JP2014181414A - Grained artificial leather, decorative molded body and method for manufacturing grained artificial leather - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a grained artificial leather comprising a surface protective membrane for imparting stain resistance property which is superior in delustering feeling and optical transparency and which can maintain a high adhesive strength.SOLUTION: A grained artificial leather comprises a nonwoven substrate containing an ultrafine fiber interlaced body, a grained layer laminated on the nonwoven substrate, and a surface protective membrane laminated on the grained layer. The surface protective membrane is a membrane having 5 to 20 μm thickness containing saponified material of ethylene-acetate vinyl copolymer (EVOH copolymer) as a main composition. The surface of the grained layer has a matt surface having 5 to 60% in glossiness according to JIS Z 8741.

Description

  The present invention relates to a matte-tone artificial leather with matte tone (matte tone) provided with an antifouling film excellent in design and adhesion. More specifically, the present invention relates to a matte-tone artificial leather with matte tone having an antifouling film, which exhibits high adhesive strength even when formed on the surface of a silver surface layer having an embossed texture.

  2. Description of the Related Art Conventionally, there is known a silver-tone artificial leather formed by laminating a silver surface layer made of a resin such as polyurethane, acrylic resin, vinyl chloride or the like resembling the appearance of natural leather on the surface of a nonwoven fabric substrate. Such artificial leather with a silver tone is widely used as a skin material for daily necessities such as shoes, bags, case covers, clothing, furniture, and automobile interior materials. In recent years, a decorative molded body in which a decorative sheet is integrated on the surface of the molded body is known as a molded body having excellent design properties used for a casing of a mobile phone, a mobile device, and a home appliance. Yes. Silver-coated artificial leather is also used as a decorative sheet used for manufacturing such a decorative molded body.

  The silver surface layer of silver-tone artificial leather is usually colored. If colored components contained in food, cosmetics, writing supplies, machine oil, grease, etc., adhere to the surface of the artificial leather with silver, the attached colored components are difficult to remove with a detergent, and also wipe off with a solvent. In this case, there is a problem that the colorant of the silver surface layer may be discolored, or the surface of the silver surface layer may be dissolved to leave a wiping trace. In addition, an elastic body such as polyurethane having flexibility and tackiness is used for the silver surface layer in order to express flexibility. When a tactile sensation is expressed in the silver surface layer, there is also a problem that dust and coloring components are attached to the surface of the silver-finished artificial leather to make it easily contaminated.

  Several techniques for solving such a problem have been proposed. For example, in Patent Document 1 below, a specific silicon-modified polyurethane is applied to the surface of a silver surface layer in a dot shape so that the average shortest distance is 10 to 100 μm, so that it does not easily fade even when it comes into contact with alcohol, and is flexible. It is disclosed that a silver-tone artificial leather that can maintain a good quality can be obtained. Further, Patent Document 2 below discloses a water- and oil-repellent artificial leather with silver repellency in which an outermost surface layer containing a fluorine-containing polymer is formed on the surface of a base layer.

  When an antifouling layer containing silicon-modified polyurethane or fluorine-containing polymer as described above is formed on the surface of the silver surface layer, the antifouling performance is imparted to some extent, but it is prevented by external forces such as bending and friction. There was a problem that the dirty layer was easily peeled off. Specifically, for example, as disclosed in Patent Document 1, in the case of forming an antifouling layer containing silicon-modified polyurethane on the surface of the silver surface layer, in order to give sufficient antifouling property, silicon Although it is necessary to increase the content ratio of the modified polyurethane, in this case, there is a problem that the adhesive force of the antifouling layer is lowered and the peeling becomes easy. Further, as disclosed in Patent Document 2, when the antifouling layer containing the fluorine-containing polymer is formed on the surface of the base layer, the fluorine molecules of the fluorine-containing polymer appearing on the surface gradually enter the resin inside over time. There was a problem that the antifouling property deteriorated over time by being buried.

  Moreover, the following patent document 3 is 40 to 90 weight% of saponified ethylene-vinyl ester copolymer as a matted film used as an antifouling layer for polyvinyl chloride (PVC) wallpaper or the like, carboxylic acid-modified polyethylene resin 5 A matted film comprising a composition comprising 30% by weight and 5 to 30% by weight of an inorganic filler and having a glossiness of at least 50% on one side is disclosed.

JP 2011-52336 A JP 2000-336348 A Japanese Patent Laid-Open No. 7-258889

  As methods for imparting antifouling properties to the surface of silver-finished artificial leather, methods such as those disclosed in Patent Document 1 and Patent Document 2 have been proposed. A suppressed matte appearance was sought. However, it has been difficult to achieve both antifouling properties and a matte appearance. In addition, for example, a matted film formed on the surface of a wallpaper as disclosed in Patent Document 3 has a problem of low adhesive strength. In addition, when such a matte film is formed on the surface of a silver-finished artificial leather, although gloss is suppressed, it is difficult to obtain a highly light-transmitting film, and the color of the silver surface layer seems to fade. Further, there is a problem that a problem of deteriorating the design property such that the printed pattern applied to the silver surface layer appears to be blurred. Further, such a matted film is not sufficient in antifouling performance.

  The present invention provides a silver-coated artificial leather comprising a surface protective film for imparting antifouling properties, having a matte feeling and light transmittance, and having a surface protective film capable of maintaining high adhesive strength. The purpose is to do.

  A silver-tone artificial leather according to the present invention includes a nonwoven fabric base material including an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less, a silver surface layer laminated on the nonwoven fabric base material, and a surface protective film laminated on the silver surface layer. The surface protective film is a film having a thickness of 5 to 20 μm mainly composed of a saponified ethylene-vinyl acetate copolymer (EVOH copolymer), and the surface on the silver surface layer side is JIS Z It has a matte surface exhibiting a glossiness of 5 to 60% specified in 8741. A surface protective film containing an EVOH copolymer as a main component is an antifouling film, but is a relatively hard film. In addition, the artificial leather base material with a silver finish that includes a nonwoven fabric base material including an ultrafine fiber entangled body and a silver surface layer laminated on the nonwoven fabric base material has a dense fiber density, so the density unevenness of the fiber is low and a sense of fulfillment. It is a highly homogenous substrate excellent in. A silver surface layer laminated on such a nonwoven fabric substrate has high resilience. By forming a film having a thickness of 5 to 20 μm containing the EVOH copolymer as a main component with such a highly solid silver surface layer as a base, a surface protective film maintaining high adhesive strength is formed. Further, the surface protective film has a thickness of 5 to 20 μm and a matte surface exhibiting a glossiness of 5 to 60%, so that the coloring of the silver surface layer seems to fade or is applied to the silver surface layer. An excellent matte appearance can be obtained while suppressing the printed pattern from appearing blurred.

  Further, the total light transmittance of the surface protective film is preferably 80% or more from the viewpoint of excellent design properties because of excellent light transmittance. By maintaining the total light transmittance at 80% or more, the color of the silver surface layer looks faded, or the printed pattern applied to the silver surface layer looks blurred. It becomes difficult to cause.

  Moreover, when a surface protective film is a film | membrane of thickness 5-10 micrometers, higher adhesive strength and design property are obtained.

  Moreover, it is preferable that a silver surface layer is a 10-200-micrometer-thick layer which has an embossed pattern with an average depth of 10-100 micrometers on the outer surface side, and contains a non-porous polyurethane elastic body. In the case of such a highly solid silver surface layer, the surface protective film can be adhered while maintaining high adhesion without entraining air on the surface of the textured pattern or losing the three-dimensional effect. it can.

  Moreover, it is preferable that the silver surface layer and the surface protective film are bonded by an adhesive layer having a thickness of 0.1 to 20 μm. By bonding with such a thin adhesive layer, a high total light transmittance can be maintained, and the surface protective film can be bonded with a high adhesive force so as to follow the surface shape of the silver surface layer. Further, even when a grain pattern is formed on the silver layer, an adhesive layer having a thickness that does not fill the grain can be formed, which is preferable from the viewpoint of design.

  As such a surface protective film, when the polyolefin resin is contained in an amount of 5 to 40% by mass, an EVOH copolymer and a polyolefin resin that is incompatible with the EVOH copolymer are appropriately roughened during film formation. It is preferable because the mat surface can be easily formed. Specifically, fine unevenness with a matte tone can be formed on the surface of the surface protective film due to the difference in the solidification temperature between the EVOH copolymer and the polyolefin resin during film formation.

  The mat surface of the surface protective film may be formed by transferring the mat surface formed on the release sheet having the mat surface.

  Further, the peel strength when peeled between the surface protective film and the silver surface layer is preferably 2 kgf / 2.5 cm or more.

The nonwoven fabric base material includes an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less and a polymer elastic body impregnated in the ultrafine fiber entangled body, and has an apparent density of 0.45 g / cm ³ or more. It is preferable from the viewpoint that the adhesion of the surface protective film is sufficiently high.

  Moreover, the decorative molded body of the present invention is a decorative molded body including a resin molded body and a decorative sheet integrated on the surface of the resin molded body, and the decorative sheet has any of the above-described silver-attached bodies. It is an artificial leather.

  In addition, the method for producing a silver-tone artificial leather according to the present invention includes a non-woven base material including an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less and a silver surface layer artificially laminated with a non-woven base material. A step of preparing a leather substrate, a step of preparing a surface protective film having a thickness of 5 to 20 μm having a gloss level of 5 to 60% as defined in JIS Z 8741, and a mat surface of the surface protective film Forming an adhesive layer on at least one of the opposite surface to the surface of the silver surface layer and the surface of the silver surface layer so as to have a total thickness of 0.1 to 20 μm; And a step of integrating them by hot pressing. According to such a manufacturing method, the above-described artificial leather with a silver finish can be manufactured without mixing air or the like into the interface between the surface protective film having a thickness of 5 to 20 μm and the silver surface layer.

  ADVANTAGE OF THE INVENTION According to this invention, the matte tone artificial leather with a matte tone provided with the antifouling film | membrane which has high adhesive strength is obtained.

FIG. 1 is a schematic cross-sectional view of a silver-tone artificial leather 10 according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional process diagram illustrating a manufacturing process of the silver-tone artificial leather 10. FIG. 3 is an explanatory view for explaining a manufacturing process of a decorative molded body using the artificial leather 10 with a silver tone.

  FIG. 1 is a schematic cross-sectional view of a silver-tone artificial leather 10 according to an embodiment of the present invention. As shown in FIG. 1, the silver-finished artificial leather 10 has a silver surface layer 2 formed of a polyurethane elastic body or the like colored on the surface of a nonwoven fabric substrate 1 including an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less. And a surface protective film having a thickness of 5 to 20 μm mainly composed of a saponified ethylene-vinyl acetate copolymer (EVOH copolymer) via an adhesive layer 3 on the surface of the silver layer 2 4 is provided. The embossed shape 2 a is exposed on the surface of the laminate composed of the silver surface layer 2, the adhesive layer 3 and the surface protective film 4. As shown in an enlarged view in FIG. 1, the surface protective film 4 on the outermost layer on the silver layer side has a matte surface 4a having a surface glossiness of 5 to 60%.

  Since the nonwoven fabric base material 1 containing an ultrafine fiber entangled body has a dense fiber density, it is a highly uniform base material with low unevenness in fiber density and excellent sense of fulfillment. Therefore, the silver surface layer 2 laminated on the nonwoven fabric substrate 1 becomes a layer with a high sense of fulfillment. Then, the surface protective film 4 formed with the silver surface layer 2 having a high sense of solidity as a base is firmly adhered to the silver surface layer 2.

  The surface protective film contains an EVOH copolymer as a main component. The content ratio of the EVOH copolymer in the surface protective film is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. When the content of the EVOH copolymer is less than 60%, the antifouling property tends to decrease.

  Moreover, the thickness of a surface protective film is 5-20 micrometers, Preferably it is 5-15 micrometers, More preferably, it is 5-10 micrometers. When the thickness of the surface protective film is less than 5 μm, the durability is insufficient, and the effect of suppressing permeation of oily substances and the like is lowered, so that the antifouling property becomes insufficient. In addition, when the thickness of the surface protective film exceeds 20 μm, the film becomes hard and the adhesion with the silver surface layer is reduced, or the three-dimensional effect of the wrinkle pattern is lost, and the light transmittance is reduced. Thus, the coloring of the silver layer tends to fade, or the printed pattern applied to the silver layer tends to appear blurred. The thickness of the surface protective film is defined as an average value obtained by measuring the thickness of the five surface protective films uniformly selected from a scanning electron micrograph of the cross section of the formed silver-tone artificial leather. .

  The total light transmittance of the surface protective film is preferably 80% or more, and more preferably 85% or more. When the total light transmittance is too low, the coloring of the silver surface layer tends to fade, or the printed pattern applied to the silver surface layer tends to appear blurred. The total light transmittance means the total light transmittance measured using a haze meter by a method according to ASTM D1003 using only the surface protective film.

  The surface of the silver-finished artificial leather has a matte surface whose glossiness is suppressed by the mat surface of the surface protective film. The glossiness of the matte surface of the surface protective film which is the surface of the silver-tone artificial leather is 5 to 60%, preferably 5 to 40%. By adjusting the glossiness within such a range, a matte appearance can be imparted to the surface. When the surface glossiness exceeds 60%, the matte appearance is lost, and when the surface glossiness is less than 5%, the total light transmittance decreases.

  Hereinafter, the silver-tone artificial leather according to the present invention will be described in detail along with an example of the production method thereof.

  In this production method, first, as shown in FIG. 2A, a surface protective film 4 having a thickness of 5 to 20 μm mainly composed of an EVOH copolymer was formed on a release sheet 5 as a supporting substrate. A surface protective film 6 with a release sheet is prepared.

  In addition, in the manufacturing method of this embodiment, the case where the surface protection film with a peeling sheet which formed the surface protection film of thickness 5-20 micrometers on the peeling sheet using the extrusion T die is used is demonstrated in detail. In addition, when the surface protective film can be formed alone without being supported by the release sheet, instead of using the surface protective film with the release sheet, only the surface protective film is formed as a single layer using an extrusion T die or the like. Also good. From the viewpoint of film formation stability, it is preferable to use a surface protective film with a release sheet, particularly when a surface protective film having a thin thickness of 5 to 10 μm is formed.

  The surface protective film with a release sheet is formed by, for example, extruding a resin composition containing, as a main component, an EVOH copolymer kneaded by a melt extruder onto the release sheet in a molten state using an extrusion T-die, and cooling with the release sheet. A surface protective film with a release sheet in which a surface protective film is laminated on a release sheet is formed by niping with a roll and cooling and solidifying simultaneously with lamination.

  Saponified ethylene-vinyl acetate copolymer (EVOH copolymer), the main component of the surface protective film, saponifies ethylene-vinyl acetate copolymer produced by solution polymerization, suspension polymerization, emulsion polymerization, etc. And is also referred to as an ethylene-vinyl alcohol copolymer.

  As a content rate (ethylene content rate) of the ethylene unit in EVOH copolymer, it is preferable that it is 20-65 mol%, Furthermore, it is preferable that it is 25-60 mol%. When the ethylene content is too low, the water resistance tends to decrease. Further, when the ethylene content is too high, the oil resistance is lowered, so that the oily substance is likely to permeate, and the contamination resistance tends to be lowered.

  The saponification degree of the vinyl acetate unit of the saponified product of ethylene-vinyl acetate copolymer is preferably 90 mol% or more, and more preferably 95 mol% or more. When the degree of saponification is too low, the oil resistance is lowered and the oily substance is likely to permeate, whereby the stain resistance tends to be lowered.

  The saponified ethylene-vinyl acetate copolymer is a unit that can be copolymerized with the ethylene-vinyl acetate copolymer within a range not impairing the effects of the present invention, for example, α-olefin, unsaturated carboxylic acid compound, A copolymer unit derived from a monomer such as an unsaturated sulfonic acid compound, (meth) acrylonitrile, (meth) acrylamide, vinyl ether, a vinyl silane compound, vinyl chloride, or styrene may be contained as necessary. Furthermore, the ethylene-vinyl acetate copolymer may be post-modified, such as urethanization, acetalization, cyanoethylation, and the like, as long as the effects of the present invention are not impaired.

  The resin composition containing the EVOH copolymer as a main component preferably contains a polyolefin resin in order to suppress surface gloss while maintaining light transmittance. A polyolefin-based resin that is incompatible with the EVOH copolymer is preferable because a mat surface that is moderately roughened by film formation can be easily formed. The matte surface is formed on the surface of the surface protective film due to the difference in solidification temperature between the EVOH copolymer and the polyolefin resin during film formation.

  Examples of polyolefin resin include polyethylene such as high-density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, copolymer of ethylene and α-olefin having 4 or more carbon atoms. , Polyolefins such as copolymers of polyolefin and maleic anhydride, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, or modified polyolefins obtained by graft-modifying these with unsaturated carboxylic acids or derivatives thereof, Graft-modifying α, β-unsaturated carboxylic acid compounds having 3 to 10 carbon atoms such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, or anhydrides of the carboxylic acid compounds onto various polyolefins Examples include acid-modified polyolefins that can be obtained. Among these, a carboxylic acid-modified polyethylene obtained by graft-modifying a carboxylic acid compound on high-density polyethylene is particularly preferable because it can appropriately impart a matte tone.

  The content ratio of the polyolefin resin contained in the resin composition containing the EVOH copolymer as a main component is preferably 3 to 40% by mass, and more preferably 5 to 30% by mass. When the content ratio of the polyolefin resin is too low, the gloss suppressing effect is not sufficiently exhibited, and when it is too high, the total light transmittance tends to be lowered and the design property tends to be lowered.

  In addition, the resin composition containing the EVOH copolymer as a main component has a small amount of fine particles for roughening the surface and adjusting gloss within a range not impairing the effects of the present invention, specifically, for example, a surface protective film It may be contained within a range of 5% by mass or less, further 3% by mass or less, particularly 1% by mass or less. Specific examples of the fine particles include aluminum, titanium, iron, cerium, yttrium, manganese, silicon, tin, zinc, copper, bismuth, cobalt, and metal oxides and talc containing these elements. The average particle diameter of the fine particles is preferably 0.05 to 2 μm, more preferably 0.1 to 1 μm.

  In addition, the resin composition containing the EVOH copolymer as a main component is a resin component other than the polyolefin resin, an antioxidant, a flame retardant, a slip agent, a photodegradation inhibitor, an ultraviolet ray, and the like within a range not impairing the effects of the present invention. You may contain an absorber, an antistatic agent, a coloring agent, etc.

  In the melt extrusion laminating method, a resin film is preferably used as the release sheet for supporting the formation of the surface protective film. Specific examples of the resin film include polyester films such as polyethylene terephthalate (PET). The thickness of the release sheet is not particularly limited, but it is 12 to 200 μm, more preferably 20 to 150 μm. This is preferable because a protective film is easily formed.

  In addition, the surface which forms a surface protective film may be roughened in order for the release sheet to adjust the surface gloss of the silver-tone artificial leather obtained. When a surface protective film containing an EVOH copolymer as a main component is formed on the surface of such a roughened release sheet, the surface of the resulting film has a fine uneven shape on the roughened surface of the release sheet. Transcribed. Even when such a film is used as a surface protective film, light is irregularly reflected by the fine uneven shape, and the gloss of the silver-tone artificial leather is suppressed.

  A surface protective film 6 with a release sheet in which the surface protective film 4 having a thickness of 5 to 20 μm mainly composed of an EVOH copolymer is formed on the release sheet 5 as shown in FIG. can get.

  Next, as shown in FIG. 2B, an adhesive layer 3 is formed on the surface of the surface protective film 4 by applying an adhesive to the surface of the surface protective film 4 and drying it. In this step, the adhesive layer 3 is formed only on the surface of the surface protective film 4, but it may be formed on the surface of the silver surface layer instead of such a form. An adhesive layer may be formed on both the surface and the surface of the silver surface layer.

  Moreover, you may form by laminating | stacking an adhesive bond layer on the surface of a surface protective film with the formation of a surface protective film by the melt extrusion multilayer lamination method. According to such a method, since the adhesive layer is also formed at the same time in the melt extrusion laminating step, it is preferable because the step of forming the adhesive layer in a separate step can be omitted.

  The adhesive for forming the adhesive layer is not particularly limited. Specific examples thereof include urethane-based and acrylic-based adhesives such as polyester polyol-acrylic copolymers, polyester-based, vinyl chloride-based adhesives such as vinyl chloride-vinyl acetate copolymer, and epoxy-based adhesives. These may be used alone or, for example, two or more layers may be laminated.

  The thickness of the adhesive layer is not particularly limited, but it is 0.1 to 20 μm, and further 0.2 to 10 μm, even if the surface of the silver surface layer is formed with wrinkles This is preferable because the protective film can be firmly adhered to the silver surface layer. The total thickness of the surface protective film and the adhesive layer is preferably about 5 to 40 μm, more preferably about 5 to 20 μm.

  And as shown in FIG.2 (c), the surface of the silver surface layer 2 of the artificial leather base material formed by laminating | stacking the silver surface layer 2 on the surface of the nonwoven fabric base material 1 via the adhesive bond layer 3 The surface protective film 6 with release sheet is placed and pressed, and the adhesive is cured to bond the surface protective film 4 and the silver surface layer 2 with the adhesive layer 3.

  Here, the silver-finished artificial leather substrate formed by laminating the silver layer 2 on the surface of the nonwoven fabric substrate 1 will be described in detail.

  The nonwoven fabric substrate 1 has a structure in which a polymer elastic body is impregnated with a fiber structure in which ultrafine fibers are entangled three-dimensionally, if necessary.

  The fiber entangled body of ultrafine fibers can be obtained, for example, by entanglement processing of ultrafine fiber generating fibers such as sea-island type composite fibers to form a fiber entangled body, and then subject the fibers to ultrafine fiber treatment. In this embodiment, the case where the sea-island type composite fiber is used as the ultra-fine fiber-generating fiber will be described in detail. However, the ultra-fine fiber-generating fiber other than the sea-island type composite fiber may be used. The fine fiber may be directly spun without using. In addition, as a specific example of the ultrafine fiber generation type fiber other than the sea-island type composite fiber, a plurality of ultrafine fibers are formed by lightly bonding immediately after spinning, and a plurality of ultrafine fibers are formed by unraveling by mechanical operation. Such as a split-divided fiber, or a petal-type fiber in which a plurality of resins are alternately gathered in a petal shape in the melt spinning process, and any fiber that can form ultrafine fibers is used without particular limitation. It is done.

  In the production of the ultrafine fiber entangled body, first, the thermoplastic resin constituting the sea component of the sea-island type composite fiber that can be selectively removed and the island component of the sea-island type composite fiber that is the resin component forming the ultrafine fiber are constituted. A sea-island type composite fiber is obtained by melt spinning and stretching a thermoplastic resin.

  As the sea component thermoplastic resin, a thermoplastic resin having a different solubility in a solvent or a decomposability in a decomposing agent is selected from the island component resin. Specific examples of the thermoplastic resin constituting the sea component include water-soluble polyvinyl alcohol resin, polyethylene, polypropylene, polystyrene, ethylene propylene resin, ethylene vinyl acetate resin, styrene ethylene resin, styrene acrylic resin, and the like.

  The thermoplastic resin, which is a resin component that forms island components and forms ultrafine fibers, is not particularly limited as long as it is a resin that can form sea-island composite fibers and ultrafine fibers. Specifically, for example, polyethylene terephthalate (PET), isophthalic acid modified PET, sulfoisophthalic acid modified PET, polybutylene terephthalate, polyhexamethylene terephthalate and other aromatic polyesters; polylactic acid, polyethylene succinate, polybutylene succinate, Aliphatic polyesters such as polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate resin; polyamides such as polyamide 6, polyamide 66, polyamide 10, polyamide 11, polyamide 12, polyamide 6-12; polypropylene, polyethylene, polybutene , Polyolefins such as polymethylpentene and chlorinated polyolefin. These may be used alone or in combination of two or more.

  As a method for producing a fiber entangled body of ultrafine fibers, for example, a sea web type composite fiber is melt spun to produce a fiber web, and after the fiber web is entangled, sea components are selectively removed from the sea island type composite fiber. And a method of forming ultrafine fibers. As a method for producing a fiber web, a method of forming a long fiber web by collecting sea-island type long fibers spun by a spunbond method or the like without cutting them on a net, or by cutting long fibers into staples. Examples thereof include a method for forming a fiber web. Further, the formed fiber web may be subjected to a fusion treatment in order to impart shape stability.

  Usually, in any process from removing sea components of a fiber web made of sea-island type composite fibers to form ultrafine fibers, fiber shrinkage treatment such as entanglement treatment, heat shrinkage treatment with water vapor is performed. It is preferable to perform a densification treatment. As the entanglement treatment, for example, a method in which about 5 to 100 obtained fiber webs are stacked and the fiber web is entangled using a known nonwoven fabric production method such as needle punching or high-pressure water flow treatment is used. It is done.

  The sea component of the sea-island type composite fiber may be removed by extraction or decomposition at an appropriate stage after the fiber web is formed. By such disassembly removal or extraction removal, the sea-island type composite fibers are made into ultrafine fibers to form ultrafine fibers.

The fineness of the ultrafine fibers is 0.9 dtex or less, preferably 0.001 to 0.9 dtex, more preferably 0.01 to 0.6 dtex, and particularly preferably 0.02 to 0.5 dtex. When the fineness is too high, the feeling of denseness is insufficient, and a nonwoven fabric substrate with a feeling of coarseness can be obtained. In addition, fibers with too low a fineness are difficult to produce, and the fibers do not unravel and converge and the resulting nonwoven fabric substrate tends to have too high rigidity. Although not particularly limited even basis weight of the fiber-entangled body, 140~3000g / m ^2, and it is more preferably about 200 to 1000 g / m ^2.

  When the nonwoven fabric substrate contains a polymer elastic body, the proportion of the polymer elastic body in the total amount of the nonwoven fabric substrate is 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and particularly 10 to 20 parts by mass. It is preferable to contain. In addition, when the content rate of a polymeric elastic body is too high, there exists a tendency for rubber | gum feeling to become strong and for a texture to be impaired.

  As the polymer elastic body, rubber or thermoplastic elastomer that can be impregnated into the ultrafine fiber entangled body is used without particular limitation. Specific examples thereof include, for example, urethane resins such as polyurethane elastomer and urethane rubber, acrylic resins such as acrylic rubber, diene rubber, silicone rubber, nitrile rubber, olefin rubber, fluorine rubber, polystyrene elastomer. And polyolefin elastomers, polyamide elastomers, and halogen elastomers. These may be used alone or in combination of two or more. Of these, urethane resins are preferred.

  The method of impregnating the ultrafine fiber entangled body with the polymer elastic body is not particularly limited. Then, after the polymer elastic body is dry-coagulated or wet-coagulated, a method of performing ultrafine fiber treatment for selectively removing sea components from the sea-island type composite fiber forming the fiber entanglement is exemplified. In addition, as another method, after performing the ultrafine fiber treatment of the fiber entangled body obtained by entanglement treatment of the sea-island type composite fiber in advance, impregnation with an emulsion or coating liquid of a polymer elastic body, The polymer elastic body may be dry coagulated or wet coagulated.

  The ultrafine fiber entangled body thus obtained is subjected to thickness adjustment and flattening treatment by slicing or buffing as necessary. In this way, a nonwoven fabric substrate is obtained. Also, finishing treatments such as sag softening treatment, reverse seal brushing treatment, antifouling treatment, hydrophilic treatment, lubricant treatment, softener treatment, antioxidant treatment, ultraviolet absorber treatment, fluorescent agent treatment, flame retardant treatment, etc. May be applied.

  Although the thickness of a nonwoven fabric base material is not specifically limited, It is preferable that it is about 0.3-3 mm, Furthermore, about 0.3-1 mm.

  A silver surface layer is laminated and formed on the surface of the nonwoven fabric substrate thus formed. The formation method of a silver surface layer is not specifically limited. For example, after applying a coating liquid containing a resin component for forming a silver surface layer on a release sheet, a silver surface layer film is formed by drying, and the silver surface layer film is applied to the surface of the nonwoven fabric substrate. And a method of peeling off the release sheet, and a method of forming by drying after applying a coating liquid containing a resin component for forming a silver surface layer to the surface of the nonwoven fabric substrate. .

  As the resin component for forming the silver surface layer, for example, a polymer elastic body such as a urethane resin or an acrylic resin is preferably used, and in particular, a non-foamed urethane resin forms a surface protective film. It is preferable from the viewpoint of forming a layer with a high degree of fullness and having excellent surface characteristics such as wear resistance. The coating liquid containing a resin component for forming a silver surface layer is prepared as a solution, emulsion, suspension or the like. In addition, the resin component for forming the silver layer contains, if necessary, a colorant, an ultraviolet absorber, a surfactant, a flame retardant, an antioxidant and the like within a range not impairing the effects of the present invention. May be.

  The thickness of the silver surface layer is preferably 10 to 200 μm, more preferably 50 to 150 μm. In addition, it is preferable from the point of the designability that a silver surface layer has the wrinkle pattern formed by embossing etc. Embossing, for example, forms a silver layer film on a release paper with a wrinkle pattern on the surface, or transfers the wrinkle pattern with the silver surface layer uncured, and then completely cures the silver layer The method of making it be mentioned.

  And as shown in FIG.2 (c), the surface protection film 6 with a peeling sheet is arrange | positioned and pressed through the adhesive layer 3 on the surface of the silver surface layer 2 of an artificial leather base material, and an adhesive agent is hardened. By doing so, the surface protective film 4 and the silver surface layer 2 are adhered by the adhesive layer 3.

  In addition, after applying and drying the adhesive, it may be subjected to an aging treatment or the like that is allowed to stand for several hours to several days at a predetermined temperature in order to advance the crosslinking of the adhesive with a curing agent and improve the adhesive strength. preferable.

  Then, after the surface protective film 4 and the silver surface layer 2 are bonded by the adhesive layer 3, as shown in FIG. 2 (d), the release sheet 5 attached to the surface protective film 4 is peeled off. Thus, the silver-finished artificial leather 10 is formed.

  The silver-finished artificial leather formed in this way can firmly adhere the surface protective film to the surface of the texture even when the silver surface layer has a deep texture pattern. Specifically, the peel strength when peeled between the surface protective film and the silver surface layer is 1 kgf / 2.5 cm or more, more preferably 1.5 kgf / 2.5 cm or more, particularly 2 kgf / 2.5 cm or more. It is preferable to show such peel strength.

  The silver-tone artificial leather thus formed is preferably used as a skin material for various products. In particular, it is used for the production of a decorative molded body in which a decorative sheet is integrated with the surface of a molded body main body known as a molded body having excellent design properties used for a casing of a mobile phone, a mobile device, a home appliance, etc. It is preferably used as a decorative sheet.

  An example of a method for producing a decorative molded body will be described with reference to FIG. In the production of the decorative molded body, as shown in FIG. 3A, a silver-tone artificial leather 10 is hot-pressed using a mold having a three-dimensional cavity made up of a male mold 11a and a female mold 11b. It shape | molds and the preform molded object 20 as shown in FIG.2 (b) is shape | molded. Then, as shown in FIG. 3C, the preform molded body 20 is inserted into the cavity of the injection insert molding die 13, and the molten resin 14 is applied to the back surface of the preform molded body 20 from the nozzle 12 of the injection molding machine. Injection insert molding is performed by molding by injection. By such injection insert molding, as shown in FIG. 3 (d), a decorative molded body in which a preform molded body 20 formed from a silver-tone artificial leather 10 is integrated on the surface of the injection molded body 21. 30 is obtained.

  The present invention will be described more specifically with reference to examples. The scope of the present invention is not limited by the examples.

[Example 1]
<Manufacture of artificial leather base material with silver>
A nozzle that uses ethylene-modified polyvinyl alcohol as the sea component and isophthalic acid-modified polyethylene terephthalate as the island component, and is set at a base temperature of 260 ° C. to form a cross section in which 25 island components having a uniform cross-sectional area are distributed in the sea component. Molten resin was supplied to a plurality of spinning nozzles in which holes were arranged in parallel, and was discharged from the nozzle holes. At this time, it supplied, adjusting pressure so that the mass ratio of a sea component and an island component might become sea component / island component = 25/75.

The discharged molten fiber was drawn by a suction device so that the average spinning speed was 3700 m / min, and a sea-island long fiber having a fineness of 2.1 dtex was spun. The spun sea-island long fibers were continuously deposited on a movable net and lightly pressed with a 42 ° C. metal roll. Then, the sea-island long fibers were peeled from the net, and hot-pressed at a linear pressure of 200 N / mm by passing between a metal roll with a lattice pattern with a surface temperature of 75 ° C. and a back roll. In this way, a web having a basis weight of 34 g / m ² was obtained.

Next, the web was piled up into 10 layers using a cross wrapper device so that the total basis weight was 340 g / m ² and needle punched to obtain an entangled web. And the densified web was obtained by carrying out the wet heat shrink process and the dry heat roll press of the obtained entangled web.

  Then, the densified web was impregnated with a cross-linked aqueous polyurethane emulsion (solid content concentration: 16%) mainly composed of polycarbonate / ether-based polyurethane, and water was dried in a drying oven at 150 ° C. to be cross-linked. In this way, a polyurethane-containing entangled web having a mass ratio of entangled web / polyurethane of 90/10 was formed.

Next, the polyurethane-containing entangled web is immersed in hot water at 95 ° C. for 20 minutes to extract and remove sea components contained in the sea-island long fibers, and dried in a drying furnace at 120 ° C. to obtain a thickness of about A 1 mm nonwoven fabric substrate was obtained. The apparent density of the ultrafine fiber entangled body contained in the obtained nonwoven fabric substrate was 0.47 g / cm ³ , and the mass ratio of the ultrafine fiber entangled body / polyurethane was 88/12. The fineness of the ultrafine single fiber of the fiber entangled body was 0.2 dtex. And the obtained nonwoven fabric base material was divided into 2 in the thickness direction, and was ground to 0.37 mm.

  On the other hand, a non-foaming material having a thickness of 30 μm is obtained by applying a polycarbonate non-yellowing type polyurethane resin solution to the surface of a 20 μm-thick textured release paper having a texture pattern having a depth of about 10 μm and drying at 80 ° C. for 10 minutes. A polyurethane film was formed. A polycarbonate non-yellowing type two-part curable polyurethane solution containing a colorant is further applied to the surface of the formed film and dried at 50 ° C. for 3 minutes to form a 120 μm-thick non-foamed polyurethane film. did. In this way, a silver surface layer having a total thickness of 150 μm was formed.

  And the silver surface layer formed in the release paper with an embossing was bonded together to one surface of the nonwoven fabric base material, and it heated at 80 degreeC for 2 minutes, Then, after aging at 40 degreeC for 3 days, the release paper was peeled. Thus, a silver-tone artificial leather base material was obtained.

<Manufacture of surface protective film with release sheet>
EVOH copolymer (Eval E105 manufactured by Kuraray Co., Ltd. having an ethylene content of 44 mol% and a saponification degree of 99%) and a maleic anhydride-modified high-density polyethylene resin (PE) having a modification rate of 0.09 mol% 20 parts by mass was kneaded with a twin-screw extruder and pelletized. Then, a 10 μm thick surface protective film is laminated on the surface of a PET sheet having a flat surface of 38 μm thickness by an extrusion laminating method using a T-die extruder using the obtained pellets. A surface protective film with a release sheet was obtained.

<Adhesion between silver-finished artificial leather substrate and surface protective film>
The surface of the surface protective film with a release sheet is coated with 5 g / m ² of urethane adhesive so that the thickness after drying with a wire bar is 2 μm, and is dried at 60 ° C. for 5 minutes. An adhesive layer was formed on the surface protective layer of the attached surface protective film. As an adhesive, urethane adhesive (Sunplex 435A manufactured by Murayama Chemical Co., Ltd.) is diluted with 20% aqueous solution of isopropanol (IPA) to a concentration of 20%, and a blocked isocyanate curing agent (manufactured by DIC Corporation) is 5%. The one to which was added was used. Further, an adhesive layer having a thickness of 4 μm after drying was also formed on the surface of the silver layer of the silver-tone artificial leather base material by the same method.

  And after arrange | positioning so that the adhesive bond layer of the surface of the silver surface layer of a silver-finished artificial leather base material and the adhesive layer of a surface protection film with a peeling sheet may oppose, it heat-presses at 150 degreeC for 2 second, Until cooled. And by peeling a PET sheet | seat, the silver-tone artificial leather which has a surface protective layer in an outermost layer was obtained, and it evaluated by the following methods.

(Glossiness)
Using a gloss checker IG-33T manufactured by HORIBA, Ltd., the glossiness specified by JIS Z8741 of the surface of the silver-coated artificial leather on the silver layer side was measured at an angle of 60 degrees.

(Total light transmittance)
The surface protective film was peeled from the surface protective film with a release sheet, and the total light transmittance was measured by a method according to ASTM D1003 using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd.

(Cellophane tape peeling)
Attaching cellophane tape made by Nichiban Co., Ltd. to the surface of the silver-coated artificial leather on the silver surface layer side, and after making sure that it adheres well, hold the cellophane tape on the non-adhered part with your hand in an oblique direction (about 45 °) ) Was pulled and abruptly peeled off. The peeled surface was visually observed and judged according to the following criteria.
A: No peeling at all.
B: Part peeled off C: All peeled off

(Peel strength)
A test piece was prepared by cutting the silver-finished artificial leather into 250 × 25 (mm). A rubber piece of 150 mm × 25 mm and a thickness of 5 mm was prepared. Then, about 0.15 g of adhesive was uniformly applied to each of the surface of the silver layer of the test piece and the surface of the rubber piece with a glass rod so as to be 50 to 70 g / m ^2, and the temperature was 110 ± 10 ° C. It heat-processed by putting in a steam dryer for about 3 minutes. In addition, what mixed the main agent (Sakai Chemical Industry Co., Ltd. US-33) and the hardening | curing agent (Sumika Bayer Urethane Co., Ltd. death module RE) was used for the adhesive agent. Then, the test piece taken out from the steam dryer and the rubber piece are overlapped with each other by 10 cm, and the adhesive application surfaces are pressure-bonded with a hand roller, and further pressed with a press pressure (gauge pressure) of 0.3 to 0.5 MPa. Crimped with a machine. Then, it was aged in a hot air dryer at 70 ° C. for 1 hour and adhered. Then, the bonded test piece and the rubber piece were pulled in a horizontal direction at a tensile speed of 100 mm / min by a tensile tester (autograph), and the measured maximum average strength was taken as the peel strength.

(Anti-fouling property)
Silver-tone artificial leather cut into 20 × 20 cm was fixed at an angle of 45 ° with respect to the vertical direction, and 20 ° C. instant coffee was showered perpendicular to the surface on the silver layer side. Instant coffee was prepared by dissolving 4 g of commercially available instant coffee powder in 100 cc of hot water and cooling to 20 ± 5 ° C. The silver-finished artificial leather after shower was left in an atmosphere of 50 ° C. and 90% for 5 hours, and then the surface on the silver layer side was wiped off with gauze moistened with water.
In addition, ketchup was applied to another artificial leather with silver cut into 20 × 20 cm, left in an atmosphere of 50 ° C. and 90% for 5 hours, and then the surface of the silver layer side was moistened with water. Wiped off. Then, the surface color difference ΔE before and after the treatment was measured.

(Creativity)
The grain pattern of the silver layer of the artificial leather with silver was observed through the surface protective layer, and the three-dimensional feeling, matte feeling, and color of the grain at that time were determined according to the following criteria.
<3D effect of grain>
A: The three-dimensional effect of the texture pattern was not lost.
B: The three-dimensional effect of the grain pattern was slightly lost.
<Matte feeling>
A: The matte feeling was high.
B: The matte feeling was low.
<Color>
A: The vivid color of the silver layer was not lost.
B: The transparency of the surface protective layer was low, and the vivid color of the silver surface layer was lost.
C: Air was entrained between the surface protective layer and the silver layer, and the vivid color of the silver layer was lost.

(Taber wear loss (scratch resistance))
Using a Taber Ablation Tester (made by TABER INSTRUMENT Corp) and wearing two wear wheels (H-22, load 500g) on the turntable, and the surface of the silver-coated artificial leather silver layer side is worn 1000 times The weight loss of wear was measured.

  The above evaluation results are shown in Table 1 below.

[Example 2]
A silver-coated artificial leather having a surface protective film on the outermost layer in the same manner as in Example 1 except that a 5 μm surface protective film was formed instead of forming a 10 μm surface protective film in Example 1. Obtained and evaluated. The results are shown in Table 1.

[Example 3]
Instead of using a release sheet to form a 10 μm surface protective film in Example 1, a 20 μm surface protective film was formed by an extrusion method using a T-die extruder without using a release sheet. Except for adhering to the surface of the face layer, the same procedure as in Example 1 was carried out to evaluate and evaluate a silver-tone artificial leather having a surface protective film on the outermost layer. The results are shown in Table 1.

[Example 4]
In place of using the surface protective film with release sheet obtained in Example 1 and using the surface protective film with release sheet obtained as described below, the surface protective film was formed on the outermost layer in the same manner. A silver-tone artificial leather having the following was obtained and evaluated. The results are shown in Table 1.
<Manufacture of surface protective film with release sheet>
60 parts by mass of an EVOH copolymer (Eval E105 manufactured by Kuraray Co., Ltd.) and 40 parts by mass of a maleic anhydride-modified high-density polyethylene resin having a modification rate of 0.09 mol% were kneaded and pelletized. And by the extrusion laminating method using the obtained pellets, the surface of the matted PET sheet (type A manufactured by Kaisei Kogyo Co., Ltd., thickness 50 μm) having a roughened surface is 10 μm thick. A surface protective film with a release sheet was obtained by laminating and forming a surface protective film.

[Example 5]
Silver having a surface protective film on the outermost layer in the same manner except that the surface protective film with release sheet obtained as described below was used instead of the surface protective film with release sheet obtained in Example 1 Toned artificial leather was obtained and evaluated. The results are shown in Table 1.
<Manufacture of surface protective film with release sheet>
90 parts by mass of EVOH copolymer (Eval E105 manufactured by Kuraray Co., Ltd.) and 10 parts by mass of maleic anhydride-modified high-density polyethylene resin having a modification rate of 0.09 mol% were kneaded and pelletized. Then, a 10 μm thick surface protective film is laminated on the surface of a PET sheet having a flat surface of 38 μm thickness by an extrusion laminating method using a T-die extruder using the obtained pellets. A surface protective film with a release sheet was obtained.

[Example 6]
Instead of forming a silver surface layer having a total thickness of 150 μm in Example 1, a surface protective film was formed on the outermost layer in the same manner as in Example 1 except that a silver surface layer having a total thickness of 100 μm was formed by the following method. A silver-tone artificial leather having the following was obtained and evaluated. The results are shown in Table 1.
A non-foamed polyurethane having a thickness of 30 μm is formed by applying a polycarbonate non-yellowing type polyurethane resin solution on the surface of a 20 μm-thick textured release paper having a texture pattern having a depth of about 10 μm and drying at 80 ° C. for 10 minutes. A film was formed. Further, a non-foamed polyurethane film having a thickness of 70 μm is formed by further applying a polycarbonate non-yellowing type two-component curable polyurethane solution containing a colorant to the surface of the formed film and drying at 50 ° C. for 3 minutes. did. In this way, a silver surface layer having a total thickness of 100 μm was formed.

[Example 7]
A silver-coated artificial leather having a surface protective film on the outermost layer was obtained and evaluated in the same manner as in Example 1 except that a 20 μm adhesive layer was formed instead of forming a 6 μm adhesive layer in Example 1. did. The results are shown in Table 1.

[Example 8]
In Example 1, an entangled web having a total basis weight of 340 g / cm ³ was obtained, and instead of producing and using an ultrafine fiber entangled body having an apparent density of 0.47 g / cm ^3, an apparent density of 0 was obtained by adjusting the press pressure. A 40 g / cm ³ ultrafine fiber entangled body was produced, and a silver-coated artificial leather having a surface protective film on the outermost layer was obtained and evaluated in the same manner as in Example 1 except that this ultrafine fiber entangled body was used. . The results are shown in Table 1.

[Comparative Example 1]
A silver-tone artificial leather having a surface protective film on the outermost layer in the same manner as in Example 1 except that a film of 30 μm surface protective film was formed instead of forming a film of 10 μm surface protective film in Example 1. Obtained and evaluated. The results are shown in Table 1.

[Comparative Example 2]
Instead of producing a microfine fiber-entangled body of density 0.47 g / cm ³ apparent in fineness 0.2dtex in Example 1, fiber-entangled body of density 0.25 g / cm ³ apparent with regular fibers having a fineness of 1.5dtex A silver-tone artificial leather having a surface protective film on the outermost layer was obtained and evaluated in the same manner as in Example 1 except that was manufactured. The results are shown in Table 1.

[Comparative Example 3]
In Example 1, instead of kneading 80 parts by mass of EVOH copolymer and 20 parts by mass of maleic anhydride-modified high-density polyethylene resin, 80 parts by mass of EVOH copolymer and 20 parts by mass of talc having a particle size of 1.5 μm; The outermost layer was formed in the same manner as in Example 1 except that a 10 μm surface protective film was formed by extrusion T-die without using a release sheet, and this film was bonded to the silver surface layer with an adhesive. Silver-coated artificial leather having a surface protective film was obtained and evaluated. The results are shown in Table 1.

[Comparative Example 4]
In Example 1, instead of kneading 80 parts by mass of EVOH copolymer and 20 parts by mass of maleic anhydride-modified high-density polyethylene resin, 80 parts by mass of EVOH copolymer and 20 parts by mass of talc having a particle size of 1.5 μm; In addition, instead of forming a 10 μm surface protective film, a 30 μm surface protective film was formed by extrusion T-die without using a release sheet, and this film was formed into a silver layer with an adhesive. Except for bonding, a silver-tone artificial leather having a surface protective film on the outermost layer was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.

The silver-coated artificial leathers obtained in Examples 1 to 8 according to the present invention all have a high matte feeling and light transmittance in the surface protective film, and have an excellent balance between the matte feeling and the coloring. Met. Moreover, it was excellent also in the adhesiveness of a surface protective film and a silver surface layer. On the other hand, in the case of the silver-coated artificial leather of Comparative Example 1 having a surface protective film thickness of 30 μm, compared to the silver-coated artificial leather of Examples 1 to 3 having a surface protective film of 5 to 20 μm in thickness, Due to the low light transmittance, the color was poor, and the texture of the texture was also poor. In addition, the silver-coated artificial leather of Comparative Example 2 using a fiber entanglement of regular fibers having an apparent density of 0.25 g / cm ³ has a surface protective film formed on a base with a low level of solidity. And the adhesion between the silver layer and the silver surface layer were low. In addition, the silver-coated artificial leather of Comparative Example 3 having a surface protective film containing 20% by mass of talc and having a matte feeling has a high glossiness and low antifouling property, and has a thickness to suppress the glossiness. Although the glossiness of the silver-finished artificial leather of Comparative Example 4 of 30 μm was suppressed, the light transmittance was significantly reduced, and the relationship between matte feeling and color development became a trade-off relationship, and the matte feeling and color development. It was inferior to the balance.

  The silver-tone artificial leather of the present invention is a shoe, sports shoe, bag, belt, school bag, camera case, balls, furniture, vehicle, etc. that require antifouling properties, design (surface gloss), and scratch resistance. It is widely used for wall coverings such as seats, clothing, gloves, baseball gloves, clothing, and dwellings. Manufacture of leather products and decorative molded bodies represented by men's shoes, sports shoes, bags, belts, camera cases, school bags, balls, furniture, vehicle seats, clothing, gloves, baseball gloves, bags, belts or bags Applicable to.

DESCRIPTION OF SYMBOLS 1 Nonwoven fabric base material 2 Silver surface layer 3 Adhesive layer 4 Surface protective film 5 Release sheet 6 Surface protective film 10 with release sheet Silver-like artificial leather 11a Male mold 11b Female mold 12 Injection molding machine nozzle 13 Injection insert molding gold Mold 14 Molten resin 21 Injection molded body 30 Decorated molded body

Claims (11)

Comprising a nonwoven fabric base material comprising an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less, a silver surface layer laminated on the nonwoven fabric base material, and a surface protective film laminated on the silver surface layer,
The surface protective film is a film having a thickness of 5 to 20 μm mainly composed of a saponified ethylene-vinyl acetate copolymer (EVOH copolymer),
The silver-finished artificial leather characterized in that the surface on the silver layer side has a matte surface exhibiting a glossiness of 5 to 60% defined by JIS Z 8741.   The artificial leather with a silver tone according to claim 1, wherein the total light transmittance of the surface protective film is 80% or more.   The silver-coated artificial leather according to claim 1, wherein the surface protective film is a film having a thickness of 5 to 10 μm.   The said silver surface layer is a 10-200-micrometer-thick layer containing a non-porous polyurethane elastic body, and has an embossed pattern with an average depth of 10-150 micrometers on the outer surface side. The artificial leather with a silver tone according to Item.   The silver-coated artificial leather according to any one of claims 1 to 4, wherein the silver surface layer and the surface protective film are bonded via an adhesive layer having a thickness of 0.1 to 20 µm.   The said surface protective film is 5 to 40 mass% of polyolefin resin further, The silver-finished artificial leather of any one of Claims 1-5.   The matte leather according to any one of claims 1 to 6, wherein the mat surface of the surface protective film is formed by transferring the mat surface of a release sheet having a mat surface.   The artificial leather with silver tone according to any one of claims 1 to 7, wherein the peel strength when peeled between the surface protective film and the silver layer is 2 kgf / 2.5 cm or more. The said nonwoven fabric base material is a silver-tone artificial leather of any one of Claims 1-8 which has an apparent density of 0.45 g / cm < ³ > or more. A decorative molded body including a resin molded body and a decorative sheet integrated on the surface of the resin molded body,
The said decorative sheet | seat is the silver-tone artificial leather of any one of Claims 1-8, The decorative molded body characterized by the above-mentioned. Preparing a silver-tone artificial leather base material comprising a non-woven base material containing an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less and a silver surface layer laminated on the non-woven base material;
Providing a surface protective film having a thickness of 5 to 20 μm having a matte surface exhibiting a glossiness of 5 to 60% defined in JIS Z 8741;
Forming an adhesive layer on at least one of the surface opposite to the mat surface of the surface protective film and the surface of the silver surface layer so that the total thickness is 0.1 to 20 μm;
A surface of the silver surface layer and the opposite surface are arranged so as to face each other with the adhesive layer interposed therebetween, and integrated by heat pressing. Production method.

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