesiveness can be obtained. Such molded products are excellent in surface gloss, scratch resistance, design, etc., such as vehicle parts such as automobiles, motorcycles, trucks, home appliances, building supplies, office supplies, sporting goods, decorative goods, miscellaneous goods, etc. It can be suitably used in the field.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the raw material used by the Example and the comparative example and the evaluation method of a decorating multilayer sheet are as follows.

(1) Raw material (1-1) Ionomer (IO)
Ionomer of ethylene / methacrylic acid copolymer with a methacrylic acid content of 15% by weight (ionic species: zinc, neutralization degree 59%, melt flow rate (190 ° C., 2160 g load) 0.9 g / 10 min)

(1-2) Ethylene copolymer polymerized by metallocene catalyst (linear low density polyethylene) (m-PE)
Product name: Evolue SP0540 (Mitsui Sumitomo Polyolefin Co., Ltd., density 903 kg / m ³ , melt flow rate (190 ° C., 2160 g load) 3.8 g / 10 min)
Product name: Evolue SP1520 (Mitsui Sumitomo Polyolefin Co., Ltd., density 913 kg / m ³ , melt flow rate (190 ° C., 2160 g load) 2.0 g / 10 min)
Product Name: Evolue SP2510 (Mitsui Sumitomo Polyolefin Co., Ltd., density 923 kg / m ³ , melt flow rate (190 ° C., 2160 g load) 1.5 g / 10 min)

(1-3) Linear low density polyethylene (LLDPE)
Product name: UZ4020L (Mitsui Sumitomo Polyolefin Co., Ltd., density 937 kg / m ³ , melt flow rate (190 ° C., 2160 g load) 2.3 g / 10 min)

(1-4) Resin composition (AD)
40 parts by weight of ethylene / vinyl acetate copolymer (vinyl acetate content 6.0% by weight, melt flow rate (190 ° C., 2160 g load) 7.5 g / 10 min), low crystalline ethylene / 1-butene copolymer ( Ethylene content 89.1 mol%, crystallinity 10%, density 886 kg / m ³ , melt flow rate (190 ° C, 2160 g load) 4.0 g / 10 min) 30 parts by weight, hydrogenated aromatic hydrocarbon resin (product) Name: Archon AM1, Arakawa Chemical Co., Ltd.) 20 parts by weight and SEBS (trade name: Clayton G1657, Shell Japan Co., Ltd.) 10 parts by weight Density 923 kg / m ³ , melt flow rate (190 ° C., 2160 g Load) 10.5 g / 10 min composition

(1-5) Polypropylene (PP)
Product name: Sumitomo Mitsui Polypro J626 (Mitsui Sumitomo Polyolefin Co., Ltd., density 910 kg / m ³ , melt flow rate (230 ° C., 2160 g load) 18 g / 10 min)
(1-6) Acrylonitrile-butadiene-styrene copolymer (ABS)
Product name: Techno ABS520, manufactured by Technopolymer Co., Ltd., density 1050 kg / m ³ , melt flow rate (220 ° C., 2160 g load) 9.0 g / 10 min

(1-7) Aluminum powder (Al powder)
Aluminum MB-1: Average particle size of 5 μm (master batch based on LLDPE)
Aluminum MB-2: average particle size 20 μm (master batch based on LLDPE)
Aluminum MB-3: Average particle size of 40 μm (master batch based on LLDPE)
Aluminum MB-4: average particle size 60 μm (master batch based on LLDPE)
(1-8) Green pigment Tokyo Ink Co., Ltd. Green pigment MB (LDPE base masterbatch)

(2) Evaluation method (2-1) Appearance The appearance of the decorated multilayer sheet was visually determined.
(I) Gloss (feeling of brightness)
○: glossy ×: no gloss (b) metallic tone, color tone ◎: good metallic tone ○: moderate metallic tone △: slightly dull ×: no metallic tone expression (c) shielding property ○: the opposite side is not visible ×: I can see the other side

(2-2) Vacuum Formability Using a multilayer cast molding machine, a decorated multilayer sheet having a thickness of each layer as shown in Table 1 was prepared. This was cut into 50 cm × 50 cm, and this multilayer sheet was heated to 90 to 130 ° C., and then subjected to vacuum forming on a polypropylene molded product having a deep concavo-convex shape on the upper surface for evaluation.
○: Deep-drawn part stretches uniformly and does not affect the appearance (Keeps glossy and does not cause whitening of the stretched part such as edges)
×: The deeply drawn part becomes thinner, affecting the appearance

(2-3) Surface scratch resistance Using a West German Erichsen model 318 scratch hardness tester, the tip of the marking bar adjusted to a constant spring pressure is used to scratch the surface of the circular molded product of the decorative multilayer sheet. Evaluation was based on the force expressed in maximum grams that did not remain.
○: 250 g or more ×: less than 250 g

(2-4) Adhesiveness The adhesive strength between the aluminum powder-containing layer (metallic layer) and the adhesive layer or the colorant-containing layer (colored layer) and the adhesive layer of the decorative multilayer sheet was measured. Further, the adhesive strength between the adhesive layer and the backing layer of the decorative multilayer sheet was measured.
○: 2N / 15mm or more ×: Less than 2N / 15mm

[Examples 1 to 3]
Using a multi-layer cast sheet molding machine, the above-mentioned ionomer (IO) as the surface layer, and the master batch (as described above) of aluminum powder having the particle size shown in Table 1 as the metallic layer as the ionomer (IO) are listed as aluminum powder. Are blended so as to have the blending ratio shown in the following, using an ethylene copolymer (m-PE) evolved SP-0540 polymerized with a metallocene catalyst as an adhesive layer, and the above-mentioned polypropylene (PP) as a backing layer. A decorative four-layer sheet having a surface layer of 250 μm, a metallic layer of 100 μm, an adhesive layer of 50 μm, and a backing layer of 50 μm was prepared. The appearance, scratch resistance, vacuum formability and adhesiveness of the obtained decorative four-layer sheet were evaluated. The results are shown in Table 1.

[Example 4]
Example 1 except that a colored layer having a thickness of 50 μm was further provided between the metallic layer and the adhesive layer, in which the above-mentioned ionomer was blended in a proportion of 5% by weight as a green pigment. In the same manner as above, a decorative sheet having a five-layer structure was obtained. The evaluation results are shown in Table 1.

[Comparative Example 1]
A 4-layer decorative sheet was obtained in the same manner as in Example 1 except that a master batch with an average particle size of 60 μm was used instead of the aluminum powder master batch with an average particle size of 5 μm as the metallic layer. The evaluation results are shown in Table 1.

[Comparative Example 2]
In Example 1, it carried out like Example 1 except having changed the resin used for the surface layer and the contact bonding layer into the above-mentioned polypropylene (PP). The evaluation results are also shown in Table 1.

＊：着色層／接着層

*: Colored layer / adhesive layer

[Example 5]
The same procedure as in Example 1 was performed except that Evolu SP1520 was used instead of Evolu SP0540 as the adhesive layer. The evaluation results of the obtained decorative four-layer sheet are shown in Table 2 together with the evaluation results of Example 1.

[Example 6]
The same procedure as in Example 1 was performed except that the resin composition (AD) described above was used instead of Evolu SP0540 as the adhesive layer, and ABS was used instead of PP as the backing layer. Table 2 shows the evaluation results of the obtained decorative four-layer sheet.

[Comparative Example 3]
In Example 4, it carried out like Example 2 except having used Evolve SP2540 instead of Evolve SP1520 as an adhesive layer. Table 2 shows the evaluation results of the obtained decorative four-layer sheet.

[Comparative Example 4]
In Example 4, it carried out like Example 4 except having used linear low density polyethylene UZ4020L instead of Evolve SP1520 as an adhesion layer. Table 2 shows the evaluation results of the obtained decorative four-layer sheet.

Claims (8)

A decorative multilayer sheet having a layer structure of at least three layers comprising a surface layer / decorative layer / adhesive layer, wherein the surface layer is a clear layer composed of an ionomer of an ethylene / unsaturated carboxylic acid copolymer, An ionomer layer of an ethylene / unsaturated carboxylic acid copolymer in which the decorative layer contains 0.3 to 5% by weight of aluminum powder having an average particle size of 0.1 to 50 μm or 0.1 to 20% by weight of a colorant. And an adhesive layer is polymerized by a metallocene catalyst, and an ethylene copolymer layer having a density of 880 to 920 kg / m ³ or an olefin polymer (A) selected from polypropylene, polyethylene and an ethylene copolymer having a polar group ) 20 to 85% by weight, amorphous or low crystalline ethylene / α-olefin copolymer (B) 10 to 50% by weight, tackifying resin (C) 5 to 30% by weight and hydrogenation Decorative multilayer sheet which is a diene-based elastomer (D) a resin composition layer consisting of 0-30 wt%. Decorative layer, the decorative multi-layer sheet according to claim 1, characterized in that a multilayer structure of layers containing a combination of layers and a coloring agent comprising the aluminum powder. The decorative multilayer sheet according to claim 1 or 2, wherein the aluminum powder in the aluminum powder blending layer is blended using a master batch using a linear low density polyethylene or an ionomer as a carrier resin. The decorative multilayer sheet according to any one of claims 1 to 3, wherein a backing layer made of a polyolefin or a styrene polymer is further provided adjacent to the adhesive layer. The decorated multilayer sheet according to any one of claims 1 to 4, which is produced by a multilayer casting method, a multilayer inflation method or an extrusion lamination method. A decorative molded product obtained by laminating the decorative multilayer sheet according to any one of claims 1 to 5 on a substrate surface. The decorative molded product according to claim 6 , wherein a decorative multilayer sheet is laminated on the surface of the base material by vacuum forming, pressure forming, film insert forming, in-mold forming or thermoject forming. The decorative molded article according to claim 6 or 7, wherein the decorative molded article is a vehicle part, a household appliance, an office article, a building article, a sports article, a decorative article, or a sundries.