WO2019188988A1 - Matériau de peau en résine synthétique, procédé de production de matériau de peau en résine synthétique, et corps moulé - Google Patents

Matériau de peau en résine synthétique, procédé de production de matériau de peau en résine synthétique, et corps moulé Download PDF

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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
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Prior art keywords
layer
synthetic resin
skin
skin material
resin
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PCT/JP2019/012519
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English (en)
Japanese (ja)
Inventor
智彦 山田
忠彦 稲垣
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共和レザー株式会社
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Priority to CN201980013798.4A priority Critical patent/CN111727118A/zh
Publication of WO2019188988A1 publication Critical patent/WO2019188988A1/fr

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    • 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.

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  • 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

La présente invention concerne un matériau de peau en résine synthétique qui comporte : une couche de matériau de base qui contient une résine thermoplastique ; une couche intermédiaire qui est disposée sur une surface de la couche de matériau de base et contient une résine de polychlorure de vinyle ; et une couche de peau qui est disposée sur une surface de la couche intermédiaire, ladite surface étant sur le côté opposé de la surface côté couche de matériau de base, et qui contient une résine fluorée, tout en ayant des évidements et des saillies sur une surface qui se trouve sur le côté opposé de la surface côté couche intermédiaire. La présente invention concerne également : un procédé de production de ce matériau de peau en résine synthétique ; et un corps moulé.
PCT/JP2019/012519 2018-03-30 2019-03-25 Matériau de peau en résine synthétique, procédé de production de matériau de peau en résine synthétique, et corps moulé WO2019188988A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04343772A (ja) * 1991-05-15 1992-11-30 Achilles Corp 機能性レザー及びその製造方法
JPH0585630U (ja) * 1992-03-02 1993-11-19 凸版印刷株式会社 収納扉部材
JP3030051U (ja) * 1996-04-11 1996-10-18 信越ポリマー株式会社 メンブレン成型用化粧シート
JP2002011754A (ja) * 2000-06-30 2002-01-15 Dainippon Printing Co Ltd 射出成形同時加飾用シート
JP2016137612A (ja) * 2015-01-27 2016-08-04 共和レザー株式会社 合成樹脂表皮材、合成樹脂表皮材の製造方法、合成樹脂表皮材を用いた成形体、及び成形体の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3500235B2 (ja) * 1995-08-31 2004-02-23 日本写真印刷株式会社 アクリルインサートフィルムとアクリルインサート成形品の製造方法
JP3514565B2 (ja) * 1995-11-07 2004-03-31 日本写真印刷株式会社 インサートフィルムとこれを用いたインサート成形品の製造方法
JP2007283665A (ja) * 2006-04-18 2007-11-01 Mitsubishi Rayon Co Ltd 熱成形用艶消しアクリル樹脂フィルム状物、熱成形用艶消しアクリル樹脂フィルム状物の製造方法、および、この熱成形用艶消しアクリル樹脂フィルム状物を含む積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04343772A (ja) * 1991-05-15 1992-11-30 Achilles Corp 機能性レザー及びその製造方法
JPH0585630U (ja) * 1992-03-02 1993-11-19 凸版印刷株式会社 収納扉部材
JP3030051U (ja) * 1996-04-11 1996-10-18 信越ポリマー株式会社 メンブレン成型用化粧シート
JP2002011754A (ja) * 2000-06-30 2002-01-15 Dainippon Printing Co Ltd 射出成形同時加飾用シート
JP2016137612A (ja) * 2015-01-27 2016-08-04 共和レザー株式会社 合成樹脂表皮材、合成樹脂表皮材の製造方法、合成樹脂表皮材を用いた成形体、及び成形体の製造方法

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