JP2017061051A - Flexible decorative laminate, and production method of flexible decorative laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel sheet material having a decorated appearance and fibrous feeling on the outside surface, and having elasticity imparting repulsive feeling when pressing the surface with a finger, as the whole sheet.SOLUTION: A flexible decorative laminate contains a non-porous thermoplastic elastomer layer, and a decorative layer containing a fiber structure arranged on the outside surface of the thermoplastic elastomer layer, and has a composite layer formed by integrating compositely a surface layer of the thermoplastic elastomer layer with a surface layer of the fiber structure contained in the decorative layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a flexible decorative laminate in which a decorative layer such as artificial leather including a fiber structure is disposed on an outer surface, and a method for manufacturing the same.

  Conventionally, sheet materials such as natural leather and artificial leather have been used as seat materials for vehicles, aircraft, and the like, and as skin materials for furniture, clothing, and the like. Such a sheet material usually has a thickness of about 0.3 to 1.5 mm. For example, a backer material (backing material) is laminated to increase the thickness and used for reinforcement.

  In addition, as a new use of artificial leather, a decorative molded body in which artificial leather is arranged on the surface is known as an exterior member of a mobile phone, a mobile device, a housing for home appliances, a building material, furniture, and the like.

  For example, in Patent Document 1 below, a reinforcing sheet having a thickness of 0.1 to 0.6 mm is bonded to the back of an artificial leather made of fibers having a fineness of 0.05 denier or more and having a thickness of 0.4 to 1.0 mm. The insert material having a feeling of feeling with silver is made into a three-dimensional shape by pre-molding, punched into the required shape and stored in the cavity in the injection mold, and then molded resin in the molten state from the reinforcing sheet side of the insert material A method for producing a molded product in which artificial leather obtained by integrating a insert material on the surface of a resin molded product having a thickness of at least 0.2 mm by molding is molded on the surface is disclosed.

  Sheet materials such as natural leather and artificial leather are flexible materials, and a sheet reinforced by increasing the thickness by stacking the above-described backer materials (backing materials) is also a flexible material. . However, although a material made by laminating a backer material on artificial leather or the like has flexibility, it is not a material that has elasticity that makes you feel a rebound when the surface is held down with your fingers, but only a hard tactile sensation was obtained . Moreover, since the artificial leather is integrated on the surface of the hard resin molded product, the molded product in which the artificial leather is arranged on the surface of the resin molded product as disclosed in Patent Document 1 has a hard tactile sensation. Have

  On the other hand, in Patent Document 2 below, an outer skin layer made of cloth, synthetic leather, leather, or the like and forming an outer surface, and an inner surface of the outer skin layer and heat-sealed to the outer skin layer to generate elasticity by external pressure from the outer skin layer. Therefore, a molded article such as an armrest comprising an elastic layer made of a thermoplastic elastomer and a structure made of a thermoplastic synthetic resin that is heat-sealed to an outer skin layer or an elastic layer is disclosed. And since such a molded article has the elastic layer made from the thermoplastic elastomer formed in the inner layer, even if it presses from an outer skin, it is disclosed that there is no hard touch and a soft touch is obtained.

  Patent Document 3 below discloses a surface base material layer including a fiber entanglement of fiber bundles made of ultrafine single fibers having an average fineness of 0.01 to 0.8 dtex, and a polymer disposed on the back surface of the surface base material layer. Disclosed is a decorative molding sheet comprising a resin layer made of an elastic body and an intermediate layer in which the interface between the surface base material layer and the resin layer is mixed.

Japanese Patent Application Laid-Open No. 2006-281592 JP-A-5-23234 JP 2013-132783 A

  There has been a demand for a material that retains the decorative appearance and the cushioning property due to the fiber feeling on the outer surface and has elasticity that makes the sheet feel rebound when the surface is held down with fingers. For example, when such a seat is used for a handle cover, a dashboard, or the like in the interior of an automobile, a high-quality impression with excellent tactile sensation can be given.

  It is an object of the present invention to provide a novel sheet material having elasticity that retains a fiber appearance on the decorated appearance and the outer surface, and gives a feeling of repulsion when the surface is suppressed with a finger as a whole sheet. And

  One aspect of the present invention includes a non-porous thermoplastic elastomer layer and a decorative layer including a fiber structure disposed on an outer surface of the thermoplastic elastomer layer, and the surface layer and the decorative layer of the thermoplastic elastomer layer Is a flexible decorative laminate having a composite layer in which the surface layer of the fiber structure contained in the composite is integrated. In such a flexible decorative laminate, when the decorative layer including the fiber structure decorates the appearance and gives a fiber feeling, the non-porous thermoplastic elastomer layer suppresses the surface with a finger. Maintain elasticity that makes you feel rebound. And since the surface layer of a thermoplastic elastomer layer penetrate | invades into the surface layer of a fiber structure, and is compounded and integrated, it is fully bonded by the anchor effect of a fiber.

  Further, the thickness of the thermoplastic elastomer layer is 1.5 times or more of the thickness of the decorative layer excluding the composite layer, and the composite layer has a fiber structure in which the surface layer of the thermoplastic elastomer layer is It is preferable that the layer is formed so as to penetrate to a thickness of 1/2 or less of the thickness. In such a case, a feeling of repulsion is felt when the surface is held down with a finger, and the tactile sensation with a fiber feeling is not lost because the fiber structure maintains voids.

  Moreover, it is preferable that a fiber structure contains the nonwoven fabric base material of an ultrafine fiber. When the surface structure of the thermoplastic elastomer layer is integrated, the fiber structure including the non-woven fabric substrate of ultrafine fibers can be allowed to enter only the surface layer without excessively intruding the thermoplastic elastomer layer. As a result, the fiber feeling can be sufficiently retained.

  Moreover, when a decoration layer is artificial leather, it is preferable from the point which can provide the leather-like appearance with a high-class feeling.

  When the thermoplastic elastomer layer contains at least one selected from a styrene isoprene-based thermoplastic elastomer, a styrene-butadiene-based thermoplastic elastomer, and a styrene-isoprene-butadiene-based thermoplastic elastomer, it has low hardness and compression set characteristics. It is preferable from the viewpoints of excellent stretchability, excellent balance between flexibility and resilience, and excellent productivity due to excellent injection moldability.

  When the thermoplastic elastomer layer is an injection-molded body having a thickness of 0.5 mm or more, the elasticity of the rebound feeling is sufficiently felt when the surface of the entire sheet is suppressed with fingers. This is preferable from the viewpoint of obtaining a flexible decorative laminate.

  Another aspect of the present invention is a step of placing a decorative sheet including a non-woven substrate of ultrafine fibers in a cavity of a mold of an injection molding machine, and a non-woven substrate side of the decorative sheet in the cavity. And a step of injecting a non-porous thermoplastic elastomer to form a non-porous thermoplastic elastomer layer. In such a manufacturing method, in an in-mold injection molding in which a decorative sheet including an ultrafine fiber nonwoven fabric substrate is placed in a mold cavity and molded, a dense fiber structure including the ultrafine fiber nonwoven fabric substrate When the surface layer of the thermoplastic elastomer layer is integrated, the fiber feeling can be sufficiently retained in order to moderately limit the penetration of the thermoplastic elastomer layer. Therefore, it is possible to suppress a decrease in the texture of the decorative sheet due to, for example, the fusion of the fiber base material by heat transmitted from the thermoplastic elastomer melted during the injection molding.

  The thermoplastic elastomer preferably contains at least one selected from styrene isoprene-based thermoplastic elastomers, styrene-butadiene-based thermoplastic elastomers, and styrene-isoprene-butadiene-based thermoplastic elastomers from the viewpoint of excellent injection moldability.

  ADVANTAGE OF THE INVENTION According to this invention, providing the novel sheet | seat material which has the elasticity which makes the external appearance decorated with the decoration layer containing a fiber structure, and feels a high repulsion feeling when the surface is suppressed with a finger | toe. it can.

FIG. 1 is a schematic cross-sectional view of a flexible decorative laminate 10 using silver-tone artificial leather. FIG. 2 is a schematic cross-sectional view of a flexible decorative laminate 20 using suede-like artificial leather. FIG. 3 is a schematic cross-sectional view illustrating each step of the manufacturing method by injection molding as an example of the manufacturing method of the flexible decorative laminate 10. 4 is a scanning microscope (SEM) photograph of a cross section of the flexible decorative laminate obtained in Example 1. FIG.

  The flexible decorative laminate according to the present invention includes a non-porous thermoplastic elastomer layer and a decorative layer including a fiber structure disposed on the outer surface of the thermoplastic elastomer layer, and the thermoplastic elastomer layer And a surface layer of the fiber structure have a composite layer. Hereinafter, as an embodiment of the flexible decorative laminate according to the present invention, an example in the case of using artificial leather with a silver tone as a decorative layer including a fiber structure will be described in detail.

  FIG. 1 is a schematic cross-sectional view of a flexible decorative laminate 10 of the present embodiment. The flexible decorative laminate 10 includes a non-porous thermoplastic elastomer layer 1 and an artificial leather 5 with a silver tone, which is a decorative layer including a fiber structure disposed on the outer surface of the thermoplastic elastomer layer 1. Including. The artificial leather 5 includes a fiber structure 2 and a silver-tone resin layer 3 laminated on the outer surface of the fiber structure 2.

  Further, in the flexible decorative laminate 10, the surface layer portion excluding the region 1b of the thermoplastic elastomer layer 1 enters the surface layer of the fiber structure 2 to form a composite layer 1a that is combined and integrated. Yes.

  The total thickness of the decorative layer is not particularly limited, but is preferably about 0.3 to 1.5 mm, and more preferably about 0.5 to 1.3 mm. When the decorative layer is too thin, the fiber feeling is lowered and the peel strength with respect to the thermoplastic elastomer layer tends to be lowered.

  Moreover, the thickness of the thermoplastic elastomer layer is 1.5 times or more, preferably 2 times or more, more preferably 2.5 times or more of the thickness of the decorative layer excluding the composite layer. When the thickness of the thermoplastic elastomer layer is less than 1.5 times the thickness of the portion excluding the composite layer of the decorative layer, elasticity that gives a feeling of rebound when the surface is suppressed with a finger is obtained. It becomes difficult to be.

  The thickness of the thermoplastic elastomer layer is not particularly limited as long as it is 1.5 times or more the thickness of the portion excluding the composite layer of the decorative layer, but 0.45 mm or more, further 0.5 to 3 mm, especially It is preferably about 0.8 to 2 mm. When the thermoplastic elastomer layer is too thin, the resilience when the surface of the obtained flexible decorative laminate is suppressed with a finger tends to decrease.

  Moreover, the overall thickness of the flexible decorative laminate is not particularly limited, but is preferably about 0.8 to 5.0 mm, and more preferably about 1.0 to 3.0 mm. When the flexible decorative laminate is too thin, the cushioning property due to the fiber feeling is lowered, the elasticity that makes the feeling of rebound when the surface is suppressed with a finger is lowered, or the conventional sheet and There is a tendency to make it difficult to feel the difference in touch.

  In the flexible decorative laminate 10, the surface layer of the thermoplastic elastomer layer 1 enters the surface layer of the fiber structure 2, and has a composite layer 1 a that is combined and integrated. Here, in the composite layer 1a, the fiber component forming the fiber structure 2 does not melt and maintains the shape as it is, so that the anchor effect is sufficiently exerted on the thermoplastic elastomer layer 1. This is preferable because the peel strength can be increased. In addition, in the fiber structure 2, in the portion excluding the portion where the composite layer 1a is formed, the gap between the fibers is retained, thereby being different from the elasticity of the thermoplastic elastomer layer on the outer surface. A feeling of fiber can be made to feel.

  The thickness of the composite layer is preferably about 0.1 to 0.5 mm, more preferably about 0.15 to 0.4 mm, from the viewpoint that the adhesion of the decorative layer to the thermoplastic elastomer layer can be sufficiently maintained.

  The degree to which the surface layer of the thermoplastic elastomer layer penetrates into the surface layer of the fiber structure and is composite-integrated is up to 1/2 or less of the thickness of the fiber structure, and further to 1/3 or less. It is preferable to penetrate in the range. When the penetration of the thermoplastic elastomer layer with respect to the thickness of the fiber structure is too deep, it becomes difficult to maintain the fiber feeling on the outer surface. Moreover, as a minimum of the grade integrated and integrated, it is about 1/10 or more of the thickness of a fiber structure from the point which can fully exhibit an anchor effect and can maintain high peeling strength. preferable.

  As described above, the flexible decorative laminate 10 using the artificial leather having a silver surface tone has been described in detail as a representative example with reference to FIG. 1, but the raised surface 15a on the surface as a fiber structure as shown in FIG. In addition to the form such as the flexible decorative laminate 20 using the suede-like artificial leather 15 having the above, the form of the fiber structure is not particularly limited as long as the effects of the present invention are exhibited.

  Next, as an example of a method for producing a flexible decorative laminate, an artificial leather in which a resin layer having a silver surface is laminated on a nonwoven fabric substrate of ultrafine fibers is used as a decorative sheet to form a decorative layer. A flexible decorative laminate 30 having artificial leather 25 as a surface layer is manufactured by placing artificial leather in a mold cavity of an injection molding machine and injection-molding a non-porous thermoplastic elastomer. The method of performing will be described in detail. In addition to the method by injection molding, a method by press molding can be used as a method for producing the flexible decorative laminate, but only the surface layer of the fiber structure is allowed to penetrate into the surface layer of the thermoplastic elastomer layer. Therefore, it is particularly preferable to use injection molding from the viewpoint of easy control and high productivity.

  First, as shown in FIG. 3 (a), an artificial leather 25 in which a resin layer 3 having a silver surface tone is laminated on a nonwoven fabric base material 12 of ultrafine fibers is decorated in a cavity of a mold 17 of an injection molding machine. Place as. The mold 17 includes a movable side mold 17a having a cavity c and a fixed side mold 17b. The artificial leather 25 is disposed so that the resin layer 3 having a silver surface faces the surface of the movable mold 17a that forms the cavity c. Then, as shown in FIG. 3B, the movable mold 17a and the fixed mold 17b are clamped.

  And as shown in FIG.3 (c), the non-porous thermoplastic elastomer 11 fuse | melted to the nonwoven fabric base material 12 side of the artificial leather 25 in the metal mold | die 17 is inject | poured and injection-molded. Specifically, in a state where the movable side mold 17a and the fixed side mold 17b are clamped, the cylinder 18 of the injection molding machine 13 is advanced until the nozzle 16 contacts the sprue bush 17f of the fixed side mold 17b. The mold 17 is filled with the molten thermoplastic elastomer 11 by injecting the melted thermoplastic elastomer 11 with the screw 19. The injected thermoplastic elastomer 11 flows through a resin flow path (not shown) including a runner and a gate in the mold 17 and fills the cavity c. At this time, the artificial thermoplastic leather 11 so that the molten thermoplastic elastomer 11 appropriately enters the nonwoven fabric substrate 12 and the non-porous thermoplastic elastomer layer 1 formed by injection molding maintains high adhesion due to the anchor effect. 25.

  The injection molding conditions are such that the resin can flow for complete filling according to the melting point and melt viscosity of the resin to be injected, the shape of the molded body, and the resin thickness (resin temperature, mold temperature, injection pressure, injection speed). , Holding pressure after injection, cooling time) is appropriately selected.

  After the injection is finished, as shown in FIG. 3D, the molten thermoplastic elastomer 11 is cooled, and the surface layer of the non-porous thermoplastic elastomer layer 1 is only the surface layer of the nonwoven fabric substrate 12 of the artificial leather 25. The flexible decorative laminated body 30 which is intruded into the composite and integrated is molded. Then, as shown in FIG. 3 (e), by opening the mold 17, the movable side mold 17 a and the fixed side mold 17 b are isolated, and the flexible decoration supported by the runner 8. The laminated body 30 is taken out. Then, as shown in FIG. 3 (f), the unnecessary runner 8 is cut off so that the surface layer of the thermoplastic elastomer layer 1 penetrates only into the surface layer of the nonwoven fabric substrate 12 of the artificial leather 25 and can be combined and integrated. A flexible decorative laminate 30 is obtained.

  Next, materials used for manufacturing the flexible decorative laminate will be described in detail.

  The non-porous thermoplastic elastomer is not particularly limited as long as it is a non-foaming thermoplastic elastomer that does not contain a component that forms a porous structure such as a foaming agent. Specific examples thereof include styrene isoprene thermoplastic elastomer, styrene butadiene thermoplastic elastomer, styrene / isoprene / butadiene thermoplastic elastomer, olefin thermoplastic elastomer, polyvinyl chloride (PVC) thermoplastic elastomer, polyurethane ( PU) -based thermoplastic elastomer, polyester-based thermoplastic elastomer, amide-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, silicone-based thermoplastic elastomer, acrylic-based elastomer and the like. These are appropriately selected according to the application. These may be used alone or in combination of two or more. Among these, styrene isoprene-based thermoplastic elastomers, styrene-butadiene-based thermoplastic elastomers, and styrene-isoprene-butadiene-based thermoplastic elastomers have a low hardness, excellent compression set properties and stretchability, and a balance between flexibility and resilience. It is preferable from the point of being excellent in productivity and in order to be excellent in injection moldability.

  Specific examples of styrene isoprene-based thermoplastic elastomers, styrene-butadiene-based thermoplastic elastomers, and styrene-isoprene-butadiene-based thermoplastic elastomers include hydrogenated derivatives of styrene-isoprene block copolymers and / or styrene-isoprene-butadiene block copolymers. Particularly preferred are hydrogenated derivatives of polymers. Preferably, a polymer block A mainly composed of at least two aromatic vinyl compounds and a polymer block B mainly composed of at least one isoprene compound (and, if necessary, a polymer block mainly composed of butadiene) And a block copolymer having a weight average molecular weight of 10,000 or more, more preferably 30,000 to 550,000, and a weight average molecular weight of 50,000 or more, more preferably 5 to 30. Examples of the block copolymer are ten thousand. As such a block polymer, Kuraray Co., Ltd. Septon 2000 series and Septon 4000 series (Kuraray Co., Ltd.), or EARNESTON (registered trademark) series, which is a compound containing them as a main component, are commercially available products. Can be mentioned.

  As the fluidity of the thermoplastic elastomer, for example, a melt flow rate (MFR) of 5 (g / 10 min JIS K7210 230 ° C. 21.18N) or more can appropriately penetrate into the nonwoven fabric base material and exhibit an anchor effect. To preferred.

  Moreover, in the manufacturing method of embodiment mentioned above, the example using the artificial leather by which the resin layer of the silver surface tone was laminated | stacked on the nonwoven fabric base material of the ultrafine fiber was shown as a decorating sheet. The decorative sheet for forming the decorative layer is not limited to artificial leather using such a non-woven fabric substrate of ultrafine fibers, and an artificial fabric using a non-woven fabric substrate of normal fineness as long as the effect of the present invention is exhibited. It may be leather. Further, instead of the artificial leather using the nonwoven fabric substrate, a fiber substrate such as synthetic leather using a woven fabric may be used. However, when the surface layer of the thermoplastic elastomer layer is infiltrated into the fiber structure and integrated, the thermoplastic elastomer layer can be easily invaded only to the surface layer, so that the tactile feeling with the fiber feeling can be further retained. From the above, artificial leather including a nonwoven fabric substrate of ultrafine fibers is particularly preferable. Hereinafter, the artificial leather including such a non-woven fabric substrate of ultrafine fibers will be described in detail.

  The nonwoven fabric substrate of ultrafine fibers contains ultrafine fibers having a fineness of 1 dtex or less, further 0.01 to 0.8 dtex, particularly 0.05 to 0.5 dtex, especially 0.07 to 0.1 dtex. Is preferred. When the fineness of the ultrafine fibers is too high, the nonwoven fabric base material is difficult to be dense, and in that case, the fiber feeling tends to decrease due to excessive penetration of the thermoplastic elastomer layer.

The apparent density of the nonwoven fabric substrate of ultrafine fibers is preferably 0.45 g / cm ³ or more, more preferably 0.45 to 0.70 g / cm ³ , and particularly preferably 0.50 to 0.65 g / cm ³ . When the nonwoven fabric base material has such a high apparent density, the thermoplastic elastomer melted in the injection molding is prevented from entering too much, and it is easy to obtain a fiber feeling that retains the voids of the nonwoven fabric base material. preferable. In addition, the apparent density of the nonwoven fabric substrate is, for example, the thickness measured by a load of 240 gf / cm ² according to JIS L1096, based on the basis weight value measured by the method described in JIS L 1096 8.4.2 (1999). Can be determined by dividing by value.

  In order to make the nonwoven fabric substrate have such a high apparent density, a plurality of ultrafine single fibers that are formed through ultrafine fiber forming fibers such as sea-island type composite fibers are converged. It is preferable to exist as a fiber bundle. Specifically, for example, it is preferable that 5 to 1000, more preferably 5 to 200, particularly preferably 10 to 50, and most preferably 10 to 30 ultrafine fibers are present as a fiber bundle. Thus, when the ultrafine fibers are present in the form of fiber bundles, the apparent density of the nonwoven fabric substrate can be increased.

Specific examples of the resin component forming the ultrafine fiber include, for example, polyethylene terephthalate (PET), modified polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polytriethylene terephthalate, polyhexamethylene terephthalate, Aromatic polyester resins such as polypropylene terephthalate and polyethylene naphthalate; aliphatic polyesters such as polylactic acid, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, and polyhydroxybutyrate-polyhydroxyvalerate copolymer Resins such as polyamide 6, polyamide 66, polyamide 610, polyamide 10, polyamide 11, polyamide 12, polyamide 6-12 -Based resins; polyolefin resins such as polypropylene, polyethylene, polybutene, polymethylpentene, chlorinated polyolefin, ethylene vinyl acetate copolymer, styrene ethylene copolymer; modified polyvinyl alcohol containing 25 to 70 mol% of ethylene units, etc. And modified elastomers such as polyurethane elastomers, polyamide elastomers, and polyester elastomers. Among these, fibers such as polyester having a glass transition temperature (T _g ) of 100 ° C. or higher, and further 105 ° C. or higher are not melted in the mold at the time of injection molding and are not integrated with the thermoplastic elastomer. From the viewpoint that the anchor effect can be exhibited while maintaining the fiber shape.

  The fiber length of the ultrafine fiber is not particularly limited, but a long fiber is particularly preferable from the viewpoint of easily increasing the apparent density. Here, the long fiber means that it is not a short fiber cut by a predetermined length. The length of the long fibers is preferably 100 mm or more, and more preferably 200 mm or more from the viewpoint that the fiber density of the ultrafine fibers can be sufficiently increased. When the length of the ultrafine fiber is too short, it tends to be difficult to increase the density of the fiber. Although an upper limit is not specifically limited, For example, the fiber length of several m, several hundreds m, several km or more spun continuously may be sufficient. Further, these fibers may be mixed with several kinds of fibers instead of single.

  Moreover, it is preferable that the nonwoven fabric base material containing ultrafine fibers contains an impregnated polymer elastic body. Such a polymer elastic body improves the shape stability of the nonwoven fabric substrate. Specific examples of such a polymer elastic body include polyurethane, acrylonitrile elastomer, olefin elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer, and the like. Of these, polyurethane is preferred.

  The polyurethane is preferably formed using an aqueous emulsion. Specific examples of the aqueous polyurethane emulsion include polycarbonate-based polyurethane, polyester-based polyurethane, polyether-based polyurethane, and polycarbonate / ether-based polyurethane aqueous emulsion that forms a crosslinked structure after drying.

  The content ratio of the polymer elastic body in the nonwoven fabric substrate is 5 to 40% by mass, more preferably 8 to 35% by mass, and particularly 12 to 30% by mass with respect to the total amount with the nonwoven fabric. This is preferable from the viewpoint of excellent formability of foam molding.

  The thickness of the nonwoven fabric substrate is preferably about 0.2 to 1.0 mm, particularly about 0.3 to 0.6 mm. When the nonwoven fabric substrate is too thin, the fiber feeling is lowered, heat from the injection resin is easily transmitted to the resin layer, and the surface of the decorative layer tends to be rough.

  On the outer surface of the artificial leather, it is preferable that a silver surface-like resin layer is formed as a decorative surface, or that the surface is raised to a suede tone, from the viewpoint of excellent design. As a polymer elastic body for forming a silver-tone resin layer, polyurethane, an acrylic elastic body, a silicone-based elastic body, and the like conventionally used for forming a silver-tone resin layer can be used. . The thickness of the resin layer is not particularly limited, but is preferably about 60 to 200 μm from the viewpoint that the balance between mechanical properties and texture can be maintained.

  The thickness of the artificial leather is preferably about 0.3 to 1.5 mm, more preferably about 0.5 to 1.3 mm. When the artificial leather is too thin, the fiber feeling is lowered and the peel strength with respect to the thermoplastic elastomer layer tends to be lowered.

  The flexible decorative laminate and one embodiment of the manufacturing method thereof have been described in detail above. Such flexible decorative laminates are made of materials for seats and interior / exterior parts of vehicles, aircraft, ships, etc .; materials for vehicle accessories, handle covers, key cases; saddles for motorcycles and skins for handles; Cases and covers for phones, smartphones and computers; cushioning materials such as helmets and protective gear; insoles and cushions for shoes; materials for bags, lids, handles, shoulders; chair seats and backrests It is preferably used for applications such as materials for parts; materials for handle parts of household appliances such as vacuum cleaners and refrigerators; and materials for handle parts of simple cleaning mops.

  In addition, if necessary, the flexible decorative laminate is bonded by hot plate, vibration, high frequency welding, sewn with another textile or cloth, bonded with an adhesive, or wrapped around a member. You can also Furthermore, the surface layer may be subjected to processing such as painting and printing.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by the Example.

[Example 1]
An apparent density of 0.53 g obtained by entanglement of fiber bundles (average 25 fibers / bundle) of ultrafine fibers having a single fiber fineness of 0.08 dtex obtained by removing sea components from a nonwoven fabric of long sea-island composite fibers A non-woven fabric substrate having a thickness of 0.5 mm was prepared by impregnating non-foamed polyurethane into a non-woven fabric of / cm ³ . The ultrafine fiber was made of an isophthalic acid-modified polyester having a Tg of 110 ° C., and the mass ratio of non-foamed polyurethane / nonwoven fabric was 15/85. And the nonwoven fabric base material was bonded together to the silver surface-like resin layer of thickness 0.15mm formed on the release paper, it heated at 80 degreeC for 2 minutes, and was then aged at 40 degreeC for 3 days. The release paper was peeled off to obtain an artificial leather with a thickness of about 0.7 mm and silver.

  The obtained artificial leather was cut into a disk shape having a diameter of 50 mm. Using the disk-shaped artificial leather as a decorative sheet, the disk-shaped disk with a diameter of 50 mm and a thickness of 2.0 mm of the mold of the injection molding machine so that the silver-tone resin layer is in contact with the mold surface A non-foaming styrene isoprene-based thermoplastic elastomer (EARNESTON CJC1202A1 manufactured by Kuraray Co., Ltd.) was injection molded under the conditions of a resin temperature of 210 ° C., a mold temperature of 30 to 50 ° C., and an injection pressure of 60 MPa. In this way, a disk-shaped flexible decorative laminate having a thickness of 2.0 mm was obtained. The photograph of the scanning microscope (SEM) of the cross section of the obtained flexible decorative laminated body is shown in FIG. The total thickness of the decorative layer measured from the obtained SEM photograph is 0.5 mm, the thickness of the thermoplastic elastomer layer is 1.5 mm, and the non-foaming thermoplastic elastomer layer is a nonwoven fabric substrate. The composite layer that penetrated and integrated into the composite layer was 0.2 mm, and the thickness of the decorative layer excluding the composite layer portion was 0.3 mm. The artificial leather with a silver tone having a thickness of about 0.7 mm was compressed by about 0.2 mm by the pressure in the mold at the time of injection molding. Moreover, the thickness of the thermoplastic elastomer layer was 5 times the thickness of the part except the composite layer of the decorating layer. And the obtained flexible decorative laminated body was evaluated as follows.

[Thickness measurement]
The thicknesses of the thermoplastic elastomer layer, the decorative layer, and the composite layer were measured from SEM photographs.

<Tactile sense>
The surface of the decorative layer of the flexible decorative laminate was pressed with a finger to evaluate the tactile sensation.
A: It had both rebound and fiber feeling.
B: Rubber elasticity was strong and the feel of the fiber material was clearly low.

<Rebound resilience>
Based on JIS K 6255, the rebound resilience (%) at 25 ° C. of the surface of the obtained decorative decorative laminate on the silver-tone side was measured using a Lüpke-type rebound resilience tester.

<Peeling strength of decorative layer>
A solvent-based adhesive was applied to the surface of the decorative layer of the flexible decorative laminate obtained in Example 1. Then, they were bonded to a rubber plate without being overlapped with each other and pressure-bonded with a press roller and cured at 20 ° C. for 24 hours. Then, the rubber plate and the end of the test piece were each sandwiched between chucks and peeled at a tensile speed of 100 mm / min with a tensile tester (universal type tensile tester Tensilon RTM-100, manufactured by Orientec Co., Ltd.). The average peel strength was determined from the flat portion of the obtained stress-strain curve (SS curve).

The results are shown in Table 1.

[Example 2]
In Example 1, instead of a disk-shaped mold having a thickness of 2.0 mm, a disk-shaped mold having a thickness of 1.5 mm was used. The resin temperature was 210 ° C., the mold temperature was 30-50 ° C., and the injection pressure was 60 MPa. In the same manner as in Example 1 except that the resin temperature is 210 ° C., the mold temperature is 30 to 50 ° C., and the injection pressure is 80 MPa. A decorative laminate was obtained. The total thickness of the decorative layer is 0.5 mm, the thickness of the thermoplastic elastomer layer is 1.0 mm, and a composite in which the non-foaming thermoplastic elastomer layer penetrates into the nonwoven fabric base material and is integrated The layer was 0.15 mm, and the thickness of the portion excluding the composite layer portion of the decorative layer was 0.35 mm. Further, the thickness of the thermoplastic elastomer layer was 2.86 times the thickness of the portion excluding the composite layer of the decorative layer. The obtained flexible decorative laminate was evaluated in the same manner as in Example 1.

[Example 3]
In Example 1, instead of the artificial leather with a silver tone having a thickness of about 0.7 mm, an artificial leather with a silver tone having a thickness of about 1.0 mm was used, and the resin temperature was 210 ° C. and the mold temperature was 30-50 ° C. In the same manner as in Example 1 except that the resin temperature is 210 ° C., the mold temperature is 30 to 50 ° C., and the injection pressure is 80 MPa, instead of the injection pressure of 60 MPa, the disk shape is 2.0 mm thick. A flexible decorative laminate was obtained. The total thickness of the decorative layer is 0.8 mm, the thickness of the thermoplastic elastomer layer is 1.0 mm, and a composite in which the non-foaming thermoplastic elastomer layer penetrates into the nonwoven fabric base material and is integrated The layer was 0.2 mm, and the thickness of the portion excluding the composite layer portion of the decorative layer was 0.6 mm. Moreover, the thickness of the thermoplastic elastomer layer was 1.67 times the thickness of the portion excluding the composite layer of the decorative layer. The obtained flexible decorative laminate was evaluated in the same manner as in Example 1.

[Example 4]
In Example 1, instead of an artificial leather having a thickness of about 0.7 mm containing an ultrafine fiber nonwoven fabric substrate having a single fiber fineness of 0.08 dtex, regular fibers having an apparent density of 0.49 g / cm ³ and a single fiber fineness of ³ dtex were used. A disc-shaped flexible decorative laminate having a thickness of 2.0 mm is obtained in the same manner as in Example 1 except that an artificial leather including a nonwoven fabric base and having a thickness of about 0.7 mm is used as the decorative sheet. It was. The total thickness of the decorative layer is 0.5 mm, the thickness of the thermoplastic elastomer layer is 1.5 mm, and a composite in which the non-foaming thermoplastic elastomer layer penetrates into the nonwoven fabric base material and is integrated The layer was 0.4 mm, and the thickness of the portion excluding the composite layer portion of the decorative layer was 0.1 mm. Moreover, the thickness of the thermoplastic elastomer layer was 15 times the thickness of the portion excluding the composite layer of the decorative layer. The obtained flexible decorative laminate was evaluated in the same manner as in Example 1.

[Comparative Example 1]
The artificial leather used in Example 1 was bonded to a thermoplastic elastomer sheet having a thickness of 1.5 mm via an adhesive layer having a thickness of 0.1 mm, and the hot plate temperature was 110 ° C. and the holding time was maintained using a flat plate press. Pressed at 1 MPa under pressure for 2 minutes to obtain a flexible decorative laminate. And it evaluated similarly to Example 1. FIG.

  INDUSTRIAL APPLICABILITY The present invention is used as a new decorative material having both rebound and fiber feeling.

DESCRIPTION OF SYMBOLS 1 Non-porous thermoplastic elastomer layer 1a Composite layer 1b Area of non-porous thermoplastic elastomer layer excluding composite layer 2 Fibrous structure 3 Silver surface resin layer 5,25 Artificial leather with silver Decoration layer)
10, 20, 30 Flexible decorative laminate 12 Non-woven fabric base material of ultrafine fiber 15 Suede-like artificial leather (decorative layer)

Claims (9)

A non-porous thermoplastic elastomer layer, and a decorative layer including a fiber structure disposed on the outer surface of the thermoplastic elastomer layer,
A flexible decorative laminate comprising a composite layer in which a surface layer of the thermoplastic elastomer layer and a surface layer of the fiber structure included in the decorative layer are combined and integrated.   2. The flexible decorative laminate according to claim 1, wherein a thickness of the thermoplastic elastomer layer is 1.5 times or more of a thickness of the decorative layer excluding the composite layer.   The flexible decoration according to claim 1 or 2, wherein the composite layer is a layer formed by intruding a surface layer of the thermoplastic elastomer layer to a thickness of 1/2 or less of a thickness of the fiber structure. Laminated body.   The flexible decorative laminate according to any one of claims 1 to 3, wherein the fiber structure includes a nonwoven fabric base material of ultrafine fibers.   The flexible decorative laminate according to any one of claims 1 to 4, wherein the decorative layer is artificial leather.   The said thermoplastic elastomer layer contains at least 1 sort (s) chosen from a styrene isoprene-type thermoplastic elastomer, a styrene butadiene-type thermoplastic elastomer, and a styrene-isoprene-butadiene-type thermoplastic elastomer, The any one of Claims 1-5. Flexible decorative laminate.   The flexible decorative laminate according to any one of claims 1 to 6, wherein the thermoplastic elastomer layer is an injection-molded body having a thickness of 0.5 mm or more. A method for producing a flexible decorative laminate,
Arranging a decorative sheet including a nonwoven fabric substrate of ultrafine fibers in a mold cavity of an injection molding machine;
And a step of injecting a non-porous thermoplastic elastomer onto the nonwoven fabric substrate side of the decorative sheet in the cavity to form a non-porous thermoplastic elastomer layer. A method for producing a decorative laminate.   The flexible decorative laminate according to claim 8, wherein the thermoplastic elastomer includes at least one selected from a styrene isoprene-based thermoplastic elastomer, a styrene-butadiene-based thermoplastic elastomer, and a styrene-isoprene-butadiene-based thermoplastic elastomer. Manufacturing method.