WO2019188988A1 - Synthetic resin skin material, method for producing synthetic resin skin material, and molded body - Google Patents

Synthetic resin skin material, method for producing synthetic resin skin material, and molded body Download PDF

Info

Publication number
WO2019188988A1
WO2019188988A1 PCT/JP2019/012519 JP2019012519W WO2019188988A1 WO 2019188988 A1 WO2019188988 A1 WO 2019188988A1 JP 2019012519 W JP2019012519 W JP 2019012519W WO 2019188988 A1 WO2019188988 A1 WO 2019188988A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
synthetic resin
skin
skin material
resin
Prior art date
Application number
PCT/JP2019/012519
Other languages
French (fr)
Japanese (ja)
Inventor
智彦 山田
忠彦 稲垣
Original Assignee
共和レザー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 共和レザー株式会社 filed Critical 共和レザー株式会社
Priority to CN201980013798.4A priority Critical patent/CN111727118A/en
Publication of WO2019188988A1 publication Critical patent/WO2019188988A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners

Definitions

  • the present disclosure relates to a synthetic resin skin material, a method for producing a synthetic resin skin material, and a molded body.
  • an insert molding method may be used as a method for producing an automotive interior part using a synthetic resin skin material.
  • a synthetic resin skin material is disposed on the surface of the molding resin material, and the molding resin material on which the synthetic resin skin material is disposed is heat-molded in a molding die, and the heated synthetic resin skin material. And the like. After the vacuum molding is performed in the mold, a fluid resin is poured into the mold from the back surface side of the skin material by injection molding, and the molding is performed by injection molding.
  • the irregularities formed on the surface of the synthetic resin skin material by heat disappear, and the appearance of the resulting thermoformed product
  • the shape of the mold which is a mold, is transferred to the surface of the synthetic resin skin material on the side exhibiting the shape, and the shape reflects the inner surface of the mold. Therefore, generally, in the molding by the insert molding method, the surface of the molded body expresses the design of the skin layer by printing or mirror surface. In the case of forming a molded body having a concavo-convex pattern on the surface, there is a problem that a mold having a concavo-convex pattern corresponding to the design is required.
  • An acrylic resin film substrate and a matting agent, a silicone-containing compound and / or a fluorine-containing resin provided as an outermost layer on one surface of the acrylic resin film substrate as a resin film whose designability does not deteriorate even when heat-molded A matte acrylic resin film for thermoforming comprising a matte layer containing a compound and a curable binder resin has been proposed (see Japanese Patent Application Laid-Open No. 2007-283665).
  • an insert film having a pattern ink layer or a printing layer on one or both sides of an acrylic film and having a fluorine film as an outermost layer and having good processability, chemical resistance, and contamination resistance has been proposed. (See Kaihei 09-066537 and JP 09-131749).
  • the problem of an embodiment of the present invention is that even when heat-molded using a mold, it has good workability, the uneven pattern formed on the outermost surface is well maintained, and the appearance is excellent. It is providing the synthetic resin skin material which can form a molded object, and its manufacturing method.
  • the problem of another embodiment of the present invention is that the appearance is excellent in solvent resistance, stain resistance, and weather resistance, and the uneven pattern on the skin layer of the synthetic resin skin material is maintained even after thermoforming.
  • An object of the present invention is to provide a good molded article.
  • Means for solving the problems include the following embodiments. ⁇ 1> A base material layer containing a thermoplastic resin, an intermediate layer provided on one surface of the base material layer, containing a polyvinyl chloride resin, and provided on the side opposite to the base material layer of the intermediate layer And a synthetic resin skin material comprising a skin layer having irregularities on the surface opposite to the intermediate layer side and containing a fluororesin.
  • the fluororesin is composed of a trifluoroethylene chloride-vinylidene fluoride copolymer, a vinylidene fluoride-6 propylene fluoride copolymer, and a vinylidene fluoride-6 fluoropropylene-4 fluoroethylene copolymer.
  • ⁇ 5> The synthetic resin skin material according to any one of ⁇ 1> to ⁇ 4>, wherein the base material layer includes an acrylonitrile / butadiene / styrene copolymer.
  • the synthetic resin skin material according to any one of ⁇ 1> to ⁇ 5> which is a skin material of a thermoformed product.
  • the synthetic resin skin material according to any one of ⁇ 1> to ⁇ 6> further including an adhesive layer on a surface opposite to the intermediate layer side of the base material layer.
  • a step of forming an intermediate layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin, a base material using a thermoplastic resin composition containing an acrylonitrile / butadiene / styrene copolymer A step of forming a layer, a step of preparing a skin layer containing a fluororesin, a step of laminating the skin layer, the intermediate layer and the base material layer in this order to obtain a laminate, and the obtained laminate
  • a method for producing a synthetic resin skin material comprising a step of applying a laminating embossing to the skin layer side of the skin layer using a squeezing roll and forming an uneven pattern on a surface of the skin layer opposite to the intermediate layer side.
  • the uneven pattern formed on the outermost surface is well maintained, and the appearance is excellent.
  • a synthetic resin skin material capable of forming a molded body and a method for producing the same can be provided.
  • the appearance is excellent in solvent resistance, stain resistance, and weather resistance, and the uneven pattern on the skin layer of the synthetic resin skin material is maintained even after thermoforming. Can be provided.
  • the synthetic resin skin material the manufacturing method of the synthetic resin skin material, and the molded body of the present disclosure will be described in detail.
  • the constituent elements described below may be described based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
  • “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
  • the term “step” is not limited to an independent step, and is included in the term if the intended purpose of the step is achieved even when it cannot be clearly distinguished from other steps.
  • the “layer containing a resin” in the present disclosure refers to a “layer formed including a resin that is a main component of the layer”. That is, the “layer containing a resin” in the present disclosure is a resin layer containing only a resin and a resin composition further containing optional components such as a plasticizer, a colorant, and an ultraviolet absorber in addition to a resin as a main component. It is used to include both formed layers.
  • the “resin that is a main component” in the present disclosure refers to a resin that is contained in an amount of 60% by mass or more based on the total amount of the resin composition containing the component.
  • the polyvinyl chloride resin may be referred to as a PVC resin.
  • An acrylonitrile / butadiene / styrene copolymer may be referred to as an ABS resin.
  • the synthetic resin skin material of the present disclosure includes a base material layer including a thermoplastic resin, an intermediate layer provided on one surface of the base material layer, including a PVC resin, and a base material layer of the intermediate layer opposite to the base material layer.
  • FIG. 1 is a schematic cross-sectional view illustrating an aspect of a layer configuration of a synthetic resin skin material 10 of the present disclosure.
  • the synthetic resin skin material 10 includes a base material layer 12 including a thermoplastic resin, an intermediate layer 14 including a PVC resin provided on one surface thereof, a design layer 16 provided as desired, and a design layer 16.
  • a skin layer 18 is provided in this order, provided on the surface opposite to the surface in contact with the intermediate layer 14, and having an uneven surface on the surface opposite to the intermediate layer 14 side, and containing a fluororesin.
  • synthetic resin skin material is referred to as “skin material”
  • base material layer including thermoplastic resin is referred to as “base material layer”
  • intermediate layer including PVC resin is referred to as “intermediate layer”.
  • the “layer” and the “skin layer containing a fluororesin” may be abbreviated as “skin layer”, respectively. That is, the synthetic resin skin material 10 shown in FIG. 1 which is an embodiment of the skin material of the present disclosure includes a base material layer 12, an intermediate layer 14, a design layer 16, and a skin layer 18 in order. The surface of the skin layer 18 opposite to the side in contact with the design layer 16 has a concavo-convex pattern also referred to as a texture pattern.
  • the concavo-convex pattern is a pattern that characterizes the appearance of the surface of the molded body made of a synthetic resin skin material, typified by a natural leather-like concavo-convex pattern.
  • the synthetic resin skin material of the present disclosure can be used as a skin material of a molded body formed by heat molding such as insert molding as described later.
  • the design layer 16 shown in FIG. 1 is an arbitrary layer provided as desired in the synthetic resin skin material of the present disclosure, and is not necessarily required.
  • the synthetic resin skin material of the present disclosure has an unevenness formed on one surface of the skin layer, having an uneven surface on one surface and a layer having good heat resistance containing a fluororesin. The pattern is not easily deformed by heating. Furthermore, the skin layer is laminated with an intermediate layer containing a PVC resin so that the synthetic resin skin material of the present disclosure is placed in the mold and molten resin is injected, or the surface of the molded substrate is disclosed. When the synthetic resin skin material is laminated and molded with a mold, the intermediate layer that is flexible and easily deforms during heat molding reduces the influence of thermal stress on the skin layer.
  • corrugated pattern formed on the surface of the skin layer is suppressed effectively, without impairing the heat moldability of a synthetic resin skin material. Therefore, by using the synthetic resin skin material of the present disclosure, the unevenness pattern (texture pattern) formed on the surface of the skin layer is high even after heat molding such as insert molding. Can be performed independently of the formation of the molded body by thermoforming, and it is possible to produce molded bodies having various uneven patterns on the surface without changing the molding die. Have.
  • the synthetic resin skin material of the present disclosure may be provided with a design layer between the skin layer and the intermediate layer. Since there is no particular limitation on the design layer provided as desired, the desired design can be formed, and the uneven pattern on the surface of the skin layer is maintained even after heat molding. The degree of freedom is high and the design properties are good.
  • the synthetic resin skin material of the present disclosure has good heat moldability such as insert molding, and the uneven pattern of the surface layer of the synthetic resin skin material is well maintained on the surface of the molded body obtained after the heat molding. For this reason, the synthetic resin skin material of the present disclosure having excellent design properties and good thermal processability is suitably used for various applications such as vehicle interior materials obtained by laminating with a molding substrate and performing thermoforming. Is done.
  • the base material layer includes a thermoplastic resin.
  • the thermoplastic resin that can be used for the base material layer is not particularly limited, and is a known thermoplastic in consideration of various conditions such as affinity with the resin constituting the molded article to be applied and stretchability when molded. It can select suitably from resin.
  • thermoplastic resin examples include polyethylene (PE), polypropylene (PP), PVC resin, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (PUR), ABS resin, acrylonitrile / Examples thereof include acrylic resins such as styrene copolymer (AS resin), polycarbonate (PC), and polymethyl methacrylate (PMMA), and fluorine resins such as polytetrafluoroethylene (PTFE).
  • PE polyethylene
  • PP polypropylene
  • PVC resin polystyrene
  • PS polyvinyl acetate
  • PUR polyurethane
  • ABS resin acrylonitrile /
  • acrylic resins such as styrene copolymer (AS resin), polycarbonate (PC), and polymethyl methacrylate (PMMA)
  • fluorine resins such as polytetrafluoroethylene (PTFE).
  • the thermoplastic resin contained in the base material layer is composed of ABS resin, AS Resin, PC, PP, and a mixture of PC and ABS resin (PC / ABS) are preferable, and ABS resin is more preferable.
  • the base material layer may contain various components other than the thermoplastic resin in addition to the thermoplastic resin.
  • examples of other components that can be included in the base material layer include colorants, plasticizers, fillers, lubricants, and processing aids.
  • a base material layer contains a coloring agent.
  • the base material layer contains a colorant, when the synthetic resin skin material is placed on the surface of the resin that becomes the base material of the molded body and the molded body is produced, the molded base material affects the appearance of the molded body. Can be suppressed.
  • Dye a pigment, etc.
  • Colorants include titanium white (titanium dioxide), zinc white, ultramarine blue, cobalt blue, dial, inorganic pigments such as vermilion, yellow lead, titanium yellow, carbon black, quinacridone, permanent red 4R, isoindolinone, and hansa yellow.
  • organic pigments or dyes such as phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments selected from the group consisting of metal foil powders such as aluminum and brass, titanium dioxide-coated mica and basic lead carbonate foil powders And nacreous (pearl) pigments selected from the group.
  • metal pigments selected from the group consisting of metal foil powders such as aluminum and brass, titanium dioxide-coated mica and basic lead carbonate foil powders And nacreous (pearl) pigments selected from the group.
  • a pigment that is a colorant having excellent weather resistance and durability is preferable, and black pigments such as carbon black, aniline black, and perylene black are more preferable from the viewpoint of effectively hiding the molding substrate.
  • the base material layer may contain extender pigments (fillers) such as calcium carbonate, silica (silicon dioxide), alumina (aluminum oxide), and barium sulfate as necessary.
  • a base material layer contains a coloring agent
  • only 1 type of coloring agents may be included and 2 or more types may be included for the purpose of toning.
  • the content of the colorant in the resin composition used for forming the base material layer is not particularly limited, and the type of the colorant to be used depends on the target hue in the synthetic resin skin material, the hiding property of the molding base material, and the like. The content may be selected as appropriate.
  • the content of a general colorant when using a colorant is preferably 1% by mass to 20% by mass with respect to the total solid content of the resin composition constituting the base material layer, and preferably 2% by mass to More preferably, it is 10 mass%.
  • solid content means the total amount of the component except the solvent in all the components of the resin composition which comprises a base material layer here.
  • the thickness of the base material layer is preferably in the range of 50 ⁇ m to 400 ⁇ m, and more preferably in the range of 100 ⁇ m to 350 ⁇ m.
  • the thickness of the base material layer and the thickness of each layer described later in the synthetic resin skin material can be measured by observing a cut surface obtained by cutting the synthetic resin skin material perpendicularly to the surface direction. Therefore, the film thickness of each layer in the synthetic resin skin material in the present disclosure refers to the film thickness after drying.
  • a well-known sheet forming method for example, the extrusion method extrusion-molding with a T die etc., a calendar method, a casting method, etc. are applicable.
  • the calendar method is preferable in terms of ease of production and easy maintenance of the apparatus.
  • the base material layer contains a colorant
  • a softened resin and a solid colorant can be supplied to a calender roll and formed into a sheet or film, so that groups containing various colorants can be used.
  • the material layer can be easily manufactured.
  • An intermediate layer is provided on one surface of the base material layer described above.
  • the intermediate layer contains a PVC resin.
  • the intermediate layer may contain other components in addition to the PVC resin.
  • examples of other components that the intermediate layer may include include a colorant, a plasticizer, a filler, a lubricant, and a processing aid.
  • other components can be used in the range which does not reduce the heat workability of an intermediate
  • the intermediate layer can include a colorant. When the intermediate layer contains a colorant, it is possible to prevent the molding base used from affecting the appearance of the molded body when producing the molded body, and to arrange a synthetic resin skin material, and therefore a synthetic resin skin material. Depth can be imparted to the color of the molded article.
  • the colorant that can be used for the intermediate layer is the same as the colorant that can be used for the base layer described above, and a desired color may be selected according to the purpose.
  • the preferred content of the colorant when used in the intermediate layer can also be appropriately selected according to the purpose. From the viewpoint of the uniformity of the layer, it is preferably 20% by mass or less based on the total solid content of the resin composition used for forming the intermediate layer.
  • the thickness of the intermediate layer is preferably in the range of 50 ⁇ m to 300 ⁇ m, and more preferably in the range of 100 ⁇ m to 250 ⁇ m.
  • the heat stress applied to the skin layer is reduced when a synthetic resin skin material is heated to form a molded body, and the unevenness pattern formed on the surface of the skin layer is retained. Is better.
  • the skin layer of the synthetic resin skin material contains a fluororesin.
  • the fluororesin that can be used for the skin layer is not particularly limited as long as it is a resin obtained by polymerization using at least one monomer containing a fluorine atom as a polymerization component.
  • a fluororesin resin obtained by superposing
  • the fluororesin include a resin that includes a polymerization component selected from ethylene tetrafluoride, trifluoroethylene chloride, vinyl fluoride, and vinylidene fluoride.
  • a trifluoride chloride is a homopolymer of a polymer component containing a fluorine atom, such as a tetrafluoroethylene resin, a vinyl fluoride resin, or a vinylidene fluoride resin, and a copolymer containing the polymer component.
  • a fluorine atom such as a tetrafluoroethylene resin, a vinyl fluoride resin, or a vinylidene fluoride resin
  • a copolymer containing the polymer component examples thereof include an ethylene-vinylidene fluoride copolymer, a vinylidene fluoride-6-propylene fluoride copolymer, and a vinylidene fluoride-6-propylene-4-tetrafluoroethylene copolymer.
  • ethylene trifluoride-vinylidene fluoride copolymer vinylidene fluoride-6-propylene fluoride copolymer, and vinylidene fluoride-6-propylene-4-tetrafluoroethylene copolymer It is preferable to include at least one selected fluororesin.
  • the skin layer may contain only one type of the fluororesin, or two or more types may be used in combination. Moreover, you may use together at least 1 sort (s) of a fluororesin, and at least 1 sort (s) of resin other than a fluororesin.
  • the skin layer contains two or more kinds of fluororesins, for example, vinylidene fluoride resin, trifluoroethylene chloride-vinylidene fluoride copolymer, vinylidene fluoride-6 fluoropropylene copolymer, and fluoride It is also a preferred embodiment to use a mixture of two or more kinds of resins selected from the group consisting of vinylidene-6 fluoropropylene-4 fluoroethylene copolymer.
  • the skin layer includes two or more kinds of resins
  • the skin layer is a mixture of two or more kinds of resins as described above
  • the skin layer is a laminated structure of two or more kinds of resins.
  • the outermost surface that is, the surface corresponding to the outside when the synthetic resin skin material is disposed on the molded body is a layer containing a fluororesin, and the skin layer and an intermediate layer or a design layer provided as desired
  • the skin layer is formed as a two-layer structure of a layer containing a fluororesin and a layer containing an acrylic resin, and the layer side containing the acrylic resin is positioned on the surface in contact with the design layer it can.
  • the skin layer may be obtained by molding, or a commercially available film may be applied.
  • the commercially available film that can be used for the skin layer include KCF film manufactured by Kureha Extec Co., Ltd., Acryprene (registered trademark) FBS006 manufactured by Mitsubishi Chemical Corporation.
  • the KFC film is a multilayer film having a laminated structure of a polyvinylidene fluoride layer and an acrylic resin layer.
  • Acryprene is a multilayer film having a laminated structure of a fluororesin-containing layer and an acrylic resin-containing layer.
  • the thickness of the skin layer is preferably in the range of 5 ⁇ m to 100 ⁇ m, more preferably in the range of 5 ⁇ m to 50 ⁇ m, from the viewpoint of strength and ruggedness pattern retention.
  • the thickness of the skin layer refers to the distance from the top of the convex portion of the surface on which the concavo-convex pattern is formed to the bottom surface of the skin layer.
  • the thickness of the skin layer is such that the bottom part and the convex part in the deepest part of the concave part of the concave-convex pattern are from the viewpoint of the retention of the concave-convex pattern formed on the side opposite to the intermediate layer in the skin layer or the design layer side provided as desired.
  • the thickness of the skin layer can be about 5 ⁇ m, and it has a shallow concave portion and a deep concave portion like a natural leather-like pattern.
  • the thickness of the skin layer is preferably 10 ⁇ m or more. Note that the thickness of the skin layer when the skin layer has a laminated structure of two or more layers as described above refers to the total thickness of a plurality of layers.
  • the method of forming the skin layer on the surface opposite to the surface on the base material layer side of the intermediate layer or the design layer provided as desired is arbitrary.
  • a pre-formed skin layer and an intermediate layer or a design layer provided as desired may be adhered, and after forming the skin layer, an intermediate layer is formed on one surface of the skin layer by the method described above. Also good.
  • a known method can be applied.
  • Known methods include a method of forming a skin layer on a release paper having a concavo-convex pattern, a method of first forming a skin layer having a smooth surface, and then embossing using a squeeze roll.
  • the thickness of each layer in the synthetic resin skin material of the present disclosure is such that the thickness of the skin layer is in the range of 5 ⁇ m to 100 ⁇ m, the thickness of the intermediate layer is in the range of 50 ⁇ m to 300 ⁇ m, and The thickness of the base material layer is preferably in the range of 50 ⁇ m to 400 ⁇ m. Further, when the thickness of the intermediate layer is 100, the thickness of the skin layer is preferably in the range of 15 to 55. In addition, about the preferable thickness of the design layer which is arbitrary layers, it mentions later.
  • the synthetic resin skin material of the present disclosure has an outer layer having a skin layer that is excellent in transparency and durability on the outermost surface, and that has good maintainability of the uneven pattern during heating, and is excellent in heat workability.
  • the synthetic resin skin material of this indication has the favorable retention of the uneven
  • the synthetic resin skin material may further have other layers in addition to the above-described base material layer, intermediate layer and skin layer as long as the effects are not impaired.
  • Examples of other layers include a design layer, an adhesive layer, and a primer layer.
  • the synthetic resin skin material may further have a design layer on the surface of the intermediate layer described above on the side opposite to the base material layer side.
  • the design layer is a layer that imparts a design to the synthetic resin skin material, and may be a printed layer formed by printing, may be a colored layer containing a colorant, or may be a layer that uses these in combination. Good.
  • the design layer is not particularly limited. Therefore, by forming various design layers according to the use of the synthetic resin skin material as desired, the molded article has excellent desired design properties. Appearance can be imparted.
  • the printing layer can be formed by, for example, a printing method on the surface of the intermediate layer or the above-described skin layer.
  • a printing layer the layer formed by the well-known printing method with the printing ink containing resin is mentioned.
  • the printing ink containing a resin is preferably a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or the like from the viewpoint that a clear print image can be formed.
  • limiting in particular in a printing method Arbitrary printing methods, such as gravure printing (intaglio printing), relief printing, offset printing, inkjet printing, and screen printing, can be applied.
  • a printing ink layer containing at least one selected from an acrylic resin and a vinyl chloride-vinyl acetate copolymer is preferable.
  • the colored layer examples include a layer formed of a resin composition containing an arbitrary colorant.
  • a resin composition containing an acrylic resin and a colorant selected from those listed as the colorant that can be used in the base material layer described above was formed into a film by a calendar method, an extrusion method, a casting method, or the like.
  • Examples include a design layer.
  • PMMA polymethyl methacrylate
  • a copolymer of alkyl methacrylate, alkyl acrylate and styrene, and a mixture of methyl methacrylate and methyl acrylate copolymer are preferred.
  • the acrylic resin is excellent in weather resistance and stretchability, and has good adhesion to other resin layers provided adjacent to each other.
  • acrylic resin since acrylic resin has good transparency, it can be synthesized by adding a colorant or the like to the acrylic resin, or adding a light scattering colorant such as a pigment having a metallic luster or a pearl pigment. Desired good hue, design excellent in gloss, etc. can be arbitrarily given to the resin skin material.
  • a more complicated arbitrary design can be provided to a synthetic resin skin material by printing a character, an image, etc.
  • the thickness of the design layer is preferably in the range of 1 ⁇ m to 15 ⁇ m, more preferably in the range of 2 ⁇ m to 10 ⁇ m, and in the range of 2 ⁇ m to 5 ⁇ m. Is more preferable.
  • a desired design can be provided to a synthetic resin skin material because the thickness of the design layer is within the above range.
  • the thickness of the design layer is within the above range, a good correlation between the skin layer and the intermediate layer is maintained when a molded body is formed by thermal processing using a synthetic resin skin material, and the thickness of the skin layer is maintained. The retainability of the uneven pattern becomes better.
  • the thickness ratio of the synthetic resin skin material layer is preferably in the range of 1 to 10 when the thickness of the intermediate layer is 100.
  • the design layer is preferably thinner than the skin layer as compared with the thickness of the skin layer described above being preferably in the range of 15 to 55 with respect to the thickness 100 of the intermediate layer.
  • the adhesive layer can be formed by applying at least one of a known adhesive and pressure-sensitive adhesive to the surface of the base material layer opposite to the intermediate layer.
  • a known adhesive and pressure-sensitive adhesive there is no restriction
  • the adhesive for example, (1) a two-component curable polyester adhesive, (2) a two-component curable urethane adhesive, and (3) a two-component curable acrylic pressure-sensitive adhesive are preferably used.
  • the adhesive used for forming the adhesive layer is also available as a commercial product.
  • the Oliveline series [Toyo Ink Co., Ltd.]
  • Welder Adhesive No. 3660 two-component curable polyurethane adhesive: No Tape Industry Co., Ltd.]
  • Daikarak 7250NT two-component curable polyester adhesive: Daido Kasei Kogyo Co., Ltd.
  • the thickness of the adhesive layer is preferably in the range of 20 ⁇ m to 50 ⁇ m.
  • An adhesive layer can be formed by forming a primer layer on the surface of the synthetic resin skin material on which an adhesive is to be formed and applying at least one of an adhesive and an adhesive to the surface of the formed primer layer.
  • a method for providing the adhesive layer on the base material layer or the primer layer any known method such as a transfer method or a coating method can be used. From the viewpoint that an adhesive layer having a uniform thickness can be easily formed, it is preferable to use a transfer method.
  • a protective sheet may be provided on the surface of the adhesive layer for the purpose of protecting the surface of the adhesive layer.
  • a resin film, release-treated paper, resin-laminated paper, or the like can be used as appropriate. What is necessary is just to peel a protective sheet, when bonding a synthetic resin skin material to the resin material for molded object formation mentioned later.
  • a primer layer is further used as a primer layer for the purpose of improving the adhesion between the base material layer and the resin molded body. You may have between material layers.
  • the primer layer can be formed by a coating method. That is, the primer layer can be formed by dissolving the resin for forming the primer layer with an appropriate solvent, applying the resin to the surface of the base material layer opposite to the skin layer side, and drying.
  • the resin contained in the primer layer is a resin such as a polyester resin from the viewpoint of good affinity with the thermoplastic resin contained in the base material layer and the adhesive contained in the adjacent adhesive layer. It is preferable to form using.
  • the range is preferably 1 g / m 2 to 5 g / m 2 , and more preferably 2 g / m 2 to 3 g / m 2 .
  • the synthetic resin skin material manufacturing method of the present disclosure includes a step of forming an intermediate layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin (step (I)), acrylonitrile / butadiene / styrene.
  • a step of forming a base material layer using a thermoplastic resin composition containing a copolymer (step (II)), a step of preparing a skin layer containing a fluororesin (step (III)), the skin layer and the intermediate
  • the layer and the base material layer are laminated in this order to obtain a laminate (step (IV)), and the skin layer side of the obtained laminate is subjected to laminate embossing using a squeeze roll,
  • a step of forming a concavo-convex pattern on the surface of the skin layer opposite to the side having the intermediate layer (step (V)).
  • the manufacturing method of the synthetic resin skin material of this indication can further include the process (process (VI)) of forming a design layer between the said skin layer and the said intermediate
  • step (I) an intermediate layer containing a polyvinyl chloride resin is formed by a known method such as a calendering method, an extrusion method, or a casting method using a resin composition containing a polyvinyl chloride resin.
  • a calendar method for example, an intermediate layer having a uniform film thickness can be easily formed as compared with a melt extrusion method or the like.
  • the intermediate layer contains a colorant
  • by applying the calender method it is easy to clean the inside of the device necessary when changing the type and amount of colorant used in the intermediate layer.
  • An example of a method of forming an intermediate layer using a PVC resin and a pigment as a colorant is a PVC resin colored by adding a predetermined amount of pigment to the PVC resin and heating and mixing with a heat mixing roll. And forming an intermediate layer by a calendar method using the obtained colored PVC resin. When no colorant is used, the process can be performed in the same manner by omitting the pigment charging step.
  • a base material layer is formed by a known method such as a calendar method, an extrusion method, or a casting method using a thermoplastic resin composition containing an ABS resin. Especially, it is preferable to form a base material layer by the calendar method from a viewpoint of workability.
  • the formation method of the base material layer by the calendar method can be performed in the same manner as the formation method of the intermediate layer in the step (I) except that the resin used is different.
  • a colorant is contained, as in step (I)
  • a predetermined amount of pigment is added to the ABS resin, and the ABS resin is colored by heating and mixing with a heat mixing roll. And forming a base material layer by a calendering method using the obtained colored ABS resin.
  • process (I) and process (II) are arbitrary, and can be performed independently.
  • a skin layer containing a fluororesin is prepared. Preparing the skin layer includes both forming a skin layer containing a fluororesin and procuring a commercially available skin layer.
  • a skin layer containing a fluororesin can be formed by a calendar method, an extrusion method, a casting method, or the like.
  • a method of forming a laminated film by coextrusion or the like of two or more resins can be applied.
  • step (III) includes preparing a commercially available film as described above in the description of the synthetic resin skin material including a fluororesin as the skin layer.
  • step (IV) the intermediate layer formed in step (I), the base material layer formed in step (II), and the skin layer prepared in step (III) are divided into a skin layer, an intermediate layer, and a base material layer. Is laminated in this order to obtain a laminate.
  • the laminate is formed by laminating an intermediate layer and a base material layer in this order on one surface of the skin layer. Each laminated layer is pressurized and heated by a pair of rollers to form a laminate.
  • step (V) laminate embossing is performed on the skin layer side of the laminate obtained in step (IV) using a squeeze roll, and a concavo-convex pattern is formed on the surface of the skin layer opposite to the intermediate layer side.
  • Step (IV) and step (V) can be performed simultaneously. That is, the intermediate layer and the base material layer are laminated in this order on one surface of the skin layer, and then the laminate is embossed with a squeezing roll to heat and pressure bond each layer, and the skin layer.
  • the desired concavo-convex pattern can be simultaneously formed on the surface.
  • the laminate embossing is embossed by using a squeezing roll on one of a pair of embossing rolls for thermocompression bonding, and a plurality of resin-containing films are bonded together by thermocompression bonding, and in contact with the squeezing roll of the resin-containing film. It refers to forming irregularities on the surface by squeezing the surface with a squeeze roll.
  • a laminate embossing method can be employed in such an arrangement that a squeeze roll is located on the skin layer side and a smooth roll is located on the substrate layer side. According to this method, lamination of each layer and formation of the uneven pattern in the skin layer can be performed sequentially or simultaneously in one step.
  • Step (VI) is an optional step of further forming a design layer in the method for producing a synthetic resin skin material.
  • a design layer is formed on one surface of the skin layer prepared in step (III) or the intermediate layer formed in step (I).
  • the method for forming the design layer include a method of adhering a pre-formed design layer to one side of the skin layer or the intermediate layer, an acrylic resin or a vinyl chloride-vinyl acetate copolymer on one side of the skin layer or the intermediate layer. And a method of performing printing using a printing ink containing. Especially, it is preferable to form the design layer by printing because the degree of freedom of the design is high.
  • a design method of a design layer in a design layer including a design, it is possible to apply a printing method. If the design layer is a colored layer, a resin composition containing a colorant can be obtained by a known method. The method etc. which shape
  • the printing method is a method of printing a known pattern with a printing ink containing a resin.
  • a printing ink containing a resin for example, a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer or the like is used as a known printing method. Examples thereof include a method of printing and forming by gravure printing (intaglio printing), letterpress printing, offset printing, ink jet printing, screen printing and the like.
  • Specific examples of the printing method include printing on one surface of the skin layer using a printing ink containing an acrylic resin by gravure printing. By adjusting the engraving size of the print roll used for gravure printing, printing can be performed while adjusting the amount of printing ink applied.
  • various designs can be formed on one surface of the skin layer. Since the design layer which is an arbitrary layer can be independently formed as desired on one surface of the skin layer or the intermediate layer, a layer having a desired design with an arbitrary hue and an arbitrary design can be formed. Therefore, by providing the design layer, various designs can be imparted to the synthetic resin skin material.
  • the above-described synthetic resin skin material of the present disclosure is suitably used for the purpose of imparting a design to the surface of the molded body when producing a molded body by thermoforming.
  • the molded body of the present disclosure is a molded body having the molded base material and the above-described synthetic resin skin material of the present disclosure disposed on the surface of the molded base material.
  • the molded body can be formed by thermoforming. There is no restriction
  • a synthetic resin skin material is placed on the surface of a molding base material that may be preformed in advance, or a synthetic resin skin material is placed in a mold and a molding base material is placed.
  • a mold for example, a method of molding under a temperature condition of 90 ° C. to 140 ° C., and a synthetic resin skin material is placed in the mold, and then a resin that becomes a molding substrate heated and melted is molded into the mold
  • molding base material used for the manufacturing process of a molded object is resin generally used for shaping
  • the heating temperature condition is preferably in the range of 90 ° C to 140 ° C.
  • the molding is performed by heating to the melting temperature of the resin as the molding substrate.
  • the synthetic resin skin material of the present disclosure has good heat moldability, and retains the uneven pattern formed on the surface of the skin layer even after heat molding using a molten resin such as insert molding. It is good. For this reason, it can be said that the effect is usually remarkable when applied to an insert molding method in which it is difficult to maintain the design layer and the uneven pattern on the surface.
  • the synthetic resin skin material of the present disclosure can be manufactured by a simple method, is excellent in appearance and durability, and is suitably used as a skin material for thermoforming. It can be suitably used in various fields such as aircraft interior parts, furniture, shoes, footwear, bags, building interior / exterior members, clothing cover materials and linings.
  • KFC film FT-50Y (trade name), Kureha Extec Co., Ltd. (a laminate of a polyvinylidene fluoride-containing layer that is a fluororesin and a polymethylmethacrylate-containing layer that is an acrylic resin) was prepared as a skin layer (process) (III)).
  • a printing ink containing acrylic resin VTP-NT (trade name), DIC Corporation) on the polymethyl methacrylate-containing layer side of the skin layer, a wood grain pattern is printed to form a 5 ⁇ m thick design layer (Step (VI)).
  • step (IV) On the side opposite to the side having the skin layer of the design layer formed in the previous step, a preformed intermediate layer and a base material layer were laminated in this order (step (IV)).
  • the embossed roll which is a drawn roll in which one of a pair of embossed rolls has a drawn pattern
  • the skin layer side is brought into contact with the drawn roll, and laminate embossing is performed on the base material layer.
  • the synthetic resin skin material of Example 1 which has an intermediate
  • the temperature conditions in the laminate embossing were such that the laminate surface temperature was 170 ° C. and the speed was 10 m / min.
  • the design layer forming step (step (VI)) which is an optional step, is performed after step (III) and before step (IV), so that the intermediate layer and the skin layer are formed.
  • a design layer was formed between the two.
  • the concave depth retention after heating was about 90%, the shape of the irregularities of the drawn pattern was maintained after heating, and the appearance after heating was also good.
  • Table 1 shows the retention ratio of the recess depth after heating.
  • the recess depth retention is 70% or more, it is at a level that can be practically used as a molded body for thermoforming.
  • the depth retention is less than 70%, it is a practically problematic level.
  • those having a recess depth retention of less than 50% are unsuitable levels as a synthetic resin skin material applied to the surface of a molded body to be heat-molded.
  • Example 1 Manufacture of molded products
  • a resin for a molding substrate acrylonitrile / butadiene / styrene copolymer (ABS)
  • ABS acrylonitrile / butadiene / styrene copolymer
  • the temperature condition is the melting temperature of the resin before injection.
  • the obtained molded body was evaluated according to the following criteria.
  • the evaluation results are shown in Table 1 below.
  • the evaluation results other than the maintainability of the concavo-convex pattern were “A” when there was no change or deterioration in appearance by visual observation, and “B” when change or deterioration was observed in appearance. “-” Indicates that the evaluation was not performed.
  • the synthetic resin skin material on the surface of the molded body after heat molding if the recess depth retention is 50% or more, for example, even if it is used for forming a molded body with heating, there is a practical problem. If it is less than 50%, a practically problematic level is determined. As a result of the evaluation, it was confirmed that the synthetic resin skin material of Example 1 has excellent ruggedness maintainability even on the surface of the molded body after heating.
  • Example 2 Example 1 except that the KFC film used as the skin layer was replaced with acrylprene (registered trademark) FBS006 (trade name), which is a laminate of a fluororesin-containing layer and an acrylic resin-containing layer, and Mitsubishi Chemical Corporation. Then, a synthetic resin skin material of Example 2 was produced, and using the obtained synthetic resin skin material, a molded body was produced in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 1 below.
  • acrylprene registered trademark
  • FBS006 trade name
  • Comparative Example 1 The KFC film used as the skin layer was replaced with acrylprene (registered trademark) film HBS010P (trade name) and Mitsubishi Chemical Corporation, which are polymethyl methacrylate films. Further, in place of the PVC resin for forming the intermediate layer, the synthetic resin skin material of Comparative Example 1 was produced in the same manner as in Example 1 except that the same ABS resin as that used for the production of the base material layer was used. Using the obtained synthetic resin skin material, a molded body was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The retention of the uneven pattern as the skin material is extremely low at 3%, and the depth of the uneven pattern after forming the molded body was difficult to measure under the same conditions. Indicated.
  • acrylprene registered trademark
  • HBS010P trade name
  • Mitsubishi Chemical Corporation Mitsubishi Chemical Corporation
  • Comparative Example 2 A synthetic resin skin material of Comparative Example 1 was prepared and obtained in the same manner as in Example 1 except that the same ABS resin as that used for the production of the base material layer was used instead of the PVC resin for forming the intermediate layer. Using the obtained synthetic resin skin material, a molded body was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
  • the synthetic resin skin materials of the examples are excellent in the retention of the unevenness (drawing) pattern on the surface even under heating conditions, and the molded products obtained using this have good insert moldability. It can be seen that it is excellent in durability such as solvent resistance and chemical resistance, and is excellent in retaining the unevenness (drawing) pattern formed on the surface of the synthetic resin skin material even after thermoforming.
  • the synthetic resin skin material of Comparative Example 1 in which the resin used for the skin layer and the intermediate layer is outside the scope of claim 1 has an extremely low unevenness retention rate, and the unevenness disappeared after the heat molding.
  • the synthetic resin skin material of Comparative Example 2 in which the resin used for the intermediate layer is outside the scope of claim 1 has an uneven pattern as the skin material.
  • the retention rate and the concavo-convex pattern retainability of the molded body obtained using the synthetic resin skin material are inferior to those of the examples, and the concavo-convex pattern retainability can be put to practical use for forming an insert molded body. There was no level.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention provides a synthetic resin skin material which is provided with: a base material layer which contains a thermoplastic resin; an intermediate layer which is provided on one surface of the base material layer and contains a polyvinyl chloride resin; and a skin layer which is provided on a surface of the intermediate layer, said surface being on the reverse side of the base material layer-side surface, and which contains a fluororesin, while having recesses and projections on a surface that is on the reverse side of the intermediate layer-side surface. The present invention also provides: a method for producing this synthetic resin skin material; and a molded body.

Description

合成樹脂表皮材、合成樹脂表皮材の製造方法及び成形体Synthetic resin skin material, method for producing synthetic resin skin material, and molded article
　本開示は、合成樹脂表皮材、合成樹脂表皮材の製造方法及び成形体に関する。 The present disclosure relates to a synthetic resin skin material, a method for producing a synthetic resin skin material, and a molded body.
　近年、自動車内装外装部品（インストルメントパネル、ドアトリム、座席、天井など）、鉄道車輌及び航空機の内装部品（トリム、座席、天井など）、家具、靴、履物、鞄、建装用内外装部材、衣類表装材及び裏地、壁装材などには、天然皮革や繊維性シートに代えて、耐久性に優れる合成樹脂表皮材が多用されている。合成樹脂表皮材は、最表面に天然皮革に類似した凹凸、即ち、絞（シボ）模様を有しており、この絞模様が外観を特徴付ける。例えば、自動車内装品については、車輌の高級化に伴い、内装用の合成樹脂表皮材についても高級感を付与させることが重要になっている。 In recent years, automotive interior / exterior parts (instrument panels, door trims, seats, ceilings, etc.), railway vehicle and aircraft interior parts (trims, seats, ceilings, etc.), furniture, shoes, footwear, bags, interior / exterior components for construction, clothing Synthetic resin skin materials having excellent durability are frequently used as the surface covering materials, lining materials, wall covering materials, and the like, instead of natural leather and fibrous sheets. The synthetic resin skin material has unevenness similar to natural leather on the outermost surface, that is, a drawn pattern, and this drawn pattern characterizes the appearance. For example, with respect to automobile interior parts, it is important to give a sense of quality to interior synthetic resin skin materials as the quality of vehicles increases.
　合成樹脂表皮材を用いて、例えば、自動車用内装部品を作製する方法としては、インサート成形方法が挙げられる。インサート成形方法としては、成形用樹脂材料表面に合成樹脂表皮材を配置して、合成樹脂表皮材が配置された成形用樹脂材料を成形金型内で加熱成形する方法、加熱した合成樹脂表皮材を金型内で真空成形した後、射出成形により表皮材裏面側から金型内に流動性の樹脂を流し込み射出成形により成形する方法等が挙げられる。しかし、いずれのインサート成形方法においても、加熱して軟化した合成樹脂表皮材を成形する際に、熱により合成樹脂表皮材の表面に形成された凹凸が消失し、得られた加熱成形体の外観を呈する側の合成樹脂表皮材表面には、成形型である金型の形状が転写され、金型の内側表面が反映された形状となる。従って、一般には、インサート成形法による成形では、成形体の表面は、印刷もしくは鏡面で表皮層の意匠を表現している。表面に凹凸模様を有する成形体を形成する場合には、意匠に応じた凹凸模様を有する金型が必要となるという問題があった。 For example, an insert molding method may be used as a method for producing an automotive interior part using a synthetic resin skin material. As an insert molding method, a synthetic resin skin material is disposed on the surface of the molding resin material, and the molding resin material on which the synthetic resin skin material is disposed is heat-molded in a molding die, and the heated synthetic resin skin material. And the like. After the vacuum molding is performed in the mold, a fluid resin is poured into the mold from the back surface side of the skin material by injection molding, and the molding is performed by injection molding. However, in any of the insert molding methods, when molding a synthetic resin skin material that has been softened by heating, the irregularities formed on the surface of the synthetic resin skin material by heat disappear, and the appearance of the resulting thermoformed product The shape of the mold, which is a mold, is transferred to the surface of the synthetic resin skin material on the side exhibiting the shape, and the shape reflects the inner surface of the mold. Therefore, generally, in the molding by the insert molding method, the surface of the molded body expresses the design of the skin layer by printing or mirror surface. In the case of forming a molded body having a concavo-convex pattern on the surface, there is a problem that a mold having a concavo-convex pattern corresponding to the design is required.
　加熱成形しても意匠性が低下しない樹脂フィルムとして、アクリル樹脂フィルム基体と、該アクリル樹脂フィルム基体の一方の面上に最外層として設けられた、艶消し剤、含シリコーン化合物及び／又は含フッ素化合物、及び硬化性バインダー樹脂を含有する艶消し層と、からなる熱成形用艶消しアクリル樹脂フィルムが提案されている（特開２００７－２８３６６５号公報参照）。また、アクリルフィルムの片面又は両面に図柄インキ層又は印刷層を有し、最外層としてフッ素フィルムを有する、加工性、耐薬品性、及び耐汚染性が良好なインサートフィルムが提案されている（特開平０９－０６６５３７号公報及び特開平０９－１３１７４９号公報参照）。 An acrylic resin film substrate and a matting agent, a silicone-containing compound and / or a fluorine-containing resin provided as an outermost layer on one surface of the acrylic resin film substrate as a resin film whose designability does not deteriorate even when heat-molded A matte acrylic resin film for thermoforming comprising a matte layer containing a compound and a curable binder resin has been proposed (see Japanese Patent Application Laid-Open No. 2007-283665). In addition, an insert film having a pattern ink layer or a printing layer on one or both sides of an acrylic film and having a fluorine film as an outermost layer and having good processability, chemical resistance, and contamination resistance has been proposed. (See Kaihei 09-066537 and JP 09-131749).
　しかしながら、上記特開２００７－２８３６６５号公報に記載の技術では、表皮材を表面に配置した成形用樹脂材料を加熱成形した場合に、表皮材が有する艶消しに有用な程度の微細な凹凸形状は維持されるが、表皮材が複雑で深い凹凸模様を有する場合には、加熱、加圧等の影響により、表皮材の最表面に形成された凹凸が変形したり、失われたりする場合がある。
　また、特開平０９－０６６５３７号公報及び特開平０９－１３１７４９号公報に記載の技術では、意匠性として鏡面又は印刷柄を表現できるのみであり、表皮材により成形体の表面に凹凸模様を形成することについては検討されていない。 However, in the technique described in Japanese Patent Application Laid-Open No. 2007-283665, when the molding resin material having the skin material disposed on the surface is thermoformed, the fine uneven shape of the skin material useful for matting is not Although it is maintained, when the skin material has a complex and deep concavo-convex pattern, the concavo-convex formed on the outermost surface of the skin material may be deformed or lost due to the influence of heating, pressurization, etc. .
Further, in the techniques described in Japanese Patent Application Laid-Open Nos. 09-066537 and 09-131749, only a mirror surface or a printed pattern can be expressed as a design, and an uneven pattern is formed on the surface of the molded body by a skin material. This has not been considered.
　本発明のある実施形態の課題は、金型を用いて加熱成形した場合においても、良好な加工性を有し、且つ、最表面に形成された凹凸模様が良好に維持され、外観に優れた成形体を形成しうる合成樹脂表皮材、及びその製造方法を提供することにある。
　また、本発明の別の実施形態の課題は、耐溶剤性、耐汚染性、及び耐候性に優れ、加熱成形後においても合成樹脂表皮材が有する表皮層上の凹凸模様が維持された、外観の良好な成形体を提供することにある。 The problem of an embodiment of the present invention is that even when heat-molded using a mold, it has good workability, the uneven pattern formed on the outermost surface is well maintained, and the appearance is excellent. It is providing the synthetic resin skin material which can form a molded object, and its manufacturing method.
The problem of another embodiment of the present invention is that the appearance is excellent in solvent resistance, stain resistance, and weather resistance, and the uneven pattern on the skin layer of the synthetic resin skin material is maintained even after thermoforming. An object of the present invention is to provide a good molded article.
　課題を解決するための手段は以下の実施形態を含む。
＜１＞　熱可塑性樹脂を含む基材層と、前記基材層の一方の面上に設けられ、ポリ塩化ビニル樹脂を含有する中間層と、前記中間層の基材層とは反対側に設けられ、前記中間層側とは反対側の表面に凹凸を有し、且つ、フッ素樹脂を含有する表皮層と、を備える合成樹脂表皮材。 Means for solving the problems include the following embodiments.
<1> A base material layer containing a thermoplastic resin, an intermediate layer provided on one surface of the base material layer, containing a polyvinyl chloride resin, and provided on the side opposite to the base material layer of the intermediate layer And a synthetic resin skin material comprising a skin layer having irregularities on the surface opposite to the intermediate layer side and containing a fluororesin.
＜２＞　前記中間層と前記表皮層の間に、さらに、意匠層を備える＜１＞に記載の合成樹脂表皮材。 <2> The synthetic resin skin material according to <1>, further including a design layer between the intermediate layer and the skin layer.
＜３＞　前記意匠層が、アクリル樹脂及び塩化ビニル－酢酸ビニル共重合体から選ばれる少なくとも１種を含む印刷インク層である＜２＞に記載の合成樹脂表皮材。
＜４＞　前記フッ素樹脂が、３フッ化塩化エチレン－フッ化ビニリデン共重合体、フッ化ビニリデン－６フッ化プロピレン共重合体、及び、フッ化ビニリデン－６フッ化プロピレン－４フッ化エチレン共重合体からなる群より選択される少なくとも１種のフッ素樹脂を含む＜１＞～＜３＞のいずれか１つに記載の合成樹脂表皮材。
＜５＞　前記基材層が、アクリロニトリル／ブタジエン／スチレン共重合体を含む＜１＞～＜４＞のいずれか１つに記載の合成樹脂表皮材。
＜６＞　加熱成形加工品の表皮材である＜１＞～＜５＞のいずれか１つに記載の合成樹脂表皮材。
＜７＞　前記基材層の、中間層側とは反対側の面に、さらに、接着層を備える＜１＞～＜６＞のいずれか１つに記載の合成樹脂表皮材。 <3> The synthetic resin skin material according to <2>, wherein the design layer is a printing ink layer containing at least one selected from an acrylic resin and a vinyl chloride-vinyl acetate copolymer.
<4> The fluororesin is composed of a trifluoroethylene chloride-vinylidene fluoride copolymer, a vinylidene fluoride-6 propylene fluoride copolymer, and a vinylidene fluoride-6 fluoropropylene-4 fluoroethylene copolymer. The synthetic resin skin material according to any one of <1> to <3>, comprising at least one fluororesin selected from the group consisting of coalescence.
<5> The synthetic resin skin material according to any one of <1> to <4>, wherein the base material layer includes an acrylonitrile / butadiene / styrene copolymer.
<6> The synthetic resin skin material according to any one of <1> to <5>, which is a skin material of a thermoformed product.
<7> The synthetic resin skin material according to any one of <1> to <6>, further including an adhesive layer on a surface opposite to the intermediate layer side of the base material layer.
＜８＞　ポリ塩化ビニル樹脂を含有する樹脂組成物を用いてポリ塩化ビニル樹脂を含有する中間層を形成する工程、アクリロニトリル／ブタジエン／スチレン共重合体を含む熱可塑性樹脂組成物を用いて基材層を形成する工程、フッ素樹脂を含む表皮層を準備する工程、前記表皮層と前記中間層と前記基材層とを、この順に積層して積層体を得る工程、及び、得られた積層体の前記表皮層側に、絞ロールを用いてラミネートエンボス加工を施し、前記表皮層の前記中間層側とは反対側の面に凹凸模様を形成する工程を含む合成樹脂表皮材の製造方法。
＜９＞　前記表皮層と前記中間層との間に、意匠層を形成する工程をさらに含む＜８＞に記載の合成樹脂表皮材の製造方法。 <8> A step of forming an intermediate layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin, a base material using a thermoplastic resin composition containing an acrylonitrile / butadiene / styrene copolymer A step of forming a layer, a step of preparing a skin layer containing a fluororesin, a step of laminating the skin layer, the intermediate layer and the base material layer in this order to obtain a laminate, and the obtained laminate A method for producing a synthetic resin skin material comprising a step of applying a laminating embossing to the skin layer side of the skin layer using a squeezing roll and forming an uneven pattern on a surface of the skin layer opposite to the intermediate layer side.
<9> The method for producing a synthetic resin skin material according to <8>, further including a step of forming a design layer between the skin layer and the intermediate layer.
＜１０＞　成形基材と、前記成形基材の表面に配置された＜１＞～＜７＞のいずれか１つに記載の合成樹脂表皮材を有する成形体。 <10> A molded body having a molded base material and the synthetic resin skin material according to any one of <1> to <7> disposed on the surface of the molded base material.
　本発明のある実施形態によれば、金型を用いて加熱成形した場合においても、良好な加工性を有し、且つ、最表面に形成された凹凸模様が良好に維持され、外観に優れた成形体を形成しうる合成樹脂表皮材、及びその製造方法を提供することができる。
　また、本発明の別の実施形態によれば、耐溶剤性、耐汚染性、及び耐候性に優れ、加熱成形後においても合成樹脂表皮材が有する表皮層上の凹凸模様が維持された、外観の良好な成形体を提供することができる。 According to an embodiment of the present invention, even when heat-molded using a mold, it has good workability, the uneven pattern formed on the outermost surface is well maintained, and the appearance is excellent. A synthetic resin skin material capable of forming a molded body and a method for producing the same can be provided.
Further, according to another embodiment of the present invention, the appearance is excellent in solvent resistance, stain resistance, and weather resistance, and the uneven pattern on the skin layer of the synthetic resin skin material is maintained even after thermoforming. Can be provided.
本開示の合成樹脂表皮材の一態様を示す概略断面図である。It is a schematic sectional drawing which shows the one aspect | mode of the synthetic resin skin material of this indication.
　以下、本開示の合成樹脂表皮材、合成樹脂表皮材の製造方法及び成形体について詳細に説明する。
　以下に記載する構成要件の説明は、本開示の代表的な実施態様に基づいてなされることがあるが、本開示はそのような実施態様に限定されない。
　なお、本開示において、数値範囲を示す「～」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
　本開示に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において、好ましい態様の組み合わせは、より好ましい態様である。
　本開示において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
　本開示において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。 Hereinafter, the synthetic resin skin material, the manufacturing method of the synthetic resin skin material, and the molded body of the present disclosure will be described in detail.
The constituent elements described below may be described based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, a combination of preferred embodiments is a more preferred embodiment.
In the present disclosure, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
In the present disclosure, the term “step” is not limited to an independent step, and is included in the term if the intended purpose of the step is achieved even when it cannot be clearly distinguished from other steps.
　本開示における「樹脂を含む層」とは、「当該層の主成分である樹脂を含んで形成された層」を指す。即ち、本開示における「樹脂を含む層」は、樹脂のみを含む樹脂層、及び、主成分である樹脂に加え、可塑剤、着色剤、紫外線吸収剤等の任意成分をさらに含む樹脂組成物により形成された層の双方を包含する意味で用いられる。
　なお、本開示における「主成分である樹脂」とは、当該成分が含まれる樹脂組成物の全量に対し、６０質量％以上含有される樹脂を指す。
　以下、本開示では、ポリ塩化ビニル樹脂をＰＶＣ樹脂と称することがある。また、アクリロニトリル／ブタジエン／スチレン共重合体をＡＢＳ樹脂と称することがある。 The “layer containing a resin” in the present disclosure refers to a “layer formed including a resin that is a main component of the layer”. That is, the “layer containing a resin” in the present disclosure is a resin layer containing only a resin and a resin composition further containing optional components such as a plasticizer, a colorant, and an ultraviolet absorber in addition to a resin as a main component. It is used to include both formed layers.
In addition, the “resin that is a main component” in the present disclosure refers to a resin that is contained in an amount of 60% by mass or more based on the total amount of the resin composition containing the component.
Hereinafter, in the present disclosure, the polyvinyl chloride resin may be referred to as a PVC resin. An acrylonitrile / butadiene / styrene copolymer may be referred to as an ABS resin.
＜合成樹脂表皮材＞
　本開示の合成樹脂表皮材は、熱可塑性樹脂を含む基材層と、前記基材層の一方の面上に設けられ、ＰＶＣ樹脂を含む中間層と、前記中間層の基材層とは反対側の面に設けられ、前記中間層側とは反対側の面に凹凸を有し、且つ、フッ素樹脂を含む表皮層と、を備える。 <Synthetic resin skin material>
The synthetic resin skin material of the present disclosure includes a base material layer including a thermoplastic resin, an intermediate layer provided on one surface of the base material layer, including a PVC resin, and a base material layer of the intermediate layer opposite to the base material layer. A skin layer provided on the side surface, having irregularities on the surface opposite to the intermediate layer side, and comprising a fluororesin.
　本開示の合成樹脂表皮材について、図１を参照して説明する。図１は、本開示の合成樹脂表皮材１０の層構成の一態様を示す概略断面図である。
　合成樹脂表皮材１０は、熱可塑性樹脂を含む基材層１２と、その一方の面上に設けられたＰＶＣ樹脂を含む中間層１４と、所望により設けられる意匠層１６と、意匠層１６の、中間層１４と接する面とは反対側の面に設けられ、中間層１４側とは反対側の面に凹凸を有し、且つ、フッ素樹脂を含む表皮層１８と、をこの順に備える。
　なお、本開示では、以下、「合成樹脂表皮材」を「表皮材」と、「熱可塑性樹脂を含む基材層」を「基材層」と、「ＰＶＣ樹脂を含む中間層」を「中間層」と、「フッ素樹脂を含む表皮層」を「表皮層」と、それぞれ略称することがある。
　即ち、本開示の表皮材の一実施形態である図１に示す合成樹脂表皮材１０は、基材層１２と、中間層１４と、意匠層１６と、表皮層１８と、を順次有する積層構造を有し、表皮層１８の意匠層１６と接する側とは反対側の面に、シボ模様とも称される凹凸模様を有する。表皮層１８の凹凸模様を有する側は、合成樹脂表皮材１０を後述する成形基材に配置し、成形体とした際に最表面に位置することから、以下、表面と称することがある。
　凹凸模様は、天然皮革様の凹凸模様に代表される、合成樹脂表皮材による成形体の表面の外観を特徴付ける模様である。
　本開示の合成樹脂表皮材は、後述するようにインサート成形などの加熱成形により形成された成形体の表皮材として用いることができる。
　なお、図１に示す意匠層１６は、本開示の合成樹脂表皮材において所望により設けられる任意の層であり、必ずしも必要ではない。 The synthetic resin skin material of the present disclosure will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view illustrating an aspect of a layer configuration of a synthetic resin skin material 10 of the present disclosure.
The synthetic resin skin material 10 includes a base material layer 12 including a thermoplastic resin, an intermediate layer 14 including a PVC resin provided on one surface thereof, a design layer 16 provided as desired, and a design layer 16. A skin layer 18 is provided in this order, provided on the surface opposite to the surface in contact with the intermediate layer 14, and having an uneven surface on the surface opposite to the intermediate layer 14 side, and containing a fluororesin.
In the present disclosure, hereinafter, “synthetic resin skin material” is referred to as “skin material”, “base material layer including thermoplastic resin” is referred to as “base material layer”, and “intermediate layer including PVC resin” is referred to as “intermediate layer”. The “layer” and the “skin layer containing a fluororesin” may be abbreviated as “skin layer”, respectively.
That is, the synthetic resin skin material 10 shown in FIG. 1 which is an embodiment of the skin material of the present disclosure includes a base material layer 12, an intermediate layer 14, a design layer 16, and a skin layer 18 in order. The surface of the skin layer 18 opposite to the side in contact with the design layer 16 has a concavo-convex pattern also referred to as a texture pattern. Since the surface having the concavo-convex pattern of the skin layer 18 is located on the outermost surface when the synthetic resin skin material 10 is disposed on a molding substrate described later and formed into a molded body, it may be hereinafter referred to as a surface.
The concavo-convex pattern is a pattern that characterizes the appearance of the surface of the molded body made of a synthetic resin skin material, typified by a natural leather-like concavo-convex pattern.
The synthetic resin skin material of the present disclosure can be used as a skin material of a molded body formed by heat molding such as insert molding as described later.
The design layer 16 shown in FIG. 1 is an arbitrary layer provided as desired in the synthetic resin skin material of the present disclosure, and is not necessarily required.
　本開示の合成樹脂表皮材は、表皮層として、一方の面に凹凸を有し、且つ、フッ素樹脂を含有する耐熱性が良好な層を有し、表皮層の一方の面に形成された凹凸模様が加熱により変形し難い。さらに、表皮層は、ＰＶＣ樹脂を含む中間層と積層されることで、金型内に本開示の合成樹脂表皮材を配置して溶融樹脂を注入したり、成形基材の面上に本開示の合成樹脂表皮材を積層して金型により成形したりする場合、加熱成形する際において、柔軟で変形しやすい中間層が、表皮層に掛る熱応力の影響を緩和する。このため、合成樹脂表皮材の加熱成形性を損なうことなく、表皮層の面上に形成された凹凸模様の熱による変形を効果的に抑制すると考えている。
　従って、本開示の合成樹脂表皮材を用いることにより、インサート成形などの加熱成形後においても、表皮層表面に形成された凹凸模様（シボ柄）の維持率が高いため、表皮層への凹凸模様の付与は、加熱成形による成形体の形成と独立して行なうことができ、成形金型を換えることなく、表面に様々な凹凸模様を有する成形体を製造することが可能となるという利点をも有する。 The synthetic resin skin material of the present disclosure has an unevenness formed on one surface of the skin layer, having an uneven surface on one surface and a layer having good heat resistance containing a fluororesin. The pattern is not easily deformed by heating. Furthermore, the skin layer is laminated with an intermediate layer containing a PVC resin so that the synthetic resin skin material of the present disclosure is placed in the mold and molten resin is injected, or the surface of the molded substrate is disclosed. When the synthetic resin skin material is laminated and molded with a mold, the intermediate layer that is flexible and easily deforms during heat molding reduces the influence of thermal stress on the skin layer. For this reason, it is thought that the deformation | transformation by the heat | fever of the uneven | corrugated pattern formed on the surface of the skin layer is suppressed effectively, without impairing the heat moldability of a synthetic resin skin material.
Therefore, by using the synthetic resin skin material of the present disclosure, the unevenness pattern (texture pattern) formed on the surface of the skin layer is high even after heat molding such as insert molding. Can be performed independently of the formation of the molded body by thermoforming, and it is possible to produce molded bodies having various uneven patterns on the surface without changing the molding die. Have.
　さらに、本開示の合成樹脂表皮材は、表皮層と中間層との間に意匠層を設けてもよい。所望により設けられる意匠層には特に制限はないため、所望の意匠を形成することができ、かつ、加熱成形後も表皮層表面の凹凸模様が維持されるため、得られた成形体はデザインの自由度が高く、意匠性が良好となる。 Furthermore, the synthetic resin skin material of the present disclosure may be provided with a design layer between the skin layer and the intermediate layer. Since there is no particular limitation on the design layer provided as desired, the desired design can be formed, and the uneven pattern on the surface of the skin layer is maintained even after heat molding. The degree of freedom is high and the design properties are good.
　本開示の合成樹脂表皮材は、インサート成形などの加熱成形性が良好であり、加熱成形後に得られた成形体表面において、合成樹脂表皮材の表面層が有する凹凸模様が良好に維持される。このため、意匠性に優れ、熱加工性が良好な本開示の合成樹脂表皮材は、成形基材と積層して加熱成形を行なって得られる車輌用内装材等の種々の用途に好適に使用される。 The synthetic resin skin material of the present disclosure has good heat moldability such as insert molding, and the uneven pattern of the surface layer of the synthetic resin skin material is well maintained on the surface of the molded body obtained after the heat molding. For this reason, the synthetic resin skin material of the present disclosure having excellent design properties and good thermal processability is suitably used for various applications such as vehicle interior materials obtained by laminating with a molding substrate and performing thermoforming. Is done.
　以下、合成樹脂表皮材について、これを構成する材料とその製造方法とともに順次説明する。
（１．基材層）
　基材層は、熱可塑性樹脂を含む。
　基材層に用い得る熱可塑性樹脂には特に制限はなく、適用される成形体を構成する樹脂との親和性、成形される場合の延伸性などの諸条件を考慮して、公知の熱可塑性樹脂から適宜選択することができる。
　基材層に使用しうる熱可塑性樹脂としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ＰＶＣ樹脂、ポリスチレン（ＰＳ）、ポリ酢酸ビニル（ＰＶＡｃ）、ポリウレタン（ＰＵＲ）、ＡＢＳ樹脂、アクリロニトリル／スチレン共重合体（ＡＳ樹脂）、ポリカーボネート（ＰＣ）、ポリメチルメタクリレート（ＰＭＭＡ）等のアクリル樹脂、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂等が挙げられる。
　なかでも、成形基材の表面に配置される合成樹脂表皮材の加熱成形時の溶融による破断を効果的に抑制するという観点からは、基材層に含まれる熱可塑性樹脂は、ＡＢＳ樹脂、ＡＳ樹脂、ＰＣ、ＰＰ、及びＰＣとＡＢＳ樹脂との混合物（ＰＣ／ＡＢＳ）等が好ましく、ＡＢＳ樹脂がより好ましい。 Hereinafter, the synthetic resin skin material will be sequentially described together with the materials constituting the same and the manufacturing method thereof.
(1. Base material layer)
The base material layer includes a thermoplastic resin.
The thermoplastic resin that can be used for the base material layer is not particularly limited, and is a known thermoplastic in consideration of various conditions such as affinity with the resin constituting the molded article to be applied and stretchability when molded. It can select suitably from resin.
Examples of the thermoplastic resin that can be used for the base material layer include polyethylene (PE), polypropylene (PP), PVC resin, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (PUR), ABS resin, acrylonitrile / Examples thereof include acrylic resins such as styrene copolymer (AS resin), polycarbonate (PC), and polymethyl methacrylate (PMMA), and fluorine resins such as polytetrafluoroethylene (PTFE).
Among these, from the viewpoint of effectively suppressing breakage due to melting at the time of thermoforming the synthetic resin skin material disposed on the surface of the molded base material, the thermoplastic resin contained in the base material layer is composed of ABS resin, AS Resin, PC, PP, and a mixture of PC and ABS resin (PC / ABS) are preferable, and ABS resin is more preferable.
　基材層は、熱可塑性樹脂に加え、熱可塑性樹脂以外の種々の成分を含んでもよい。基材層が含み得るその他の成分としては、着色剤、可塑剤、充填剤、滑剤、加工助剤等が挙げられる。
　なかでも、基材層は着色剤を含むことが好ましい。基材層が着色剤を含むことで、合成樹脂表皮材を成形体基材となる樹脂の表面に配置し、成形体を作製した場合、成形基材が成形体の外観に影響を与えることを抑制することができる。 The base material layer may contain various components other than the thermoplastic resin in addition to the thermoplastic resin. Examples of other components that can be included in the base material layer include colorants, plasticizers, fillers, lubricants, and processing aids.
Especially, it is preferable that a base material layer contains a coloring agent. When the base material layer contains a colorant, when the synthetic resin skin material is placed on the surface of the resin that becomes the base material of the molded body and the molded body is produced, the molded base material affects the appearance of the molded body. Can be suppressed.
　基材層が着色剤を含む場合の着色剤には特に制限はなく、染料、顔料などを適宜選択して使用することができる。
　着色剤としては、チタン白（二酸化チタン）、亜鉛華、群青、コバルトブルー、弁柄、朱、黄鉛、チタン黄、カーボンブラック等の無機顔料、キナクリドン、パーマネントレッド４Ｒ、イソインドリノン、ハンザイエローＡ、フタロシアニンブルー、インダスレンブルーＲＳ、アニリンブラック等の有機顔料又は染料、アルミニウム及び真鍮等金属の箔粉からなる群より選択される金属顔料、二酸化チタン被覆雲母及び塩基性炭酸鉛の箔粉からなる群より選択される真珠光沢（パール）顔料等が挙げられる。なかでも、耐候性及び耐久性に優れる着色剤である顔料が好ましく、成形基材を効果的に隠蔽しうるという観点から、カーボンブラック、アニリンブラック、ペリレンブラック等の黒色顔料がより好ましい。
　また、基材層には、必要に応じて、炭酸カルシウム、シリカ（二酸化硅素）、アルミナ（酸化アルミニウム）、硫酸バリウム等の体質顔料（充填剤）を含有してもよい。 There is no restriction | limiting in particular in the coloring agent in case a base material layer contains a coloring agent, Dye, a pigment, etc. can be selected suitably and can be used.
Colorants include titanium white (titanium dioxide), zinc white, ultramarine blue, cobalt blue, dial, inorganic pigments such as vermilion, yellow lead, titanium yellow, carbon black, quinacridone, permanent red 4R, isoindolinone, and hansa yellow. A, organic pigments or dyes such as phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments selected from the group consisting of metal foil powders such as aluminum and brass, titanium dioxide-coated mica and basic lead carbonate foil powders And nacreous (pearl) pigments selected from the group. Among these, a pigment that is a colorant having excellent weather resistance and durability is preferable, and black pigments such as carbon black, aniline black, and perylene black are more preferable from the viewpoint of effectively hiding the molding substrate.
The base material layer may contain extender pigments (fillers) such as calcium carbonate, silica (silicon dioxide), alumina (aluminum oxide), and barium sulfate as necessary.
　基材層が着色剤を含む場合、着色剤を１種のみ含んでもよく、調色などの目的で２種以上を含んでいてもよい。
　基材層の形成に用いられる樹脂組成物における着色剤の含有量には特に制限はなく、合成樹脂表皮材において目的とする色相、成形基材の隠蔽性などに応じて、用いる着色剤の種類、含有量などを適宜選択すればよい。
　着色剤を用いる際の一般的な着色剤の含有量は、基材層を構成する樹脂組成物の全固形分中に対し、１質量％～２０質量％であることが好ましく、２質量％～１０質量％であることがより好ましい。なお、ここで固形分とは、基材層を構成する樹脂組成物の全成分中、溶剤を除いた成分の総量を指す。 When a base material layer contains a coloring agent, only 1 type of coloring agents may be included and 2 or more types may be included for the purpose of toning.
The content of the colorant in the resin composition used for forming the base material layer is not particularly limited, and the type of the colorant to be used depends on the target hue in the synthetic resin skin material, the hiding property of the molding base material, and the like. The content may be selected as appropriate.
The content of a general colorant when using a colorant is preferably 1% by mass to 20% by mass with respect to the total solid content of the resin composition constituting the base material layer, and preferably 2% by mass to More preferably, it is 10 mass%. In addition, solid content means the total amount of the component except the solvent in all the components of the resin composition which comprises a base material layer here.
　基材層の厚みは５０μｍ～４００μｍの範囲であることが好ましく、１００μｍ～３５０μｍの範囲であることがより好ましい。厚みが上記範囲にあることで、合成樹脂表皮材を用いて熱加工により成形体を形成する際の、合成樹脂表皮材の溶融による破断が効果的に抑制され、さらに、成形体に用いる成形基材の隠蔽性がより良好となる。
　基材層の厚み、及び合成樹脂表皮材における後述の各層の厚みは、合成樹脂表皮材を面方向に垂直に切断した切断面を観察することで測定することができる。従って、本開示における合成樹脂表皮材における各層の膜厚は、乾燥後の膜厚を指す。 The thickness of the base material layer is preferably in the range of 50 μm to 400 μm, and more preferably in the range of 100 μm to 350 μm. When the thickness is in the above range, when the molded body is formed by thermal processing using the synthetic resin skin material, the fracture due to melting of the synthetic resin skin material is effectively suppressed, and further, the molding base used for the molded body is used. The concealability of the material becomes better.
The thickness of the base material layer and the thickness of each layer described later in the synthetic resin skin material can be measured by observing a cut surface obtained by cutting the synthetic resin skin material perpendicularly to the surface direction. Therefore, the film thickness of each layer in the synthetic resin skin material in the present disclosure refers to the film thickness after drying.
　基材層の形成方法には特に制限はなく、公知のシート成形方法、例えば、Ｔダイなどで押し出し成形する押出し法、カレンダー法、キャスティング法等を適用することができる。
　なかでも、カレンダー法が、製造の簡易性、装置のメンテナンスが容易である点で好ましい。特に、基材層が着色剤を含有する場合、軟化した樹脂と固体状の着色剤とをカレンダーロールに供給し、シート又はフィルム状に成形することができるため、種々の着色剤を含有する基材層を簡易に製造することができる。
　また、カレンダー法を適用することにより、押出し法等の成形法に比較して、着色剤の種類や添加量を変更する際に必要な装置内の清掃を、より容易に行うことができる。このため、基材層として着色剤を含む物を形成する際にカレンダー法を適用することで、所望の色相を有する様々な基材層を簡易に製造することができ、合成樹脂表皮材の小ロット生産にも適する。 There is no restriction | limiting in particular in the formation method of a base material layer, A well-known sheet forming method, for example, the extrusion method extrusion-molding with a T die etc., a calendar method, a casting method, etc. are applicable.
Of these, the calendar method is preferable in terms of ease of production and easy maintenance of the apparatus. In particular, when the base material layer contains a colorant, a softened resin and a solid colorant can be supplied to a calender roll and formed into a sheet or film, so that groups containing various colorants can be used. The material layer can be easily manufactured.
In addition, by applying the calendar method, it is possible to more easily clean the inside of the apparatus required when changing the type and amount of the colorant compared to a molding method such as an extrusion method. For this reason, by applying the calendering method when forming a material containing a colorant as the base material layer, various base material layers having a desired hue can be easily manufactured. Also suitable for lot production.
（２．中間層）
　既述の基材層の一方の面上には、中間層を有する。中間層はＰＶＣ樹脂を含有する。 (2. Intermediate layer)
An intermediate layer is provided on one surface of the base material layer described above. The intermediate layer contains a PVC resin.
　中間層は、ＰＶＣ樹脂に加え、その他の成分を含んでもよい。中間層が含み得るその他の成分としては、着色剤、可塑剤、充填剤、滑剤、加工助剤等が挙げられる。なお、その他の成分は、中間層の熱加工性を低下させない範囲で用いることができる。
　中間層は着色剤を含むことができる。中間層が着色剤を含むことで、成形体の作製に際して、用いる成形基材が成形体の外観に影響を与えることを抑制し、合成樹脂表皮材、惹いては、合成樹脂表皮材を配置してなる成形体の色味に深みを付与することができる。
　なお、中間層に用い得る着色剤は、既述の基材層に用いうる着色剤と同様であり、所望の色味を目的に応じて選択すればよい。中間層に用いる場合の着色剤の好ましい含有量も目的に応じて適宜選択することができる。なお、層の均一性の観点からは、中間層の形成に用いる樹脂組成物の全固形分中に対し、２０質量％以下であることが好ましい。 The intermediate layer may contain other components in addition to the PVC resin. Examples of other components that the intermediate layer may include include a colorant, a plasticizer, a filler, a lubricant, and a processing aid. In addition, other components can be used in the range which does not reduce the heat workability of an intermediate | middle layer.
The intermediate layer can include a colorant. When the intermediate layer contains a colorant, it is possible to prevent the molding base used from affecting the appearance of the molded body when producing the molded body, and to arrange a synthetic resin skin material, and therefore a synthetic resin skin material. Depth can be imparted to the color of the molded article.
The colorant that can be used for the intermediate layer is the same as the colorant that can be used for the base layer described above, and a desired color may be selected according to the purpose. The preferred content of the colorant when used in the intermediate layer can also be appropriately selected according to the purpose. From the viewpoint of the uniformity of the layer, it is preferably 20% by mass or less based on the total solid content of the resin composition used for forming the intermediate layer.
　中間層の厚みは５０μｍ～３００μｍの範囲であることが好ましく、１００μｍ～２５０μｍの範囲であることがより好ましい。厚みが上記範囲にあることで、合成樹脂表皮材を用いて加熱して成形体を形成する際の、表皮層に掛る熱応力が緩和され、表皮層の表面に形成された凹凸模様の保持性がより良好となる。 The thickness of the intermediate layer is preferably in the range of 50 μm to 300 μm, and more preferably in the range of 100 μm to 250 μm. When the thickness is in the above range, the heat stress applied to the skin layer is reduced when a synthetic resin skin material is heated to form a molded body, and the unevenness pattern formed on the surface of the skin layer is retained. Is better.
（３．表皮層）
　合成樹脂表皮材の表皮層は、フッ素樹脂を含有する。 (3. Skin layer)
The skin layer of the synthetic resin skin material contains a fluororesin.
　表皮層に用い得るフッ素樹脂としては、フッ素原子を含む単量体の少なくとも１種を重合成分として、重合して得られる樹脂であれば、特に制限はない。なかでも、フッ素樹脂としては、フッ素原子を含むオレフィンを重合して得られる樹脂が好ましい。
　フッ素樹脂としては、例えば、４フッ化エチレン、３フッ化塩化エチレン、フッ化ビニル、及びフッ化ビニリデンから選ばれる重合成分を含んで構成される樹脂が挙げられる。より具体的には、４フッ化エチレン樹脂、フッ化ビニル樹脂、フッ化ビニリデン樹脂などのフッ素原子を含む重合成分の単独重合体、及び前記重合成分を含む共重合体である、３フッ化塩化エチレン－フッ化ビニリデン共重合体、フッ化ビニリデン－６フッ化プロピレン共重合体、フッ化ビニリデン－６フッ化プロピレン－４フッ化エチレン共重合体などが挙げられる。なかでも、３フッ化塩化エチレン－フッ化ビニリデン共重合体、フッ化ビニリデン－６フッ化プロピレン共重合体、及び、フッ化ビニリデン－６フッ化プロピレン－４フッ化エチレン共重合体からなる群より選択される少なくとも１種のフッ素樹脂を含むことが好ましい。 The fluororesin that can be used for the skin layer is not particularly limited as long as it is a resin obtained by polymerization using at least one monomer containing a fluorine atom as a polymerization component. Especially, as a fluororesin, resin obtained by superposing | polymerizing the olefin containing a fluorine atom is preferable.
Examples of the fluororesin include a resin that includes a polymerization component selected from ethylene tetrafluoride, trifluoroethylene chloride, vinyl fluoride, and vinylidene fluoride. More specifically, a trifluoride chloride is a homopolymer of a polymer component containing a fluorine atom, such as a tetrafluoroethylene resin, a vinyl fluoride resin, or a vinylidene fluoride resin, and a copolymer containing the polymer component. Examples thereof include an ethylene-vinylidene fluoride copolymer, a vinylidene fluoride-6-propylene fluoride copolymer, and a vinylidene fluoride-6-propylene-4-tetrafluoroethylene copolymer. Among these, from the group consisting of ethylene trifluoride-vinylidene fluoride copolymer, vinylidene fluoride-6-propylene fluoride copolymer, and vinylidene fluoride-6-propylene-4-tetrafluoroethylene copolymer It is preferable to include at least one selected fluororesin.
　表皮層には、上記フッ素樹脂を１種のみを含有してもよく、２種以上を併用してもよい。また、フッ素樹脂の少なくとも１種と、フッ素樹脂以外の樹脂の少なくとも１種とを併用してもよい。
　表皮層が、２種以上のフッ素樹脂を含む場合、例えば、フッ化ビニリデン樹脂、３フッ化塩化エチレン－フッ化ビニリデン共重合体、フッ化ビニリデン－６フッ化プロピレン共重合体、及び、フッ化ビニリデン－６フッ化プロピレン－４フッ化エチレン共重合体からなる群より選択される２種以上の樹脂の混合物などを用いることも好ましい態様である。 The skin layer may contain only one type of the fluororesin, or two or more types may be used in combination. Moreover, you may use together at least 1 sort (s) of a fluororesin, and at least 1 sort (s) of resin other than a fluororesin.
When the skin layer contains two or more kinds of fluororesins, for example, vinylidene fluoride resin, trifluoroethylene chloride-vinylidene fluoride copolymer, vinylidene fluoride-6 fluoropropylene copolymer, and fluoride It is also a preferred embodiment to use a mixture of two or more kinds of resins selected from the group consisting of vinylidene-6 fluoropropylene-4 fluoroethylene copolymer.
　表皮層が２種以上の樹脂を含む場合、既述のように２種以上の樹脂の混合物である態様に加え、２種以上の樹脂の積層構造の態様をとることもできる。例えば、表皮層として、最表面、即ち、成形体上に合成樹脂表皮材を配置した場合の外側に当たる面を、フッ素樹脂を含む層とし、表皮層と、中間層又は所望により設けられる意匠層との接着性をより向上させる目的で、表皮層を、フッ素樹脂を含む層と、アクリル樹脂を含む層との２層構造として、アクリル樹脂を含む層側を意匠層と接する面に位置させることができる。 When the skin layer includes two or more kinds of resins, in addition to the aspect in which the skin layer is a mixture of two or more kinds of resins as described above, it is possible to take a form of a laminated structure of two or more kinds of resins. For example, as the skin layer, the outermost surface, that is, the surface corresponding to the outside when the synthetic resin skin material is disposed on the molded body is a layer containing a fluororesin, and the skin layer and an intermediate layer or a design layer provided as desired For the purpose of further improving the adhesion of the surface layer, the skin layer is formed as a two-layer structure of a layer containing a fluororesin and a layer containing an acrylic resin, and the layer side containing the acrylic resin is positioned on the surface in contact with the design layer it can.
　表皮層は、成形して得てもよいし、市販のフィルムを適用してもよい。
　表皮層に用いることができる市販のフィルムとしては、クレハエクステック（株）製のＫＣＦフィルム、三菱ケミカル（株）製のアクリプレン（登録商標）ＦＢＳ００６等が挙げられる。ＫＦＣフィルムは、ポリフッ化ビニリデン層と、アクリル樹脂層との積層構造を有する多層フィルムである。アクリプレンは、フッ素樹脂含有層と、アクリル樹脂含有層との積層構造を有する多層フィルムである。 The skin layer may be obtained by molding, or a commercially available film may be applied.
Examples of the commercially available film that can be used for the skin layer include KCF film manufactured by Kureha Extec Co., Ltd., Acryprene (registered trademark) FBS006 manufactured by Mitsubishi Chemical Corporation. The KFC film is a multilayer film having a laminated structure of a polyvinylidene fluoride layer and an acrylic resin layer. Acryprene is a multilayer film having a laminated structure of a fluororesin-containing layer and an acrylic resin-containing layer.
　表皮層の厚みは、強度及び凹凸模様保持性の観点から、５μｍ～１００μｍの範囲であることが好ましく、５μｍ～５０μｍの範囲がより好ましい。
　ここで、表皮層の厚みとは、凹凸模様が形成された面の凸部の頂部から、表皮層の底面までの距離を指す。
　表皮層の厚みは、表皮層における中間層又は所望により設けられる意匠層側の面とは反対側に形成される凹凸模様の保持性の観点から、凹凸模様の凹部の最深部における底部と凸部の頂部との距離よりも大きいことが好ましい。例えば、凹部の深さが１μｍ以下である如き凹凸模様を形成する際には、表皮層の厚みは５μｍ程度とすることができ、天然の皮革様模様の如く、浅い凹部と深い凹部とを有し、深い凹部が２μｍ～５μｍである場合には、表皮層の厚みは１０μｍ以上であることが好ましい。
　なお、表皮層が既述のように２層以上の積層構造をとる場合の表皮層の厚みは、複数の層の総厚みを指す。 The thickness of the skin layer is preferably in the range of 5 μm to 100 μm, more preferably in the range of 5 μm to 50 μm, from the viewpoint of strength and ruggedness pattern retention.
Here, the thickness of the skin layer refers to the distance from the top of the convex portion of the surface on which the concavo-convex pattern is formed to the bottom surface of the skin layer.
The thickness of the skin layer is such that the bottom part and the convex part in the deepest part of the concave part of the concave-convex pattern are from the viewpoint of the retention of the concave-convex pattern formed on the side opposite to the intermediate layer in the skin layer or the design layer side provided as desired. It is preferable that it is larger than the distance with the top part of. For example, when forming a concavo-convex pattern in which the depth of the concave portion is 1 μm or less, the thickness of the skin layer can be about 5 μm, and it has a shallow concave portion and a deep concave portion like a natural leather-like pattern. When the deep concave portion is 2 μm to 5 μm, the thickness of the skin layer is preferably 10 μm or more.
Note that the thickness of the skin layer when the skin layer has a laminated structure of two or more layers as described above refers to the total thickness of a plurality of layers.
　中間層又は所望により設けられる意匠層の、基材層側の面とは反対側の面に表皮層を形成する方法は任意である。例えば、予め成形した表皮層と中間層又は所望により設けられる意匠層とを接着させてもよく、表皮層を形成後、表皮層の一方の面に、既述の方法により中間層を形成してもよい。 The method of forming the skin layer on the surface opposite to the surface on the base material layer side of the intermediate layer or the design layer provided as desired is arbitrary. For example, a pre-formed skin layer and an intermediate layer or a design layer provided as desired may be adhered, and after forming the skin layer, an intermediate layer is formed on one surface of the skin layer by the method described above. Also good.
　また、表皮層の、中間層側の面とは反対側の面に凹凸模様を形成する方法には特に制限はなく、公知の方法を適用することができる。公知の方法としては、凹凸模様を有する離型紙上に表皮層を形成する方法、まず、表面が平滑な表皮層を形成し、その後、絞ロールを用いてエンボスする方法等が挙げられる。 Also, there is no particular limitation on the method for forming the uneven pattern on the surface of the skin layer opposite to the surface on the intermediate layer side, and a known method can be applied. Known methods include a method of forming a skin layer on a release paper having a concavo-convex pattern, a method of first forming a skin layer having a smooth surface, and then embossing using a squeeze roll.
　なお、本開示の合成樹脂表皮材における各層の厚みは、既述のように、表皮層の厚みは５μｍ～１００μｍの範囲であること、中間層の厚みは５０μｍ～３００μｍの範囲であること、及び基材層の厚みは５０μｍ～４００μｍの範囲であること、がそれぞれ好ましい。
　さらに、中間層の厚みを１００としたとき、表皮層の厚みは１５～５５の範囲であることが好ましい。
　なお、任意の層である意匠層の好ましい厚みなどについては後述する。 As described above, the thickness of each layer in the synthetic resin skin material of the present disclosure is such that the thickness of the skin layer is in the range of 5 μm to 100 μm, the thickness of the intermediate layer is in the range of 50 μm to 300 μm, and The thickness of the base material layer is preferably in the range of 50 μm to 400 μm.
Further, when the thickness of the intermediate layer is 100, the thickness of the skin layer is preferably in the range of 15 to 55.
In addition, about the preferable thickness of the design layer which is arbitrary layers, it mentions later.
　本開示の合成樹脂表皮材は、最表面に、透明性、耐久性に優れ、加熱時の凹凸模様の維持性が良好な表皮層を有しており、且つ、熱加工性に優れた中間層を有する。このため、本開示の合成樹脂表皮材は、加熱成形後も、表皮層の凹凸模様の保持性が良好である。従って、加熱成形を必要とする成形体の表皮材として好適に使用され、得られた成形体は合成樹脂表皮材の意匠性が反映されて外観に優れ、耐溶剤性等の耐久性にも優れたものとなる。
　従って、熱加工を必要とする成形体の表面に意匠性を付与する合成樹脂表皮材、即ち、加熱成形加工品の表皮材として、種々の用途に適用しうる。 The synthetic resin skin material of the present disclosure has an outer layer having a skin layer that is excellent in transparency and durability on the outermost surface, and that has good maintainability of the uneven pattern during heating, and is excellent in heat workability. Have For this reason, the synthetic resin skin material of this indication has the favorable retention of the uneven | corrugated pattern of a skin layer even after thermoforming. Therefore, it is suitably used as a skin material for molded products that require heat molding, and the resulting molded product reflects the design of the synthetic resin skin material and has an excellent appearance and excellent durability such as solvent resistance. It will be.
Therefore, it can be applied to various uses as a synthetic resin skin material that imparts designability to the surface of a molded body that requires heat processing, that is, a skin material of a thermoformed product.
（４．その他の層）
　合成樹脂表皮材は、既述の基材層、中間層及び表皮層に加え、効果を損なわない限り、その他の層をさらに有していてもよい。
　その他の層としては、意匠層、接着層、プライマー層等が挙げられる。 (4. Other layers)
The synthetic resin skin material may further have other layers in addition to the above-described base material layer, intermediate layer and skin layer as long as the effects are not impaired.
Examples of other layers include a design layer, an adhesive layer, and a primer layer.
（４－１．意匠層）
　合成樹脂表皮材は、既述の中間層の、基材層側とは反対側の面にさらに意匠層を有してもよい。意匠層は合成樹脂表皮材に意匠を付与する層であり、印刷により形成される印刷層であってもよく、着色剤を含む着色層であってもよく、これらを併用した層であってもよい。
　本開示の合成樹脂表皮材では、意匠層には特に制限はないため、所望により合成樹脂表皮材の用途に応じた種々の意匠層を形成することで、成形体に所望の意匠性に優れた外観を付与することができる。 (4-1. Design layer)
The synthetic resin skin material may further have a design layer on the surface of the intermediate layer described above on the side opposite to the base material layer side. The design layer is a layer that imparts a design to the synthetic resin skin material, and may be a printed layer formed by printing, may be a colored layer containing a colorant, or may be a layer that uses these in combination. Good.
In the synthetic resin skin material of the present disclosure, the design layer is not particularly limited. Therefore, by forming various design layers according to the use of the synthetic resin skin material as desired, the molded article has excellent desired design properties. Appearance can be imparted.
　印刷層は、例えば、中間層又は既述の表皮層の面上に印刷法により形成することができる。印刷層としては、樹脂を含む印刷インクにより公知の印刷法により形成された層が挙げられる。樹脂を含む印刷インクとしては、クリアな印刷画像の形成が可能であるという観点から、アクリル樹脂、塩化ビニル－酢酸ビニル共重合体等を含む印刷インクが好ましい。
　印刷方法には特に制限はなく、グラビヤ印刷（凹版印刷）、凸版印刷、オフセット印刷、インクジェット印刷、スクリーン印刷など、任意の印刷方法を適用することができる。
　意匠層としては、アクリル樹脂及び塩化ビニル－酢酸ビニル共重合体から選ばれる少なくとも１種を含む印刷インク層が好ましい。 The printing layer can be formed by, for example, a printing method on the surface of the intermediate layer or the above-described skin layer. As a printing layer, the layer formed by the well-known printing method with the printing ink containing resin is mentioned. The printing ink containing a resin is preferably a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or the like from the viewpoint that a clear print image can be formed.
There is no restriction | limiting in particular in a printing method, Arbitrary printing methods, such as gravure printing (intaglio printing), relief printing, offset printing, inkjet printing, and screen printing, can be applied.
As the design layer, a printing ink layer containing at least one selected from an acrylic resin and a vinyl chloride-vinyl acetate copolymer is preferable.
　着色層としては、任意の着色剤を含有する樹脂組成物により形成された層が挙げられる。例えば、アクリル樹脂に、既述の基材層に用い得る着色剤として挙げたものから選択した着色剤を含有させた樹脂組成物を、カレンダー法、押出し法、キャスティング法などによりフィルム状に成形した意匠層等が挙げられる。 Examples of the colored layer include a layer formed of a resin composition containing an arbitrary colorant. For example, a resin composition containing an acrylic resin and a colorant selected from those listed as the colorant that can be used in the base material layer described above was formed into a film by a calendar method, an extrusion method, a casting method, or the like. Examples include a design layer.
　意匠層の形成に用い得るアクリル樹脂としては、具体的には、たとえば、ポリメチルメタクリレート（ＰＭＭＡ）に代表されるメタクリル酸又はメタクリル酸エステルの重合体或いは共重合体、メタクリル酸アルキルとアクリル酸アルキルとスチレンの共重合体などが挙げられ、成形性の観点からは、メタクリル酸アルキルとアクリル酸アルキルとスチレンの共重合体及びメタクリル酸メチルとアクリル酸メチルの共重合体の混合物が好ましい。 Specific examples of the acrylic resin that can be used for forming the design layer include, for example, a polymer or copolymer of methacrylic acid or a methacrylic ester represented by polymethyl methacrylate (PMMA), an alkyl methacrylate, and an alkyl acrylate. From the viewpoint of moldability, a copolymer of alkyl methacrylate, alkyl acrylate and styrene, and a mixture of methyl methacrylate and methyl acrylate copolymer are preferred.
　アクリル樹脂は、耐候性、延伸性に優れ、隣接して設けられる他の樹脂層との密着性が良好である。
　また、アクリル樹脂は透明性が良好であることから、アクリル樹脂に着色剤等を添加したり、金属光沢を有する顔料、パール顔料等の光散乱性の着色剤を添加したりすることにより、合成樹脂表皮材に所望の良好な色相、光沢に優れた意匠等を任意に付与することができる。
　また、アクリル樹脂を含む印刷インクを用いて印刷インク層を形成する場合、文字、画像等を印刷することで、合成樹脂表皮材にさらに複雑な任意の意匠を付与することができる。 The acrylic resin is excellent in weather resistance and stretchability, and has good adhesion to other resin layers provided adjacent to each other.
In addition, since acrylic resin has good transparency, it can be synthesized by adding a colorant or the like to the acrylic resin, or adding a light scattering colorant such as a pigment having a metallic luster or a pearl pigment. Desired good hue, design excellent in gloss, etc. can be arbitrarily given to the resin skin material.
Moreover, when forming a printing ink layer using the printing ink containing an acrylic resin, a more complicated arbitrary design can be provided to a synthetic resin skin material by printing a character, an image, etc.
　本開示の合成樹脂表皮材が意匠層を有する場合の意匠層の厚みは１μｍ～１５μｍの範囲であることが好ましく、２μｍ～１０μｍの範囲であることがより好ましく、２μｍ～５μｍの範囲であることがさらに好ましい。意匠層の厚みが上記範囲にあることで、所望の意匠を合成樹脂表皮材に付与することができる。さらに、意匠層の厚みが上記範囲にあることで、合成樹脂表皮材を用いて熱加工により成形体を形成する際における、表皮層と中間層との良好な相関性が維持され、表皮層の凹凸模様の保持性がより良好となる。
　意匠層を形成する場合の、合成樹脂表皮材の層の厚み比としては、中間層の厚みを１００としたとき、意匠層の厚みは１～１０の範囲であることが好ましい。このように、既述の表皮層の厚みが、好ましくは中間層の厚み１００に対して１５～５５の範囲であることに比較し、意匠層は表皮層よりも厚みが薄いことが好ましい。 When the synthetic resin skin material of the present disclosure has a design layer, the thickness of the design layer is preferably in the range of 1 μm to 15 μm, more preferably in the range of 2 μm to 10 μm, and in the range of 2 μm to 5 μm. Is more preferable. A desired design can be provided to a synthetic resin skin material because the thickness of the design layer is within the above range. Furthermore, when the thickness of the design layer is within the above range, a good correlation between the skin layer and the intermediate layer is maintained when a molded body is formed by thermal processing using a synthetic resin skin material, and the thickness of the skin layer is maintained. The retainability of the uneven pattern becomes better.
When the design layer is formed, the thickness ratio of the synthetic resin skin material layer is preferably in the range of 1 to 10 when the thickness of the intermediate layer is 100. As described above, the design layer is preferably thinner than the skin layer as compared with the thickness of the skin layer described above being preferably in the range of 15 to 55 with respect to the thickness 100 of the intermediate layer.
（４－２．接着層）
　合成樹脂表皮材を成形基材面上に配置するか、又は、金型上に合成樹脂表皮材を配置して成形基材をインサートして成形を行なう場合には、基材層の中間層側とは反対側の面に、成形基材との接着性を向上させるための接着層を備えていてもよい。
　接着層は、基材層の中間層側とは反対側の面に、公知の接着剤及び粘着剤の少なくとも一方を付与することで形成することができる。
　合成樹脂表皮材に所望により設けられる接着層の形成に使用される接着剤としては特に制限はなく、成形基材の種類により適宜選択される。接着剤としては、例えば（１）２液硬化型ポリエステル系接着剤、（２）２液硬化型ウレタン接着剤、（３）２液硬化型アクリル粘着剤などが好適に使用される。
　なお、接着層の形成に使用される接着剤は市販品としても入手可能であり、例えば、オリバインシリーズ〔東洋インキ（株）〕、ウェルダー用接着剤Ｎｏ．３６６０〔２液硬化型ポリウレタン接着剤：ノーテープ工業（株）〕、ダイカラック７２５０ＮＴ〔２液硬化型ポリエステル接着剤：大同化成工業（株）〕などが好適である。
　接着層の厚さは、２０μｍ～５０μｍの範囲であることが好ましい。 (4-2. Adhesive layer)
When the synthetic resin skin material is placed on the molding substrate surface, or when the synthetic resin skin material is placed on the mold and the molding substrate is inserted for molding, the intermediate layer side of the base material layer An adhesive layer for improving the adhesiveness to the molding substrate may be provided on the opposite surface.
The adhesive layer can be formed by applying at least one of a known adhesive and pressure-sensitive adhesive to the surface of the base material layer opposite to the intermediate layer.
There is no restriction | limiting in particular as an adhesive agent used for formation of the contact bonding layer provided in a synthetic resin skin material as needed, It selects suitably by the kind of shaping | molding base material. As the adhesive, for example, (1) a two-component curable polyester adhesive, (2) a two-component curable urethane adhesive, and (3) a two-component curable acrylic pressure-sensitive adhesive are preferably used.
The adhesive used for forming the adhesive layer is also available as a commercial product. For example, the Oliveline series [Toyo Ink Co., Ltd.], Welder Adhesive No. 3660 [two-component curable polyurethane adhesive: No Tape Industry Co., Ltd.], Daikarak 7250NT [two-component curable polyester adhesive: Daido Kasei Kogyo Co., Ltd.] and the like are suitable.
The thickness of the adhesive layer is preferably in the range of 20 μm to 50 μm.
　なお、基材層に接着層を形成する場合には、合成樹脂表皮材と接着層との間に、接着性を向上させる目的で、以下に詳述するプライマー層を形成してもよい。合成樹脂表皮材の接着剤を形成する面に、プライマー層を形成し、形成したプライマー層表面に、接着剤及び粘着剤の少なくとも一方を付与することにより、接着層を形成することができる。
　基材層又はプライマー層上に接着層を付与する方法としては、転写法、塗布法など公知の方法をいずれも使用できる。均一な厚みの接着層を簡易に形成しうるという観点からは、転写法を用いることが好ましい。
　基材層等に接着層を形成する場合には、接着層の表面保護を目的として、接着層表面に保護シートを有していてもよい。保護シートとしては、樹脂フィルム、離型処理された紙、樹脂をラミネートした紙などを、適宜用いることができる。保護シートは、後述する成形体形成用樹脂材料に合成樹脂表皮材を接着する際に剥離すればよい。 In addition, when forming an adhesive layer in a base material layer, you may form the primer layer explained in full detail below between the synthetic resin skin material and an adhesive layer for the purpose of improving adhesiveness. An adhesive layer can be formed by forming a primer layer on the surface of the synthetic resin skin material on which an adhesive is to be formed and applying at least one of an adhesive and an adhesive to the surface of the formed primer layer.
As a method for providing the adhesive layer on the base material layer or the primer layer, any known method such as a transfer method or a coating method can be used. From the viewpoint that an adhesive layer having a uniform thickness can be easily formed, it is preferable to use a transfer method.
When an adhesive layer is formed on the base material layer or the like, a protective sheet may be provided on the surface of the adhesive layer for the purpose of protecting the surface of the adhesive layer. As the protective sheet, a resin film, release-treated paper, resin-laminated paper, or the like can be used as appropriate. What is necessary is just to peel a protective sheet, when bonding a synthetic resin skin material to the resin material for molded object formation mentioned later.
（４－３．プライマー層）
　合成樹脂表皮材において、基材層に隣接してさらに接着層を設ける際には、基材層と樹脂成形体との密着性向上を目的として、さらにプライマー層としての樹脂層を接着層と基材層との間に有していてもよい。
　プライマー層は塗布法により形成することができる。即ち、プライマー層を形成するための樹脂を適切な溶媒で溶解し、基材層の、表皮層側とは反対側の面に塗布し、乾燥することでプライマー層を形成することができる。
　プライマー層に含まれる樹脂は、基材層に含まれる熱可塑性樹脂、及び、隣接して設けられる接着層に含まれる接着剤等との親和性が良好であるという観点から、ポリエステル樹脂などの樹脂を用いて形成されることが好ましい。
　樹脂層の塗布量には特に制限はなく、目的に応じて適宜選択される。一般的には、接着性向上効果の観点から、１ｇ／ｍ２～５ｇ／ｍ２の範囲であることが好ましく、２ｇ／ｍ２～３ｇ／ｍ２の範囲であることがさらに好ましい。 (4-3. Primer layer)
In the synthetic resin skin material, when an adhesive layer is further provided adjacent to the base material layer, a primer layer is further used as a primer layer for the purpose of improving the adhesion between the base material layer and the resin molded body. You may have between material layers.
The primer layer can be formed by a coating method. That is, the primer layer can be formed by dissolving the resin for forming the primer layer with an appropriate solvent, applying the resin to the surface of the base material layer opposite to the skin layer side, and drying.
The resin contained in the primer layer is a resin such as a polyester resin from the viewpoint of good affinity with the thermoplastic resin contained in the base material layer and the adhesive contained in the adjacent adhesive layer. It is preferable to form using.
There is no restriction | limiting in particular in the application quantity of a resin layer, According to the objective, it selects suitably. In general, from the viewpoint of the effect of improving adhesiveness, the range is preferably 1 g / m 2 to 5 g / m 2 , and more preferably 2 g / m 2 to 3 g / m 2 .
＜合成樹脂表皮材の製造方法＞
　既述の本開示の合成樹脂表皮材の製造方法には特に制限はなく、公知の製造方法を適宜採用することができる。
　なかでも、以下に詳述する本開示の合成樹脂表皮材の製造方法により製造されることが好ましい。 <Method for producing synthetic resin skin material>
There is no restriction | limiting in particular in the manufacturing method of the synthetic resin skin material of this indication as stated above, A well-known manufacturing method can be employ | adopted suitably.
Especially, it is preferable to manufacture with the manufacturing method of the synthetic resin skin material of this indication explained in full detail below.
　本開示の合成樹脂表皮材の製造方法は、ポリ塩化ビニル樹脂を含有する樹脂組成物を用いてポリ塩化ビニル樹脂を含有する中間層を形成する工程（工程（Ｉ））、アクリロニトリル／ブタジエン／スチレン共重合体を含む熱可塑性樹脂組成物を用いて基材層を形成する工程（工程（ＩＩ））、フッ素樹脂を含む表皮層を準備する工程（工程（ＩＩＩ））、前記表皮層と前記中間層と前記基材層とを、この順に積層して積層体を得る工程（工程（ＩＶ））、及び、得られた積層体の表皮層側に、絞ロールを用いてラミネートエンボス加工を施し、前記表皮層の前記中間層を有する側とは反対側の面に凹凸模様を形成する工程（工程（Ｖ））を含む。
　本開示の合成樹脂表皮材の製造方法は、前記表皮層と前記中間層との間に、意匠層を形成する工程（工程（ＶＩ））をさらに含むことができる。 The synthetic resin skin material manufacturing method of the present disclosure includes a step of forming an intermediate layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin (step (I)), acrylonitrile / butadiene / styrene. A step of forming a base material layer using a thermoplastic resin composition containing a copolymer (step (II)), a step of preparing a skin layer containing a fluororesin (step (III)), the skin layer and the intermediate The layer and the base material layer are laminated in this order to obtain a laminate (step (IV)), and the skin layer side of the obtained laminate is subjected to laminate embossing using a squeeze roll, A step of forming a concavo-convex pattern on the surface of the skin layer opposite to the side having the intermediate layer (step (V)).
The manufacturing method of the synthetic resin skin material of this indication can further include the process (process (VI)) of forming a design layer between the said skin layer and the said intermediate | middle layer.
（工程（Ｉ））
　工程（Ｉ）では、まず、ポリ塩化ビニル樹脂を含有する樹脂組成物を用いてカレンダー法、押出し法、キャスティング法等の公知の方法によりポリ塩化ビニル樹脂を含有する中間層を形成する。なかでも、加工性の観点から、中間層は、カレンダー法により形成することが好ましい。中間層をカレンダー法により形成することで、例えば、溶融押出し法等に比較して、簡易に、均一な膜厚の中間層を形成することができる。また、中間層に着色剤を含有させる際にも、カレンダー法を適用することで、中間層に使用する着色剤の種類や添加量を変更する際に必要な装置内の清掃を容易に行うことができる。
　ＰＶＣ樹脂と着色剤としての顔料を用いて中間層を形成する方法の一例を挙げれば、ＰＶＣ樹脂に対して、顔料を所定量投入し、熱ミキシングロールで加熱混合することにより着色されたＰＶＣ樹脂を得ること、得られた着色されたＰＶＣ樹脂を用いて中間層をカレンダー法により形成すること、を含む方法が挙げられる。着色剤を用いない場合には、顔料の投入工程を省いて同様にして行なうことができる。 (Process (I))
In step (I), first, an intermediate layer containing a polyvinyl chloride resin is formed by a known method such as a calendering method, an extrusion method, or a casting method using a resin composition containing a polyvinyl chloride resin. Especially, it is preferable to form an intermediate | middle layer by a calendar method from a viewpoint of workability. By forming the intermediate layer by a calendar method, for example, an intermediate layer having a uniform film thickness can be easily formed as compared with a melt extrusion method or the like. In addition, when the intermediate layer contains a colorant, by applying the calender method, it is easy to clean the inside of the device necessary when changing the type and amount of colorant used in the intermediate layer. Can do.
An example of a method of forming an intermediate layer using a PVC resin and a pigment as a colorant is a PVC resin colored by adding a predetermined amount of pigment to the PVC resin and heating and mixing with a heat mixing roll. And forming an intermediate layer by a calendar method using the obtained colored PVC resin. When no colorant is used, the process can be performed in the same manner by omitting the pigment charging step.
（工程（ＩＩ））
　工程（ＩＩ）では、ＡＢＳ樹脂を含む熱可塑性樹脂組成物を用いてカレンダー法、押出し法、キャスティング法等の公知の方法により基材層を形成する。なかでも、加工性の観点からカレンダー法により基材層を形成することが好ましい。
　カレンダー法による基材層の形成方法は、用いる樹脂が異なる他は、工程（Ｉ）における中間層の形成方法と同様にして行なうことができる。
　基材層においても、着色剤を含有させる場合には、工程（Ｉ）と同様に、ＡＢＳ樹脂に対して、顔料を所定量投入し、熱ミキシングロールで加熱混合することにより着色されたＡＢＳ樹脂を得ること、得られた着色されたＡＢＳ樹脂を用いて基材層をカレンダー法により形成すること、を含む方法により形成することができる。 (Process (II))
In step (II), a base material layer is formed by a known method such as a calendar method, an extrusion method, or a casting method using a thermoplastic resin composition containing an ABS resin. Especially, it is preferable to form a base material layer by the calendar method from a viewpoint of workability.
The formation method of the base material layer by the calendar method can be performed in the same manner as the formation method of the intermediate layer in the step (I) except that the resin used is different.
Also in the base material layer, when a colorant is contained, as in step (I), a predetermined amount of pigment is added to the ABS resin, and the ABS resin is colored by heating and mixing with a heat mixing roll. And forming a base material layer by a calendering method using the obtained colored ABS resin.
　工程（Ｉ）と工程（ＩＩ）との実施順は任意であり、それぞれ独立して行なうことができる。 The execution order of process (I) and process (II) is arbitrary, and can be performed independently.
（工程（ＩＩＩ））
　工程（ＩＩＩ）では、フッ素樹脂を含む表皮層を準備する。表皮層を準備することは、フッ素樹脂を含む表皮層を形成すること、及び、市販の表皮層を調達することの双方を含む。
　工程（ＩＩＩ）では、フッ素樹脂を含む表皮層を、カレンダー法、押出し法、キャスティング法などにより形成することができる。
　フッ素樹脂を含む表皮層を形成する際に、積層構造を有する表皮層を形成する場合には、２種以上の樹脂を共押出し法等により、積層フィルムを成形する方法を適用することができる。
　また、工程（ＩＩＩ）は、表皮層として、フッ素樹脂を含む、合成樹脂表皮材の説明において既述した如き市販のフィルムを準備することを含む。 (Step (III))
In step (III), a skin layer containing a fluororesin is prepared. Preparing the skin layer includes both forming a skin layer containing a fluororesin and procuring a commercially available skin layer.
In step (III), a skin layer containing a fluororesin can be formed by a calendar method, an extrusion method, a casting method, or the like.
When forming a skin layer containing a fluororesin, when forming a skin layer having a laminated structure, a method of forming a laminated film by coextrusion or the like of two or more resins can be applied.
In addition, step (III) includes preparing a commercially available film as described above in the description of the synthetic resin skin material including a fluororesin as the skin layer.
（工程（ＩＶ））
　工程（ＩＶ）では、工程（Ｉ）で形成された中間層、工程（ＩＩ）で形成された基材層及び工程（ＩＩＩ）で準備された表皮層を、表皮層、中間層及び基材層の順に積層して積層体を得る。
　積層体は、表皮層の一方の面に、中間層、及び基材層をこの順に積層することで形成される。積層された各層は、一対のローラーにより加圧、加熱され、積層体が形成される。 (Process (IV))
In step (IV), the intermediate layer formed in step (I), the base material layer formed in step (II), and the skin layer prepared in step (III) are divided into a skin layer, an intermediate layer, and a base material layer. Is laminated in this order to obtain a laminate.
The laminate is formed by laminating an intermediate layer and a base material layer in this order on one surface of the skin layer. Each laminated layer is pressurized and heated by a pair of rollers to form a laminate.
（工程（Ｖ））
　工程（Ｖ）では、工程（ＩＶ）で得られた積層体の表皮層側に、絞ロールを用いてラミネートエンボス加工を施し、表皮層の、中間層側とは反対側の面に凹凸模様を形成する。
　工程（ＩＶ）と工程（Ｖ）とは、同時に行なうことができる。即ち、表皮層の一方の面上に、中間層及び基材層をこの順に積層し、その後、積層体に対し、絞ロールを用いてラミネートエンボスを行い、各層の加熱加圧接着と、表皮層の面上における所望の凹凸模様の形成を同時に行なうことができる。
　本開示における、ラミネートエンボスとは、加熱圧着を行う一対のエンボスロールの一方に絞ロールを用いてエンボスし、複数の樹脂含有フィルムを熱圧着により貼り合わせ、且つ、樹脂含有フィルムの絞ロールと接する面に絞ロールによる絞押しを行って表面に凹凸を形成することを指す。工程（Ｖ）では、表皮層側に絞ロール、基材層側に平滑なロールが位置する配置にてラミネートエンボスする方法をとることができる。この方法によれば、各層の積層と表皮層における凹凸模様の形成が逐次又は同時に一工程で実施できる。 (Process (V))
In step (V), laminate embossing is performed on the skin layer side of the laminate obtained in step (IV) using a squeeze roll, and a concavo-convex pattern is formed on the surface of the skin layer opposite to the intermediate layer side. Form.
Step (IV) and step (V) can be performed simultaneously. That is, the intermediate layer and the base material layer are laminated in this order on one surface of the skin layer, and then the laminate is embossed with a squeezing roll to heat and pressure bond each layer, and the skin layer. The desired concavo-convex pattern can be simultaneously formed on the surface.
In the present disclosure, the laminate embossing is embossed by using a squeezing roll on one of a pair of embossing rolls for thermocompression bonding, and a plurality of resin-containing films are bonded together by thermocompression bonding, and in contact with the squeezing roll of the resin-containing film. It refers to forming irregularities on the surface by squeezing the surface with a squeeze roll. In the step (V), a laminate embossing method can be employed in such an arrangement that a squeeze roll is located on the skin layer side and a smooth roll is located on the substrate layer side. According to this method, lamination of each layer and formation of the uneven pattern in the skin layer can be performed sequentially or simultaneously in one step.
　表皮層の面上に予め天然皮革様の凹凸模様などの任意の凹凸模様を形成した絞ロールを用いてラミネートエンボスすることにより、複数の樹脂含有フィルムの貼り合わせと樹脂含有フィルムの一方の表面への絞押しとが、一工程で行われ、形成された合成樹脂表皮材において表皮層の最表面に天然皮革様の凹凸など、任意の意匠の凹凸模様が転写される。
　絞ロールに形成する凹凸模様の形状を選択することで、合成樹脂表皮材の表面に、天然皮革様の模様のみならず、任意の凹凸形状を有する模様を形成することができる。
　ラミネートエンボスにおける加熱温度は、１００℃～１９０℃が好適である。 By laminating and embossing with a squeeze roll that has an irregular pattern such as a natural leather-like irregular pattern formed in advance on the surface of the skin layer, to one surface of the resin-containing film The squeezing is performed in one step, and a concavo-convex pattern of an arbitrary design such as a natural leather-like concavo-convex pattern is transferred to the outermost surface of the skin layer in the formed synthetic resin skin material.
By selecting the shape of the concavo-convex pattern formed on the squeezing roll, not only a natural leather-like pattern but also a pattern having an arbitrary concavo-convex shape can be formed on the surface of the synthetic resin skin material.
The heating temperature in laminating embossing is preferably from 100 ° C to 190 ° C.
（工程（ＶＩ））
　工程（ＶＩ）は、合成樹脂表皮材の製造方法において、さらに意匠層を形成する任意の工程である。
　工程（ＶＩ）では、前記工程（ＩＩＩ）で準備した表皮層又は前記工程（Ｉ）で形成した中間層の片面に、意匠層を形成する。
　意匠層を形成する方法としては、例えば、表皮層又は中間層の片面に、予め形成した意匠層を接着する方法、表皮層又は中間層の片面に、アクリル樹脂又は塩化ビニル－酢酸ビニル共重合体を含む印刷インクを用いて印刷を行なう方法などが挙げられる。
　なかでも、印刷により意匠層を形成することが、意匠の自由度が高いため好ましい。意匠層の形成方法としては、図柄を含む意匠層では、印刷法を適用することが挙げられ、着色層としての意匠層であれば、着色剤を含有させた樹脂組成物を、公知の方法によりフィルム状に成形して意匠層とする方法などが適用できる。 (Process (VI))
Step (VI) is an optional step of further forming a design layer in the method for producing a synthetic resin skin material.
In step (VI), a design layer is formed on one surface of the skin layer prepared in step (III) or the intermediate layer formed in step (I).
Examples of the method for forming the design layer include a method of adhering a pre-formed design layer to one side of the skin layer or the intermediate layer, an acrylic resin or a vinyl chloride-vinyl acetate copolymer on one side of the skin layer or the intermediate layer. And a method of performing printing using a printing ink containing.
Especially, it is preferable to form the design layer by printing because the degree of freedom of the design is high. As a design method of a design layer, in a design layer including a design, it is possible to apply a printing method. If the design layer is a colored layer, a resin composition containing a colorant can be obtained by a known method. The method etc. which shape | mold into a film form and use as a design layer are applicable.
　印刷法は、樹脂を含む印刷インクにより公知の図柄を印刷する方法であり、樹脂を含む印刷インク、例えば、アクリル樹脂、塩化ビニル－酢酸ビニル共重合体等を含む印刷インクを、公知の印刷方法、例えば、グラビヤ印刷（凹版印刷）、凸版印刷、オフセット印刷、インクジェット印刷、スクリーン印刷などにより印刷して形成する方法が挙げられる。
　印刷法としては、具体的には、表皮層の片面に、グラビヤ印刷により、アクリル樹脂を含む印刷インクを用いて印刷を行なうことなどが挙げられる。グラビヤ印刷に用いるプリントロールの彫刻の大きさを調整することで、印刷インクの塗布量を調整しながら印刷を行なうことができ、例えば、表皮層の片面に、種々の意匠を形成できる。
　任意の層である意匠層は、表皮層又は中間層の一方の面上に所望により独立して形成することができることから、任意の色相、任意の意匠で所望の意匠を有する層が形成できる。従って、意匠層を設けることで、合成樹脂表皮材に種々の意匠を付与することができる。 The printing method is a method of printing a known pattern with a printing ink containing a resin. A printing ink containing a resin, for example, a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer or the like is used as a known printing method. Examples thereof include a method of printing and forming by gravure printing (intaglio printing), letterpress printing, offset printing, ink jet printing, screen printing and the like.
Specific examples of the printing method include printing on one surface of the skin layer using a printing ink containing an acrylic resin by gravure printing. By adjusting the engraving size of the print roll used for gravure printing, printing can be performed while adjusting the amount of printing ink applied. For example, various designs can be formed on one surface of the skin layer.
Since the design layer which is an arbitrary layer can be independently formed as desired on one surface of the skin layer or the intermediate layer, a layer having a desired design with an arbitrary hue and an arbitrary design can be formed. Therefore, by providing the design layer, various designs can be imparted to the synthetic resin skin material.
＜成形体＞
　既述の本開示の合成樹脂表皮材は、加熱成形による成形体を作製する際に、成形体表面に意匠を付与する目的で好適に使用される。
　本開示の成形体は、成形基材と、成形基材の表面に配置された既述の本開示の合成樹脂表皮材を有する成形体である。
　成形体は、加熱成形により形成することができる。
　加熱成形の方法には特に制限はない。加熱成形方法としては、既述のインサート成形方法が挙げられる。インサート成形方法としては、予め予備成形されていてもよい成形基材の面上に合成樹脂表皮材を配置するか、或いは、金型内に合成樹脂表皮材を配置し、成形基材を配置し、金型内で、例えば、９０℃～１４０℃の温度条件で成形する方法、及び、金型内に合成樹脂表皮材を配置し、その後、加熱、溶融した成形基材となる樹脂を金型内に注入する射出成形方法が挙げられ、上記いずれのインサート成形方法も成形体の形成に適用できる。 <Molded body>
The above-described synthetic resin skin material of the present disclosure is suitably used for the purpose of imparting a design to the surface of the molded body when producing a molded body by thermoforming.
The molded body of the present disclosure is a molded body having the molded base material and the above-described synthetic resin skin material of the present disclosure disposed on the surface of the molded base material.
The molded body can be formed by thermoforming.
There is no restriction | limiting in particular in the method of thermoforming. Examples of the heat molding method include the above-described insert molding method. As an insert molding method, a synthetic resin skin material is placed on the surface of a molding base material that may be preformed in advance, or a synthetic resin skin material is placed in a mold and a molding base material is placed. In a mold, for example, a method of molding under a temperature condition of 90 ° C. to 140 ° C., and a synthetic resin skin material is placed in the mold, and then a resin that becomes a molding substrate heated and melted is molded into the mold There is an injection molding method for injecting into any one of them, and any of the above-mentioned insert molding methods can be applied to the formation of a molded body.
　成形体の製造工程に用いられる成形基材に含まれる樹脂は、一般に成形用に使用される樹脂であれば、特に制限はない。
　なかでも、ＡＢＳ樹脂、ＰＰ、ＰＣ、ＰＣとＡＢＳ樹脂との混合物（ＰＣ／ＡＢＳ）等を用いることが好ましい。
　加熱温度条件は、９０℃～１４０℃の範囲とすることが好ましい。インサート成形する場合には、成形基材である樹脂の溶融温度まで加熱して成形が行なわれる。
　本開示の合成樹脂表皮材は、加熱成形性が良好であり、また、インサート成形などの溶融樹脂を用いた加熱成形を行なった後も、表皮層の表面に形成された凹凸模様の保持性が良好である。このため、通常は、意匠層、表面の凹凸模様の保持が困難であるインサート成形方法に適用した場合に、効果が著しいといえる。 If resin contained in the shaping | molding base material used for the manufacturing process of a molded object is resin generally used for shaping | molding, there will be no restriction | limiting in particular.
Among these, it is preferable to use ABS resin, PP, PC, a mixture of PC and ABS resin (PC / ABS), or the like.
The heating temperature condition is preferably in the range of 90 ° C to 140 ° C. In the case of insert molding, the molding is performed by heating to the melting temperature of the resin as the molding substrate.
The synthetic resin skin material of the present disclosure has good heat moldability, and retains the uneven pattern formed on the surface of the skin layer even after heat molding using a molten resin such as insert molding. It is good. For this reason, it can be said that the effect is usually remarkable when applied to an insert molding method in which it is difficult to maintain the design layer and the uneven pattern on the surface.
　本開示の合成樹脂表皮材は、簡易な方法で製造することができ、外観、耐久性に優れ、加熱成形用の表皮材として好適に使用されることから、自動車用内装外装材、鉄道車輌及び航空機の内装部品、家具、靴、履物、鞄、建装用内外装部材、衣類表装材及び裏地、など種々の分野に好適に使用しうる。 The synthetic resin skin material of the present disclosure can be manufactured by a simple method, is excellent in appearance and durability, and is suitably used as a skin material for thermoforming. It can be suitably used in various fields such as aircraft interior parts, furniture, shoes, footwear, bags, building interior / exterior members, clothing cover materials and linings.
　以下、実施例を挙げて本開示の合成樹脂表皮材について具体的に説明するが、本開示はこれらに制限されるものではない。 Hereinafter, the synthetic resin skin material of the present disclosure will be specifically described with reference to examples, but the present disclosure is not limited thereto.
〔実施例１〕
（合成樹脂表皮材の製造）
　まず、ＰＶＣ樹脂〔Ｓ１００８Ｃ（商品名）、（株）カネカ〕１００ｋｇに、顔料（カーボンブラック）２ｋｇを投入し、２００℃に加熱しながらカレンダー法により、乾燥後の厚みが２００μｍになるようにシート状に成形して中間層を得た（工程（Ｉ））。
　別工程にて、ＡＢＳ樹脂〔ＴＭ－３０Ｇ６（商品名）、ＵＧＭ－ＡＢＳ（株）〕１００ｋｇに、顔料（カーボンブラック）２ｋｇを投入し、２００℃に加熱しながらカレンダー法により、乾燥後の厚みが２００μｍになるようにシート状に成形して基材層を得た（工程（ＩＩ））。
　表皮層として、ＫＦＣフィルム　ＦＴ－５０Ｙ（商品名）、クレハエクステック（株）（フッ素樹脂であるポリフッ化ビニリデン含有層とアクリル樹脂であるポリメチルメタクリレート含有層との積層体）を準備した（工程（ＩＩＩ））。
　表皮層におけるポリメチルメタクリレート含有層側に、アクリル樹脂を含む印刷インク（ＶＴＰ－ＮＴ（商品名）、ＤＩＣ（株））を用いて、木目柄を印刷して、厚さ５μｍの意匠層を形成した（工程（ＶＩ））。 [Example 1]
(Manufacture of synthetic resin skin material)
First, 100 kg of PVC resin [S1008C (trade name), Kaneka Co., Ltd.] is charged with 2 kg of pigment (carbon black) and heated to 200 ° C. by a calendar method so that the thickness after drying becomes 200 μm. To obtain an intermediate layer (step (I)).
In a separate process, 100 kg of ABS resin [TM-30G6 (trade name), UGM-ABS Co., Ltd.] was charged with 2 kg of pigment (carbon black), and the thickness after drying by calendering while heating to 200 ° C. Was formed into a sheet shape so as to be 200 μm to obtain a base material layer (step (II)).
KFC film FT-50Y (trade name), Kureha Extec Co., Ltd. (a laminate of a polyvinylidene fluoride-containing layer that is a fluororesin and a polymethylmethacrylate-containing layer that is an acrylic resin) was prepared as a skin layer (process) (III)).
Using a printing ink containing acrylic resin (VTP-NT (trade name), DIC Corporation) on the polymethyl methacrylate-containing layer side of the skin layer, a wood grain pattern is printed to form a 5 μm thick design layer (Step (VI)).
　前工程で形成された意匠層の表皮層を有する側とは反対側に、予め形成した中間層と、基材層とをこの順に積層した（工程（ＩＶ））。
　得られた積層体を、一対のエンボスロールの一方が絞模様を有する絞ロールであるエンボスロールを用いて、表皮層側を絞ロールに接触させて、ラミネートエンボスを行い、基材層上に、中間層、意匠層及び表面に絞模様を有する表皮層を有する実施例１の合成樹脂表皮材を得た（工程（Ｖ））。ラミネートエンボスにおける温度条件は、積層体表面温度が１７０℃であり、速度は１０ｍ／分で行った。
　既述の如く、実施例１では、任意の工程である意匠層の形成工程（工程（ＶＩ））を、工程（ＩＩＩ）の後、工程（ＩＶ）に先だって行なうことで、中間層と表皮層との間に意匠層を形成した。 On the side opposite to the side having the skin layer of the design layer formed in the previous step, a preformed intermediate layer and a base material layer were laminated in this order (step (IV)).
Using the embossed roll, which is a drawn roll in which one of a pair of embossed rolls has a drawn pattern, the skin layer side is brought into contact with the drawn roll, and laminate embossing is performed on the base material layer. The synthetic resin skin material of Example 1 which has an intermediate | middle layer, a design layer, and the skin layer which has a drawing pattern on the surface was obtained (process (V)). The temperature conditions in the laminate embossing were such that the laminate surface temperature was 170 ° C. and the speed was 10 m / min.
As described above, in Example 1, the design layer forming step (step (VI)), which is an optional step, is performed after step (III) and before step (IV), so that the intermediate layer and the skin layer are formed. A design layer was formed between the two.
（合成樹脂表皮材の評価：凹凸模様の保持維持性）
　得られた合成樹脂表皮材において、絞模様が形成された表皮層の表面粗さを、表面粗さ計（（株）東京精密製、サーフコム１３０Ａ）にて測定した。
　その後、合成樹脂表皮材における表皮層の表面が１３０℃になるまで加熱して１分間維持し、常温（２５℃）まで降温し、加熱後の表皮層の表面について、表面粗さを、加熱前と同様の条件で測定し、加熱前後の表面粗さを対比して、以下の式により凹部深さ保持率を算出した。
　凹部深さ保持率（％）＝〔加熱後の凹部の深さ／加熱前の凹部の深さ〕×１００ (Evaluation of synthetic resin skin material: retention and maintenance of uneven pattern)
In the obtained synthetic resin skin material, the surface roughness of the skin layer on which the drawn pattern was formed was measured with a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.).
Thereafter, the surface of the skin layer in the synthetic resin skin material is heated to 130 ° C. and maintained for 1 minute, the temperature is lowered to room temperature (25 ° C.), and the surface roughness of the surface of the skin layer after heating is measured before heating. The recess depth retention was calculated according to the following formula by comparing the surface roughness before and after heating.
Recess depth retention ratio (%) = [depth of recess after heating / depth of recess before heating] × 100
　その結果、加熱後の凹部深さ保持率は９０％程度であり、絞模様の凹凸の形状が加熱後も維持されており、加熱後の外観も良好であった。加熱後の凹部深さの保持率を表１に示した。
　なお、合成樹脂表皮材の加熱後の凹凸模様の保持性評価において、凹部深さ保持率が７０％以上である場合には、加熱成形用の成形体用として実用に供しうるレベルであり、凹部深さ保持率が７０％未満の場合には、実用上問題のあるレベルである。なかでも、凹部深さ保持率が５０％未満のものは、加熱成形する成形体表面に適用する合成樹脂表皮材としては不適なレベルである。 As a result, the concave depth retention after heating was about 90%, the shape of the irregularities of the drawn pattern was maintained after heating, and the appearance after heating was also good. Table 1 shows the retention ratio of the recess depth after heating.
In the evaluation of the retention of the uneven pattern after heating of the synthetic resin skin material, when the recess depth retention is 70% or more, it is at a level that can be practically used as a molded body for thermoforming. When the depth retention is less than 70%, it is a practically problematic level. Among them, those having a recess depth retention of less than 50% are unsuitable levels as a synthetic resin skin material applied to the surface of a molded body to be heat-molded.
（成形体の製造）
　得られた実施例１の合成樹脂表皮材を金型内に配置し、成形基材用の樹脂（アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ））を２００℃～３００℃の温度条件にて加熱溶融し、金型内に供給して射出成形し、成形基材表面に合成樹脂表皮材が配置された成形体を得た。なお、上記温度条件は、射出前の樹脂の溶融温度である。 (Manufacture of molded products)
The obtained synthetic resin skin material of Example 1 was placed in a mold, and a resin for a molding substrate (acrylonitrile / butadiene / styrene copolymer (ABS)) was heated at a temperature of 200 ° C. to 300 ° C. It was melted, supplied into a mold, and injection molded to obtain a molded body in which a synthetic resin skin material was disposed on the surface of the molding substrate. The temperature condition is the melting temperature of the resin before injection.
（成形体の評価）
　得られた成形体を以下の基準にて評価した。評価の結果を下記表１に示す。
　なお、凹凸模様の維持性以外の評価結果は、目視による観察において外観上の変化及び劣化がなかったものを「Ａ」、外観上、変化或いは劣化が認められたものを「Ｂ」とした。また、「－」は、その評価が行われなかったことを示す。 (Evaluation of molded body)
The obtained molded body was evaluated according to the following criteria. The evaluation results are shown in Table 1 below.
In addition, the evaluation results other than the maintainability of the concavo-convex pattern were “A” when there was no change or deterioration in appearance by visual observation, and “B” when change or deterioration was observed in appearance. “-” Indicates that the evaluation was not performed.
１．凹凸模様の維持性
　得られた実施例１の合成樹脂表皮材を用いて作製した成形体の表面の表面粗さを、表面粗さ計（（株）東京精密製、サーフコム１３０Ａ）にて測定した。
　その結果を、既述の成形前の合成樹脂表皮材における表面粗さと対比して、凹部深さ保持率を算出したところ、加熱後の凹部深さ保持率は、５０％程度であった。実施例１の合成樹脂表皮材は、インサート成形という厳しい条件で加熱成形を行なっても、凹凸模様の保持性が良好であり、加熱後の外観も良好であることがわかる。結果を表１に示した。
　なお、加熱成形した後の、成形体表面における合成樹脂表皮材においては、凹部深さ保持率が５０％以上であれば、例えば、加熱を伴う成形体の形成に使用しても実用上問題のないレベルであり、５０％未満であると実用上問題のあるレベルであると判断される。
　評価の結果、加熱後の成形体の表面においても、実施例１の合成樹脂表皮材が優れた凹凸模様の維持性を有することが確認された。 1. Surface roughness of the molded body produced using the synthetic resin skin material of Example 1 obtained was measured with a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.). .
When the result was compared with the surface roughness of the synthetic resin skin material before molding described above, the recess depth retention was calculated, and the recess depth retention after heating was about 50%. It can be seen that the synthetic resin skin material of Example 1 has good ruggedness retention and good appearance after heating even when heat molding is performed under severe conditions such as insert molding. The results are shown in Table 1.
In addition, in the synthetic resin skin material on the surface of the molded body after heat molding, if the recess depth retention is 50% or more, for example, even if it is used for forming a molded body with heating, there is a practical problem. If it is less than 50%, a practically problematic level is determined.
As a result of the evaluation, it was confirmed that the synthetic resin skin material of Example 1 has excellent ruggedness maintainability even on the surface of the molded body after heating.
２．耐溶剤性（耐ガソリン、耐ケロシン）、耐薬品性（硫酸、水酸化ナトリウム水溶液）
　得られた実施例及び比較例の成形体について、溶剤としてのガソリン、ケロシン（灯油）、薬品としての硫酸、水酸化ナトリウム０．４質量％水溶液に、それぞれ３０分浸漬後、成形体を引き上げて１週間放置した。
　放置後の成形体を、ガソリン浸漬品、ケロシン浸漬品、硫酸浸漬品、及び水酸化ナトリウム水溶液浸漬品のそれぞれについて、目視にて外観評価を行った。以下の基準で評価した。
Ａ：目視による観察では、成形体の溶剤又は薬品による劣化は確認されなかった。
Ｂ：目視による観察で、成形体の溶剤又は薬品による劣化に起因して外観の低下が認められた。 2. Solvent resistance (gasoline resistance, kerosene resistance), chemical resistance (sulfuric acid, sodium hydroxide aqueous solution)
About the obtained molded bodies of Examples and Comparative Examples, the molded bodies were pulled up after being immersed in gasoline, kerosene (kerosene) as a solvent, sulfuric acid as a chemical, and a 0.4% by mass aqueous solution of sodium hydroxide for 30 minutes, respectively. Left for a week.
The appearance after the standing was visually evaluated for each of a gasoline-immersed product, a kerosene-immersed product, a sulfuric acid-immersed product, and a sodium hydroxide aqueous solution-immersed product. Evaluation was made according to the following criteria.
A: Deterioration due to the solvent or chemicals of the molded product was not confirmed by visual observation.
B: As a result of visual observation, a decrease in appearance was observed due to deterioration of the molded product by a solvent or chemicals.
３．インサート成形性
　得られた実施例及び比較例の成形体について、目視にて外観評価を行った。以下の基準で評価した。
Ａ：目視による観察では、成形体表面のシワ、樹脂漏れ、ゲートダメージ、及び白化のいずれも確認されなかった。
Ｂ：目視による観察で、成形体表面のシワ、樹脂漏れ、ゲートダメージ、及び白化のうち１つ以上が確認され、実用上問題となる劣化が確認された。
　結果を下記表１に示した。 3. Insert Moldability The appearance of the molded bodies obtained in Examples and Comparative Examples was visually evaluated. Evaluation was made according to the following criteria.
A: Visual observation did not confirm any wrinkles, resin leakage, gate damage, or whitening on the surface of the molded body.
B: One or more of wrinkles, resin leakage, gate damage, and whitening on the surface of the molded body were confirmed by visual observation, and deterioration that was a problem in practice was confirmed.
The results are shown in Table 1 below.
〔実施例２〕
　表皮層として用いたＫＦＣフィルムを、フッ素樹脂含有層とアクリル樹脂含有層との積層体であるアクリプレン（登録商標）ＦＢＳ００６（商品名）、三菱ケミカル（株）に代えた以外は実施例１と同様にして、実施例２の合成樹脂表皮材を作製し、得られた合成樹脂表皮材を用いて、実施例１と同様にして成形体を作製し、同様にして評価した。結果を下記表１に示した。 [Example 2]
Example 1 except that the KFC film used as the skin layer was replaced with acrylprene (registered trademark) FBS006 (trade name), which is a laminate of a fluororesin-containing layer and an acrylic resin-containing layer, and Mitsubishi Chemical Corporation. Then, a synthetic resin skin material of Example 2 was produced, and using the obtained synthetic resin skin material, a molded body was produced in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 1 below.
〔比較例１〕
　表皮層として用いたＫＦＣフィルムを、ポリメチルメタクリレートフィルムであるアクリプレン（登録商標）フィルムＨＢＳ０１０Ｐ（商品名）、三菱ケミカル（株）に代えた。
　さらに、中間層形成用のＰＶＣ樹脂に代えて、基材層の作製に用いたのと同じＡＢＳ樹脂を用いた以外は実施例１と同様にして、比較例１の合成樹脂表皮材を作製し、得られた合成樹脂表皮材を用いて、実施例１と同様にして成形体を作製し、実施例１と同様にして評価した。
　表皮材としての凹凸模様の保持性は３％と極めて低く、その後の成形体の形成後の凹凸模様の深さは同条件では測定し難かったため、下記表１において凹凸維持性は「－」で示した。 [Comparative Example 1]
The KFC film used as the skin layer was replaced with acrylprene (registered trademark) film HBS010P (trade name) and Mitsubishi Chemical Corporation, which are polymethyl methacrylate films.
Further, in place of the PVC resin for forming the intermediate layer, the synthetic resin skin material of Comparative Example 1 was produced in the same manner as in Example 1 except that the same ABS resin as that used for the production of the base material layer was used. Using the obtained synthetic resin skin material, a molded body was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
The retention of the uneven pattern as the skin material is extremely low at 3%, and the depth of the uneven pattern after forming the molded body was difficult to measure under the same conditions. Indicated.
〔比較例２〕
　中間層形成用のＰＶＣ樹脂に代えて、基材層の作製に用いたのと同じＡＢＳ樹脂を用いた以外は実施例１と同様にして、比較例１の合成樹脂表皮材を作製し、得られた合成樹脂表皮材を用いて、実施例１と同様にして成形体を作製し、実施例１と同様にして評価した。結果を下記表１に示した。 [Comparative Example 2]
A synthetic resin skin material of Comparative Example 1 was prepared and obtained in the same manner as in Example 1 except that the same ABS resin as that used for the production of the base material layer was used instead of the PVC resin for forming the intermediate layer. Using the obtained synthetic resin skin material, a molded body was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
 
　表１の結果より、実施例の合成樹脂表皮材は、加熱条件下でも、表面の凹凸（絞）模様の保持性に優れ、これを用いて得た成形体は、インサート成形性が良好であり、耐溶剤性、耐薬品などの耐久性に優れ、加熱成形後も、合成樹脂表皮材表面に形成された凹凸（絞）模様の保持性に優れることがわかる。
　他方、表皮層及び中間層に用いる樹脂が請求項１の範囲外である比較例１の合成樹脂表皮材は、凹凸保持率が極めて低く、加熱成形後には凹凸が消滅していた。また、表皮材として、実施例１と同様の樹脂フィルムを用いても、中間層に用いる樹脂が請求項１の範囲外である比較例２の合成樹脂表皮材は、表皮材としての凹凸模様の保持率、合成樹脂表皮材を用いて得た成形体の凹凸模様の保持性のいずれも実施例に比較して劣り、凹凸模様の保持性において、インサート成形体の形成用として、実用に供し得ないレベルであった。 From the results in Table 1, the synthetic resin skin materials of the examples are excellent in the retention of the unevenness (drawing) pattern on the surface even under heating conditions, and the molded products obtained using this have good insert moldability. It can be seen that it is excellent in durability such as solvent resistance and chemical resistance, and is excellent in retaining the unevenness (drawing) pattern formed on the surface of the synthetic resin skin material even after thermoforming.
On the other hand, the synthetic resin skin material of Comparative Example 1 in which the resin used for the skin layer and the intermediate layer is outside the scope of claim 1 has an extremely low unevenness retention rate, and the unevenness disappeared after the heat molding. Moreover, even if the resin film similar to Example 1 is used as the skin material, the synthetic resin skin material of Comparative Example 2 in which the resin used for the intermediate layer is outside the scope of claim 1 has an uneven pattern as the skin material. The retention rate and the concavo-convex pattern retainability of the molded body obtained using the synthetic resin skin material are inferior to those of the examples, and the concavo-convex pattern retainability can be put to practical use for forming an insert molded body. There was no level.
（符号の説明）
　１０　　　　　　合成樹脂表皮材
　１２　　　　　　基材層
　１４　　　　　　中間層
　１６　　　　　　意匠層
　１８　　　　　　表皮層 (Explanation of symbols)
DESCRIPTION OF SYMBOLS 10 Synthetic resin skin material 12 Base material layer 14 Intermediate | middle layer 16 Design layer 18 Skin layer
　２０１８年３月３０日に出願された日本国特許出願２０１８－０６６６７６の開示は参照により本開示に取り込まれる。
　本開示に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本開示中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2018-066666 filed on Mar. 30, 2018 is incorporated into this disclosure by reference.
All documents, patent applications, and technical standards mentioned in this disclosure are as if they were specifically and individually stated that each individual document, patent application, and technical standard was incorporated by reference. Incorporated by reference in the disclosure.

Claims (10)

  1. 　熱可塑性樹脂を含む基材層と、
    　前記基材層の一方の面上に設けられ、ポリ塩化ビニル樹脂を含有する中間層と、
    　前記中間層の基材層とは反対側に設けられ、前記中間層側とは反対側の表面に凹凸を有し、且つ、フッ素樹脂を含有する表皮層と、を備える合成樹脂表皮材。     A base material layer containing a thermoplastic resin;
    An intermediate layer provided on one surface of the base material layer and containing a polyvinyl chloride resin;
    A synthetic resin skin material provided with a skin layer provided on a side opposite to the base material layer of the intermediate layer, having an unevenness on a surface opposite to the intermediate layer side, and containing a fluororesin.
  2. 　前記中間層と前記表皮層の間に、さらに、意匠層を備える請求項１に記載の合成樹脂表皮材。 The synthetic resin skin material according to claim 1, further comprising a design layer between the intermediate layer and the skin layer.
  3. 　前記意匠層が、アクリル樹脂及び塩化ビニル－酢酸ビニル共重合体から選ばれる少なくとも１種を含む印刷インク層である請求項２に記載の合成樹脂表皮材。 The synthetic resin skin material according to claim 2, wherein the design layer is a printing ink layer containing at least one selected from an acrylic resin and a vinyl chloride-vinyl acetate copolymer.
  4. 　前記フッ素樹脂が、３フッ化塩化エチレン－フッ化ビニリデン共重合体、フッ化ビニリデン－６フッ化プロピレン共重合体、及び、フッ化ビニリデン－６フッ化プロピレン－４フッ化エチレン共重合体からなる群より選択される少なくとも１種のフッ素樹脂を含む請求項１～請求項３のいずれか１項に記載の合成樹脂表皮材。 The fluororesin comprises a trifluoroethylene chloride-vinylidene fluoride copolymer, a vinylidene fluoride-6 propylene fluoride copolymer, and a vinylidene fluoride-6 fluoropropylene-4 fluoroethylene copolymer. The synthetic resin skin material according to any one of claims 1 to 3, comprising at least one fluororesin selected from the group.
  5. 　前記基材層が、アクリロニトリル／ブタジエン／スチレン共重合体を含む請求項１～請求項４のいずれか１項に記載の合成樹脂表皮材。 The synthetic resin skin material according to any one of claims 1 to 4, wherein the base material layer contains an acrylonitrile / butadiene / styrene copolymer.
  6. 　加熱成形加工品の表皮材である請求項１～請求項５のいずれか１項に記載の合成樹脂表皮材。 The synthetic resin skin material according to any one of claims 1 to 5, which is a skin material of a thermoformed product.
  7. 　前記基材層の、中間層側とは反対側の面に、さらに、接着層を備える請求項１～請求項６のいずれか１項に記載の合成樹脂表皮材。 The synthetic resin skin material according to any one of claims 1 to 6, further comprising an adhesive layer on a surface opposite to the intermediate layer side of the base material layer.
  8. 　ポリ塩化ビニル樹脂を含有する樹脂組成物を用いてポリ塩化ビニル樹脂を含有する中間層を形成する工程、
    　アクリロニトリル／ブタジエン／スチレン共重合体を含む熱可塑性樹脂組成物を用いて基材層を形成する工程、
    　フッ素樹脂を含む表皮層を準備する工程、
    　前記表皮層と前記中間層と前記基材層とを、この順に積層して積層体を得る工程、及び、
    　得られた積層体の前記表皮層側に、絞ロールを用いてラミネートエンボス加工を施し、前記表皮層の前記中間層側とは反対側の面に凹凸模様を形成する工程を含む合成樹脂表皮材の製造方法。     Forming an intermediate layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin;
    Forming a base material layer using a thermoplastic resin composition containing an acrylonitrile / butadiene / styrene copolymer;
    A step of preparing a skin layer containing a fluororesin,
    The step of laminating the skin layer, the intermediate layer and the base material layer in this order to obtain a laminate, and
    A synthetic resin skin material comprising a step of laminating embossing using a squeezing roll on the skin layer side of the obtained laminate, and forming a concavo-convex pattern on the surface of the skin layer opposite to the intermediate layer side Manufacturing method.
  9. 　前記表皮層と前記中間層との間に、意匠層を形成する工程をさらに含む請求項８に記載の合成樹脂表皮材の製造方法。 The method for producing a synthetic resin skin material according to claim 8, further comprising a step of forming a design layer between the skin layer and the intermediate layer.
  10. 　成形基材と、成形基材の表面に配置された請求項１～請求項７のいずれか１項に記載の合成樹脂表皮材を有する成形体。 A molded body having a molded base material and the synthetic resin skin material according to any one of claims 1 to 7 disposed on a surface of the molded base material.
PCT/JP2019/012519 2018-03-30 2019-03-25 Synthetic resin skin material, method for producing synthetic resin skin material, and molded body WO2019188988A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980013798.4A CN111727118A (en) 2018-03-30 2019-03-25 Synthetic resin skin material, method for producing synthetic resin skin material, and molded body

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-066676 2018-03-30
JP2018066676A JP7040724B2 (en) 2018-03-30 2018-03-30 Synthetic resin skin material, manufacturing method of synthetic resin skin material and molded product

Publications (1)

Publication Number Publication Date
WO2019188988A1 true WO2019188988A1 (en) 2019-10-03

Family

ID=68060067

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/012519 WO2019188988A1 (en) 2018-03-30 2019-03-25 Synthetic resin skin material, method for producing synthetic resin skin material, and molded body

Country Status (3)

Country Link
JP (1) JP7040724B2 (en)
CN (1) CN111727118A (en)
WO (1) WO2019188988A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04343772A (en) * 1991-05-15 1992-11-30 Achilles Corp Functional leather and production thereof
JPH0585630U (en) * 1992-03-02 1993-11-19 凸版印刷株式会社 Storage door member
JP3030051U (en) * 1996-04-11 1996-10-18 信越ポリマー株式会社 Decorative sheet for membrane molding
JP2002011754A (en) * 2000-06-30 2002-01-15 Dainippon Printing Co Ltd Injection molding in-mold decorating sheet
JP2016137612A (en) * 2015-01-27 2016-08-04 共和レザー株式会社 Synthetic resin skin material, method for producing synthetic resin skin material, molded body using synthetic resin skin material and method for producing molded body

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3500235B2 (en) * 1995-08-31 2004-02-23 日本写真印刷株式会社 Manufacturing method of acrylic insert film and acrylic insert molded product
JP3514565B2 (en) * 1995-11-07 2004-03-31 日本写真印刷株式会社 Insert film and method for manufacturing insert molded product using the same
JP2007283665A (en) * 2006-04-18 2007-11-01 Mitsubishi Rayon Co Ltd Matted acrylic resin film material for thermoforming, production method thereof and laminate including matted acrylic resin film material for thermoforming

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04343772A (en) * 1991-05-15 1992-11-30 Achilles Corp Functional leather and production thereof
JPH0585630U (en) * 1992-03-02 1993-11-19 凸版印刷株式会社 Storage door member
JP3030051U (en) * 1996-04-11 1996-10-18 信越ポリマー株式会社 Decorative sheet for membrane molding
JP2002011754A (en) * 2000-06-30 2002-01-15 Dainippon Printing Co Ltd Injection molding in-mold decorating sheet
JP2016137612A (en) * 2015-01-27 2016-08-04 共和レザー株式会社 Synthetic resin skin material, method for producing synthetic resin skin material, molded body using synthetic resin skin material and method for producing molded body

Also Published As

Publication number Publication date
JP2019177499A (en) 2019-10-17
CN111727118A (en) 2020-09-29
JP7040724B2 (en) 2022-03-23

Similar Documents

Publication Publication Date Title
US6364992B1 (en) Decorative sheet and process for producing the same
WO2019225386A1 (en) Decorative film, decorative film production method, decorative molded body and decorative molded body production method
JP2016137612A (en) Synthetic resin skin material, method for producing synthetic resin skin material, molded body using synthetic resin skin material and method for producing molded body
JP2014184726A (en) Decorative sheet, simultaneous injection molding decorative method and decorative molding article
JP5119638B2 (en) Irregular decorative injection molded product
JPH11147237A (en) Acrylic film for bonding simultaneously with injection molding
US11660836B2 (en) Decorative sheet
JP6745189B2 (en) Method for manufacturing synthetic resin molded body
JP6151994B2 (en) Synthetic resin skin material for heat molding, method for producing the same, and method for producing a molded body using the synthetic resin skin material for heat molding
WO2019188988A1 (en) Synthetic resin skin material, method for producing synthetic resin skin material, and molded body
US20230039705A1 (en) Decorative sheet for vacuum forming, method for producing decorative material, and decorative material
JP2023090516A (en) Synthetic resin skin material, method for manufacturing synthetic resin skin material, and molding
JP4962612B2 (en) Decorative sheet manufacturing method, decorative molded product, and injection molding simultaneous decoration method
JP7358717B2 (en) Decorative film, method for manufacturing a decorative film, and method for manufacturing a decorative molded object
JP7371827B2 (en) Vehicle exterior protective film and method for manufacturing vehicle exterior protective film
JP4119697B2 (en) Decorative sheet and method for producing decorative sheet
JP5240358B2 (en) Irregular decorative injection molded product
JP2021070300A (en) Decorative film, method for producing decorative film, decorative molding, and method for producing decorative molding
JP4514849B2 (en) Manufacturing method of decorative sheet
JP6311419B2 (en) Glittering decorative sheet
US11890845B2 (en) Decorative sheet
JP5015996B2 (en) Sheet for simultaneous injection molding
JP2002187161A (en) Decorative sheet, injection molding in-mold decorating method, and decorative molded article
JP2022054340A (en) Decorative film, manufacturing method of decorative film, decorative compact, manufacturing method of decorative compact
JP2002347185A (en) Decorative sheet

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19777642

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19777642

Country of ref document: EP

Kind code of ref document: A1