WO2020149215A1 - 合成樹脂表皮材及びその製造方法 - Google Patents

合成樹脂表皮材及びその製造方法 Download PDF

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Publication number
WO2020149215A1
WO2020149215A1 PCT/JP2020/000528 JP2020000528W WO2020149215A1 WO 2020149215 A1 WO2020149215 A1 WO 2020149215A1 JP 2020000528 W JP2020000528 W JP 2020000528W WO 2020149215 A1 WO2020149215 A1 WO 2020149215A1
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Prior art keywords
layer
vinyl chloride
skin
chloride resin
resin
Prior art date
Application number
PCT/JP2020/000528
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English (en)
French (fr)
Inventor
隆太郎 鈴木
昌人 山岡
Original Assignee
共和レザー株式会社
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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 US17/260,342 priority Critical patent/US20210292965A1/en
Priority to CN202080003995.0A priority patent/CN112423985A/zh
Publication of WO2020149215A1 publication Critical patent/WO2020149215A1/ja

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Definitions

  • the present disclosure relates to a synthetic resin skin material and a manufacturing method thereof.
  • FIG. 3 is a schematic cross-sectional view of a conventional synthetic resin skin material 30 having a skin layer 32 containing a vinyl chloride resin.
  • the known synthetic resin skin material 30 has a vinyl chloride foam layer as the foam resin layer 18 adhered to the surface of the base fabric 14 via the adhesive layer 20, and a skin containing the vinyl chloride resin on the surface of the foam resin layer 18.
  • the layer 32 and the surface treatment layer 16 are provided.
  • the foamed resin layer 18 is a layer containing bubbles and having high elasticity.
  • the surface treatment layer 16 is located on the surface of the skin layer 32 containing a vinyl chloride resin, and has the function of adjusting the appearance and feel, and imparting abrasion resistance to the synthetic resin skin material.
  • the skin material for vehicle interiors requires a moist feel and a soft texture comparable to natural leather.
  • a layer (skin layer) containing a vinyl chloride resin excellent in flexibility and dimensional stability is used near the surface.
  • a layer containing a vinyl chloride resin having excellent flexibility is arranged near the surface of the skin material, there is a problem that the abrasion resistance of the surface of the synthetic resin skin material is lowered.
  • Interior parts for automobiles, skin materials for furniture, etc. that are used for a long period of time every day require durability, and therefore it is important to be able to maintain a good appearance and texture for a long period of time.
  • the thickness of the skin layer containing vinyl chloride resin existing near the surface For the purpose of improving wear resistance, increase the thickness of the skin layer containing vinyl chloride resin existing near the surface, increase the thickness of the surface treatment layer, and form a high-strength chloride for forming the skin layer containing vinyl chloride resin. It is possible to take measures such as using a vinyl resin. However, in the measures described above, the texture of the skin material may be impaired, and the flexibility and flexibility of the skin material may deteriorate. Therefore, according to the above-mentioned measures, it is difficult to apply the obtained skin material to a molded product having complicated irregularities as an interior material such as a seat of an automobile.
  • a synthetic resin skin material having a vinyl chloride resin layer, a water-based crosslinked polyurethane layer, and a surface-treated layer containing a resin and organic particles in this order is proposed as a synthetic resin skin material that can achieve both abrasion resistance and texture.
  • the vinyl chloride resin layer is cross-linked with a vinyl chloride resin layer containing a specific amount of silicone/acrylic copolymer and a mixture of polycarbonate polyurethane and ester polyurethane with a crosslinking agent containing a carbodisimide group.
  • a synthetic resin leather provided with a surface-treated layer formed of the above is proposed (see International Publication No. 2017/061611).
  • the synthetic resin skin material described in JP-A-2005-66889 has good durability, but on the vinyl chloride resin layer, a surface treatment layer for improving the feel of the surface, and for improving durability. It has two layers, a cross-linked polyurethane layer and there is room for improvement in terms of manufacturability.
  • a surface treatment layer having a thickness on the surface of a vinyl chloride resin skin layer or a crosslinked structure is included to improve wear resistance. When a surface-treated layer or the like is provided, the soft feel and appearance of the vinyl chloride resin skin layer may be impaired.
  • An object of one embodiment of the present invention made in consideration of the above-mentioned conventional art is to provide a synthetic resin skin material having excellent wear resistance and good design flexibility. Moreover, the subject of another embodiment of this invention is providing the manufacturing method of the synthetic resin skin material which is excellent in abrasion resistance and has the degree of freedom of design.
  • Means for solving the above problems include the following aspects. ⁇ 1> A base cloth, a vinyl chloride resin formed on the base cloth and having a degree of polymerization of 1600 to 3000, and 3 to 20 parts by mass of a silicone/acrylic copolymer with respect to 100 parts by mass of the vinyl chloride resin. A synthetic resin skin material having a vinyl chloride resin skin layer containing,.
  • ⁇ 2> The synthetic resin skin material according to ⁇ 1>, which does not have an abrasion resistant layer including a crosslinked structure on the surface of the vinyl chloride resin skin layer opposite to the base fabric side.
  • ⁇ 3> The synthetic resin skin material according to ⁇ 1> or ⁇ 2>, which has at least one adhesive layer between the base cloth and the vinyl chloride resin skin layer.
  • ⁇ 4> The synthetic resin skin material according to any one of ⁇ 1> to ⁇ 3>, which has a foamed resin layer between the base cloth and the vinyl chloride resin skin layer.
  • the synthetic resin skin material according to ⁇ 1> or ⁇ 2> which has an adhesive layer and a foamed resin layer in this order from the base cloth side between the base cloth and the vinyl chloride resin skin layer.
  • ⁇ 6> The synthetic resin skin material according to ⁇ 4> or ⁇ 5>, wherein the foamed resin layer contains a vinyl chloride resin.
  • a vinyl chloride resin skin layer which comprises a vinyl chloride resin having a degree of polymerization of 1600 to 3000 and 3 to 20 parts by weight of a silicone/acrylic copolymer with respect to 100 parts by weight of the vinyl chloride resin.
  • a method for producing a synthetic resin skin material comprising: a step of forming a vinyl chloride resin skin layer using the composition; and a step of adhering a base cloth to one surface of the vinyl chloride resin skin layer.
  • a composition layer for forming a foamed resin layer containing a foaming agent and a resin is formed on the side of the vinyl chloride resin skin layer that is to be bonded to the base cloth, and the vinyl chloride resin skin layer and the foamed resin are formed.
  • ⁇ 7> having a step of forming a laminate with a layer-forming composition layer and a step of foaming a foaming agent in the foamed resin layer-forming composition by heating to form a foamed resin layer.
  • the synthetic resin skin material according to ⁇ 8>, wherein the step of adhering the base cloth includes a step of providing an adhesive layer between the vinyl chloride foam resin layer-forming composition layer and the base cloth.
  • the synthetic resin skin material of the present disclosure includes a vinyl chloride resin having a lower polymerization degree by including a vinyl chloride resin having a polymerization degree of 1600 to 3000 as the vinyl chloride resin used for forming the vinyl chloride resin skin layer.
  • the abrasion resistance of the vinyl chloride resin skin layer when formed into a sheet is improved.
  • the vinyl chloride resin skin layer contains the silicone/acrylic copolymer, the surface energy can be lowered without affecting the hue of the skin layer and the abrasion resistance is further improved. Therefore, the vinyl chloride resin skin layer exhibits sufficient durability such as abrasion resistance without increasing the thickness, and it is possible to provide a synthetic resin skin material utilizing the inherent flexibility of the vinyl chloride resin.
  • the vinyl chloride resin skin layer has good wear resistance, it is not necessary to further provide a surface treatment layer for imparting wear resistance, and by providing an appearance according to the design of the skin layer, The degree of freedom of is good. As long as the appearance of the synthetic resin skin material is not impaired, it is possible to further have an arbitrary layer such as a thin surface treatment layer for improving the feel of the surface on the surface of the vinyl chloride resin skin layer. Do not disturb
  • the base fabric used for the synthetic resin skin material of the present disclosure is not particularly limited, but as the base fabric, a knitted fabric having good elasticity and stretchability, for example, a knitted fabric such as a knitted fabric can be selected. Further, it has an advantage that the stretchability and flexibility of the synthetic resin skin material are further improved.
  • the synthetic resin skin material of the present disclosure has excellent surface abrasion resistance and durability, and is flexible and has a high degree of freedom in design, and therefore, it is a vehicle interior material such as a vehicle seat or a chair. It is suitable for use as a surface material of, and can give any design to a product.
  • a synthetic resin skin material having excellent wear resistance and a high degree of freedom in design. Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a synthetic resin skin material which is excellent in abrasion resistance and has a high degree of freedom in design.
  • FIG. 3 is a schematic cross-sectional view showing one embodiment of the synthetic resin skin material of the present disclosure having an arbitrary layer such as a surface treatment layer and a foamed resin layer in addition to the vinyl chloride resin skin layer. It is a schematic sectional drawing which shows one aspect of the conventional synthetic resin skin material.
  • the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition, unless there is a plurality of substances corresponding to each component in the composition, unless otherwise specified. means.
  • the term “process” is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes.
  • the phrase “the degree of freedom in design is good” in the present disclosure means that “the occurrence of a phenomenon called white blurring due to light scattering on the surface of the synthetic resin skin material is suppressed”.
  • the synthetic resin skin material of the present disclosure a reduction in the degree of freedom in design due to white blur is suppressed, and the degree of freedom in design that imparts a good appearance is achieved.
  • FIG. 1 is a schematic cross-sectional view showing one aspect of the layer configuration of the synthetic resin skin material 10 of the present disclosure.
  • the embodiment shown in FIG. 1 shows the simplest configuration of the synthetic resin skin material of the present disclosure.
  • the synthetic resin skin material 10 has a vinyl chloride resin skin layer 12 on a base cloth 14.
  • the constituent elements indicated by the same reference numerals in the drawings mean the same constituent elements.
  • the vinyl chloride resin skin layer (hereinafter, also referred to as “skin layer”) in the synthetic resin skin material of the present disclosure is specified as a vinyl chloride resin having a polymerization degree of 1600 to 3000 (hereinafter, also referred to as “specific vinyl chloride resin”). 3 to 20 parts by weight of a silicone/acrylic copolymer is included with respect to 100 parts by weight of a vinyl chloride resin. Due to this composition, the vinyl chloride resin skin layer has flexibility and a good feel peculiar to the vinyl chloride resin and is excellent in abrasion resistance. Therefore, it is not necessary to additionally provide another layer on the surface of the vinyl chloride resin skin layer opposite to the base cloth for the purpose of improving abrasion resistance.
  • the synthetic resin skin material has the feel and good appearance of the vinyl chloride resin, and has an appearance that makes full use of the various designs given when the vinyl chloride resin skin layer was formed. Therefore, the synthetic resin skin material of the present disclosure has a high degree of freedom in design.
  • the synthetic resin skin material of the present disclosure is not particularly limited as long as it has a base cloth described in detail below and a vinyl chloride resin skin layer.
  • the synthetic resin skin material may have other layers as long as the effect is not impaired. The other layers will be described later.
  • the synthetic resin skin material of the present disclosure (hereinafter, may be simply referred to as “skin material”) will be sequentially described along with the materials constituting the skin material and the manufacturing method thereof.
  • the base fabric of the skin material of the present disclosure is not particularly limited as long as it has necessary strength and durability, and can be appropriately selected and used from known base fabrics according to the purpose.
  • the base fabric may be a knitted fabric, a woven fabric, or a non-woven fabric.
  • the base fabric for example, when it is used as a skin material for a vehicle seat, a knitted fabric such as a knitted fabric or a modified knitted fabric is preferable from the viewpoint of stretchability and ease of thickness control.
  • a three-dimensional non-woven fabric or the like is also preferably used as the base fabric from the viewpoint of easy adjustment of the thickness.
  • Examples of the material of the fibers (threads) used for knitting and weaving the base cloth include threads made of polyester, polyamide, rayon, etc., and mixed spun threads containing polyester, polyamide, rayon, etc.
  • the base fabric in addition to the knitted fabric, it is also possible to use, for example, a base fabric for synthetic leather using the pontoroma knitting described in JP2013-72141A.
  • the thickness of the base cloth is appropriately selected according to the purpose of use of the skin material. Above all, a range that is excellent in touch and does not deteriorate the flexibility of the skin material, for example, a range of 0.15 mm to 0.6 mm is preferable, and a range of 0.3 mm to 0.5 mm is more preferable.
  • the surface of the base cloth on the skin layer side may be brushed if necessary. Further, as the base cloth, a pile knitted fabric in which a pile is formed on the surface of the base cloth on the surface layer side may be used. By having the raised or piled surface on the surface of the base fabric, the adhesiveness with an adjacent layer, for example, a skin layer or an adhesive layer, is further improved.
  • the skin layer in the skin material of the present disclosure contains a specific vinyl chloride resin having a degree of polymerization of 1600 to 3000, and 3 to 20 parts by mass of a silicone/acrylic copolymer with respect to 100 parts by mass of the specific vinyl chloride resin, Other components may be included if desired.
  • the skin layer is formed using a vinyl chloride resin skin layer forming composition containing at least a specific vinyl chloride resin, a silicone/acrylic copolymer, and preferably a plasticizer.
  • a resin having a degree of polymerization of about 1000 to 1300 is generally used.
  • the skin layer in the skin material of the present disclosure uses a specific vinyl chloride resin having a degree of polymerization of 1600 to 3000, and further contains a silicone/acrylic copolymer described below to improve the strength and abrasion resistance. There is.
  • the degree of polymerization of the specific vinyl chloride resin is 1600 to 3000, preferably 1700 to 2900, and more preferably 1700 to 2800.
  • the catalog value can be referred to.
  • the specific vinyl chloride resin contained in the surface layer any one can be used as long as the degree of polymerization is in the above range.
  • the specific vinyl chloride resin a commercially available product may be used, and examples thereof include TH-2800 manufactured by Taiyo PVC Co., Ltd.
  • the skin layer may contain only one kind of the specific vinyl chloride resin, or may contain two or more kinds thereof.
  • the skin layer may contain resins other than vinyl chloride resin.
  • the content of the vinyl chloride resin with respect to the total resin contained in the skin layer is preferably 30% by mass to 80% by mass, and more preferably 40% by mass to 50% by mass.
  • the skin layer preferably contains a plasticizer.
  • the skin layer contains at least one silicone/acrylic copolymer.
  • the silicone/acrylic copolymer is a copolymer containing a siloxane structural unit shown below and a structural unit derived from an acrylic monomer.
  • the silicone/acrylic copolymer can be obtained by, for example, copolymerizing a polyorganosiloxane having a radically polymerizable group at the terminal and a (meth)acrylic acid ester by a conventional method.
  • the copolymerization ratio of the siloxane structural unit and the acrylic monomer-derived structural unit is not particularly limited, but the molar ratio of the siloxane structural unit: the acrylic monomer-derived structural unit is 60:40 to 90:10.
  • the copolymerization ratio of the siloxane structural unit: the structural unit derived from the acrylic monomer is preferably 65:35 to 75:25, and 70:30 It is more preferably to 75:25.
  • the skin layer may include only one type or two or more types of the silicone/acrylic copolymer.
  • the content of the silicone/acrylic copolymer in the skin layer is 3 to 20 parts by mass, preferably 5 to 15 parts by mass, based on 100 parts by mass of the vinyl chloride resin contained in the skin layer.
  • the range of 7 parts by mass to 13 parts by mass is more preferable.
  • the surface abrasion resistance and flexibility of the skin material are in the suitable range.
  • the skin layer may contain other components in addition to the specific vinyl chloride resin and the silicone/acrylic copolymer.
  • Other components include synthetic resins other than the above, plasticizers, stabilizers, fillers, colorants, flame retardants, gelation accelerators, plasticizer compatibilizers, and the like.
  • the skin layer preferably contains a plasticizer in order to improve the flexibility of the vinyl chloride resin.
  • a plasticizer for vinyl chloride resin can be used without limitation.
  • the plasticizer include phthalate ester plasticizers such as diisodecyl phthalate, di-2-ethylhexyl phthalate and diisononyl phthalate, fatty acid ester plasticizers such as dioctyl adipate and dioctyl sebacate, and trioctyl trimellitate.
  • the skin layer may include only one type of plasticizer, or may include two or more types.
  • the epidermis layer may include a colorant.
  • a colorant When the skin layer contains the colorant, a desired hue can be imparted to the skin material, and the skin material having excellent designability can be obtained.
  • the colorant is not particularly limited, and dyes, pigments and the like can be appropriately selected and used. From the viewpoint of better durability and light resistance, the colorant is preferably a pigment.
  • the colorant titanium white (titanium dioxide), zinc white, ultramarine blue, cobalt blue, red pearl, vermilion, yellow lead, titanium yellow, inorganic pigments such as carbon black, quinacridone, permanent red 4R, isoindolinone, hansa yellow.
  • A phthalocyanine blue, indanthrene blue RS, aniline black or other organic pigments or dyes
  • 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
  • pearlescent pigments selected from the group consisting of:
  • the skin layer may include only one type of colorant, or may include two or more types of colorants.
  • a pigment dispersant such as a surfactant or a polymer dispersant may be used together.
  • the epidermis layer may contain a filler.
  • the filler include inorganic fillers such as calcium carbonate, silica (silicon dioxide), alumina (aluminum oxide), mica (mica), talc and barium sulfate.
  • the skin layer may include only one type of filler, or may include two or more types of filler.
  • the epidermis layer may contain a stabilizer.
  • the inclusion of the stabilizer improves the heat resistance of the skin layer.
  • examples of the stabilizer include magnesium stearate, aluminum stearate, calcium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, fatty acid metal salts such as zinc laurate, sodium compounds such as phenol and naphthol, zinc.
  • Metal salts such as barium, dibutyltin dilaurate, organotin compounds such as dibutyltin dimaleate, diethyl phosphite, dibutyl phosphite, dioctyl phosphite, diphenylisodecyl phosphite, tricresyl phosphite, triphenyl phosphite, tris( Examples thereof include phosphites such as nonylphenyl)phosphite and triisooctylphosphite.
  • the skin layer may contain only one type of stabilizer, or may contain two or more types of stabilizers.
  • the skin layer may contain a flame retardant.
  • a flame retardant it is possible to impart flame retardancy to the skin material.
  • the flame retardant a known inorganic or organic flame retardant can be appropriately selected and used.
  • the skin layer may include only one type of flame retardant, or may include two or more types.
  • the skin layer may contain other synthetic resins other than the vinyl chloride resin and the silicone/acrylic copolymer for the purpose of improving the physical properties of the film.
  • Other synthetic resins include thermoplastic polyurethane resin (TPU) and the like.
  • TPU thermoplastic polyurethane resin
  • the content of the other resin is preferably 10 parts by mass or less based on 100 parts by mass of the total solid content of the skin layer.
  • the method for forming the skin layer is not particularly limited.
  • a method for forming a skin layer by preparing a composition for forming a skin layer containing each of the above-mentioned components, and forming the skin layer by a calendar method, a paste processing method, a melt extrusion method or the like is used.
  • the composition for forming a skin layer is applied to the base cloth directly or via an adhesive layer described below to form a composition layer for forming a skin layer, and the composition is cured to form a skin on the base cloth.
  • the method of forming a layer can also be taken.
  • the thickness of the skin layer is not particularly limited, the skin layer according to the present disclosure has good wear resistance and strength even if it is a thin layer, and therefore it is not always necessary to increase the thickness to improve the strength.
  • the thickness of the skin layer is preferably 170 ⁇ m to 650 ⁇ m, more preferably 200 ⁇ m to 300 ⁇ m.
  • the skin material of the present disclosure may be composed of only the base fabric and the skin layer, but may have other known layers.
  • FIG. 2 is a schematic cross-sectional view showing another example of the skin material of the present disclosure.
  • the skin material 22 shown in FIG. 2 includes a foamed resin layer 18, which is an arbitrary layer, the above-described skin layer 12, and an arbitrary layer, on the base cloth 14 with an adhesive layer 20 which is an arbitrary layer interposed therebetween. And a certain surface treatment layer 16 in this order. Since the skin material 22 has the adhesive layer 20, the adjacent layers are more stably and strongly adhered via the adhesive layer 20. Further, since the skin material 22 has the foamed resin layer 18, the skin material 22 becomes more flexible and appropriate elasticity can be imparted to the skin material 22.
  • the skin material 22 has the surface treatment layer 16, it is possible to give the skin material 22 an arbitrary good feel. Since the skin layer 12 in the present disclosure has good wear resistance, a thick surface treatment layer having a crosslinked structure or the like for the purpose of improving the strength such as abrasion resistance, as in the known surface treatment layer 16, It is not necessary to form an abrasion resistant layer having a crosslinked structure.
  • any layer that the skin material of the present disclosure may have will be described.
  • the skin material of the present disclosure may have an adhesive layer.
  • the adhesive layer is provided for the purpose of improving the adhesiveness between adjacent layers such as the base cloth and the skin layer.
  • the adhesive layer can be formed, for example, by laminating an adhesive on the surface of the base fabric and drying. The lamination of the adhesive may be performed by a transfer method or a coating method.
  • the adhesive used for forming the adhesive layer optionally provided is not particularly limited and may be appropriately selected depending on the purpose. For example, (1) urethane emulsion adhesive, (2) vinyl chloride adhesive , (3) two-component curing type polyester adhesive, and (4) two-component curing urethane adhesive are preferably used.
  • the adhesive layer can be usually formed by applying an adhesive to the surface of the base cloth.
  • the adhesive layer 20 and the foamed resin layer 18, which are arbitrary layers, are formed between the base cloth 14 and the skin layer 12.
  • a composition layer for forming a skin layer for forming the skin layer 12 is formed, and then a composition layer for forming a foamed resin layer, which will be described later, is formed on the surface of the composition layer for forming a skin layer.
  • the adhesive layer 20 can be formed by applying an adhesive to the layer forming composition layer.
  • the skin material may have only one adhesive layer, or may have two or more layers as required.
  • any known method such as a transfer method or a coating method can be used, but from the viewpoint of easily forming an adhesive layer having a uniform thickness, the transfer method can be used. It is preferable to use the method.
  • a protective sheet may be provided on the surface of the adhesive layer in order to protect the surface of the adhesive layer prepared in advance.
  • a resin film, release-treated paper, resin-laminated paper, or the like can be appropriately used.
  • the skin material of the present disclosure may have a foamed resin layer.
  • the foamed resin layer is provided for the purpose of imparting elasticity to the skin material and further improving the feel.
  • the resin contained in the foamed resin layer include a vinyl chloride resin and a urethane resin from the viewpoint of easy foaming, and from the viewpoint of excellent affinity with the skin layer, a foamed resin layer containing a vinyl chloride resin is used. preferable.
  • the foamed resin layer is formed by forming a foamed resin layer forming composition layer containing a foaming agent and a resin, and then foaming the foaming agent by heating to generate fine bubbles in the resin layer.
  • a foamed resin layer containing fine bubbles is formed.
  • the foamed resin layer contains a vinyl chloride resin
  • the vinyl chloride resin the same examples as the vinyl chloride resin contained in the above-mentioned skin layer can be mentioned.
  • the vinyl chloride resin contained in the foamed resin layer may be the same as or different from the vinyl chloride resin contained in the skin layer.
  • the foaming agent is not particularly limited as long as it can form fine bubbles that give elasticity and thickness required for the foamed resin layer.
  • Examples of the foaming agent include chemical foaming agents such as azodicarbonamide (ADCA) and p,p'-oxybisbenzenesulfonyl hydrazide (OBSH) that foam by heating; thermal expansion beads and the like.
  • the thermal expansion beads used in the preparation of the composition for forming a foamed resin layer are particles obtained by encapsulating an organic solvent such as a hydrocarbon solvent in hollow thermoplastic resin particles, and the volume expansion of the organic solvent by heating. As a result, the volume of the particles is increased, and as a result, a foamed resin layer in which bubbles are contained in the resin matrix (dispersion medium) is formed.
  • the thermal expansion beads used in the present disclosure any one may be used as long as it can be expanded by heating to form bubbles in the resin matrix and maintain the state of the formed bubbles.
  • the thermal expansion beads are also available as a commercial product, and examples thereof include Expancel series (trade name) manufactured by Nippon Ferrite Co., Ltd., and any of them can be used in the present disclosure.
  • the addition amount of the thermal expansion beads is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin contained in the foamed resin layer. More preferably, it is from 7 to 7 parts by mass.
  • composition for forming a foamed resin layer it is preferable to use an organic solvent instead of water as a solvent from the viewpoint of efficiently drying.
  • thermal expansion beads it is preferable to select an organic solvent that does not dissolve the resin forming the thermal expansion beads. This is because when the resin that constitutes the thermal expansion beads is dissolved by the organic solvent, the hollow portion cannot be maintained, and it becomes difficult to form a foamed resin layer containing desired bubbles.
  • the thermal expansion beads to be used are immersed in an organic solvent to be evaluated (including a simple substance and a mixture) at room temperature (25° C.) for 3 days, and then visually determined There is a method of selecting an organic solvent which has no evidence of foaming.
  • an organic solvent including a simple substance and a mixture
  • the resin that constitutes the thermal expansion beads dissolves in an organic solvent, the outer shell of the resin beads is damaged, and the gas or hydrocarbon solvent contained in the thermal expansion beads flows out into the immersed organic solvent and bubbles are observed.
  • such an organic solvent is not included in the “solvent that does not dissolve the resin constituting the thermal expansion beads” in the present disclosure.
  • usable solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol (IPA), toluene, styrene, acetone, ethyl acetate, ethylene glycol. , N-hexane, cyclohexane, methyl ethyl ketone (MEK), and propylene glycol monomethyl ether (PGME).
  • IPA isopropyl alcohol
  • MEK methyl ethyl ketone
  • PGME propylene glycol monomethyl ether
  • the heating temperature for expanding the thermal expansion beads contained in the foamed resin layer-forming composition layer is preferably in the range of 130°C to 230°C, more preferably in the range of 190°C to 230°C. preferable.
  • the film thickness of the foamed resin layer is not particularly limited and is appropriately selected depending on the purpose. Generally, from the viewpoint of strength and touch, the film thickness of the foamed resin layer is preferably in the range of 150 ⁇ m to 700 ⁇ m, more preferably 170 ⁇ m to 450 ⁇ m as the film thickness before foaming.
  • the film thickness of the foamed resin layer containing bubbles after foaming is preferably in the range of 220 ⁇ m to 1300 ⁇ m, and more preferably in the range of 400 ⁇ m to 900 ⁇ m. As shown in FIG. 2, in the synthetic resin skin material 22, having the adhesive layer 20 between the base cloth 14 and the foamed resin layer 18 further improves the durability and shape following of the skin material 22. It is preferable from the viewpoint of
  • the skin material may have a surface treatment layer for the purpose of improving the appearance and feel.
  • the surface-treated layer is provided for the purpose of further improving the feel, contains at least a resin, and may optionally contain, as a feel-improving agent, organic particles as a filler, a colorant for the purpose of improving the design.
  • the surface treatment layer which is formed on the outermost surface of the surface material and is formed as desired, is colored or printed according to the purpose, or has natural leather-like irregularities such as a striation pattern. You may.
  • the resin that can be contained in the surface treatment layer examples include polyurethane, acrylic resin, fluororesin, vinyl chloride resin, and the like, and polyurethane is preferably used as a main material from the viewpoint of good feel.
  • the "main material” means a resin having the highest content ratio when a plurality of kinds of resins are used in combination.
  • the polyurethane used for the surface treatment layer water-based polyurethane is preferably mentioned.
  • the acrylic resin used for the surface treatment layer include polymers or copolymers of methacrylic acid or methacrylic acid ester represented by polymethyl methacrylate (PMMA), alkyl methacrylate, alkyl acrylate, and styrene. Examples thereof include copolymers.
  • organic particles As a filler in the surface treatment layer, compared with the case of using an amorphous inorganic filler that was conventionally used as a matting agent, it imparts a moist and warm touch to the skin material. be able to.
  • the organic particles include organic resin particles such as urethane beads and acrylic beads, and protein-based fillers such as collagen particles.
  • the shape of the organic particles is preferably a true sphere or a sphere close to a true sphere, from the viewpoint of improving the feeling.
  • the shape of the organic particles is preferably such that the ratio of the major axis to the minor axis is 1.5 or less.
  • the average particle size of the organic particles is preferably in the range of 1 ⁇ m to 20 ⁇ m, more preferably in the range of 5 ⁇ m to 10 ⁇ m.
  • the average particle size of the organic particles is determined by an optical particle size analyzer (model number: CAPA-300) manufactured by HORIBA, Ltd., and the disk rotation speed is 3000 rpm (rotation/minute) by a light transmission centrifugal precipitation method using water as a dispersion medium. The value measured by the method of measuring the volume-based median diameter is used.
  • the surface treatment layer may include only one type of organic particles or may include two or more types of organic particles.
  • the surface-treated layer may contain a coloring agent for imparting a design property, if necessary.
  • a coloring agent for imparting a design property
  • the colorant the general-purpose colorants listed for the skin layer can be used in the same manner, and the preferable contents are also the same.
  • the thickness of the surface treatment layer is preferably in the range of 1 ⁇ m to 5 ⁇ m, more preferably in the range of 2 ⁇ m to 3 ⁇ m.
  • the skin material of the present disclosure has a skin layer containing a specific vinyl chloride resin and a specific amount of a silicone/acrylic copolymer, the surface of the skin layer opposite to the base fabric side, that is, the skin. Good wear resistance can be obtained without having a wear resistant layer containing a crosslinked structure on the outermost surface of the material.
  • the method for producing the synthetic resin skin material of the present disclosure is not particularly limited.
  • the synthetic resin skin material of the present disclosure is preferably produced by the following method for producing a synthetic resin skin material of the present disclosure (hereinafter sometimes referred to as the production method of the present disclosure).
  • the production method of the present disclosure includes a vinyl chloride resin having a polymerization degree of 1600 to 3000 (specific vinyl chloride resin), and 3 to 20 parts by mass of a silicone/acrylic copolymer with respect to 100 parts by mass of the specific vinyl chloride resin.
  • the production method of the present disclosure further includes a foaming agent and a resin, if desired, on the side of the vinyl chloride resin skin layer to be adhered to the base cloth.
  • a step of forming a resin layer forming composition layer to form a laminate of a vinyl chloride resin skin layer and a foaming resin layer forming composition layer (step (III)), and heating to form the foamed resin layer.
  • the step (step (IV)) of foaming the foaming agent contained in the composition to form a foamed resin layer may be included.
  • step (II) is the step of providing an adhesive layer between the foamed resin layer-forming composition layer and the base cloth (step (V )) may be included.
  • step (VI) the process of forming a surface treatment layer in the surface on the opposite side to the base fabric side of a skin layer.
  • Step (I) is a vinyl chloride resin containing a specific vinyl chloride resin having a degree of polymerization of 1600 to 3000 and 3 to 20 parts by mass of a silicone/acrylic copolymer with respect to 100 parts by mass of the specific vinyl chloride resin.
  • This is a step of forming a skin layer by using the composition for forming a skin layer, which comprises 3 parts by mass to 20 parts by mass of a specific vinyl chloride resin having a degree of polymerization of 1600 to 3000 and 100 parts by mass of the specific vinyl chloride resin.
  • a composition for forming a vinyl chloride resin skin layer which contains a silicone/acrylic copolymer and, if desired, optional components such as a plasticizer and a colorant, is prepared, and the obtained composition is used to form a skin.
  • the method for forming the skin layer is arbitrary, but as described above, the prepared vinyl chloride resin skin layer forming composition is formed into a sheet by a calendering method, a paste processing method, a melt extrusion method, or the like. Examples of the method include forming a layer, and preferably a method of forming the composition into a sheet by a calendar method to form a skin layer.
  • Process (III) In the case of forming a foamed resin layer as an arbitrary layer, subsequently to the step of forming a skin layer, to form a foamed resin layer forming composition layer made of a composition containing a foaming agent and a resin, You may perform the process (process (III)) of forming the laminated body of the skin layer and the foaming resin layer forming composition layer.
  • the laminate When carrying out the step (III), the laminate may be formed by simultaneously calendering or simultaneously extruding the skin layer and the foamed resin layer forming composition layer.
  • a composition layer for forming a foamed resin layer is formed, and a skin layer (or a composition layer for forming a skin layer) is formed on the surface of the composition layer by a paste processing machine or an extrusion machine to form a composition for forming a foamed resin layer.
  • You may form the laminated body of a layer and a skin layer.
  • the step (II) is a lamination of a skin layer previously formed in the step (I) or a skin layer formed by performing the step (I) and the step (III) and a composition layer for forming a foamed resin layer. This is the step of adhering the body to the base cloth. Even in place of the step (II) or in addition to the step (II), a step (step (V)) of providing an adhesive layer between the composition layer for forming a foamed resin layer and the base fabric may be performed. Good. In the case of adhering the laminate and the base fabric (step (V)), the base fabric may be adhered to the surface of the laminate on the foamed resin layer forming composition layer side.
  • a base fabric subjected to a raising treatment by a conventional method may be used on the side in contact with the skin layer or the composition layer for forming a foamed resin layer.
  • the adhesion may be carried out by forming an adhesive layer on the surface of the composition layer for forming the skin layer or the foamed resin layer, or on the surface of the base fabric, and then bonding the both via the adhesive layer. Further, in the case of adhering the laminate and the base cloth, for example, before curing the foamed resin layer forming composition layer, after laminating together with the base cloth, the adhesive layer and the foamed resin layer are cured. You may make it adhere.
  • the adhesive layer can be formed, for example, by laminating the adhesive on the surface of the composition layer for forming the skin layer or the foamed resin layer or the surface of the base fabric, and drying.
  • the adhesive used for forming the adhesive layer optionally provided is as described in the section of the adhesive layer.
  • an adhesive layer is formed by applying an adhesive to the surface of the layer forming the adhesive layer or the base fabric. Examples of the method for applying the adhesive include a transfer method and a coating method, and the transfer method is preferably used from the viewpoint that an adhesive layer having a uniform thickness can be easily formed.
  • the step (I) or step (III) and the step (II) or step (V) may be performed simultaneously or sequentially. That is, the skin layer or the laminate is formed by a calendar method or the like, and while being conveyed, the surface of the skin layer or the laminate on the foamed resin layer-forming composition layer side is heated with a nip roll or the like while pressing the base fabric. You may adhere. Further, when the base cloth and the desired layer are bonded via the adhesive layer, the adhesive layer is formed on the surface of the desired layer, and then the adhesive layer and the base cloth are combined and pressure bonded. You may. By heating and drying the adhesive layer, a desired layer and the adhesive layer are formed on the skin layer.
  • Step (VI) in order to improve the feel and appearance of the surface of the skin layer, a surface treatment layer (improving the feel) is formed on the surface of the skin layer (the surface of the skin layer opposite to the base fabric side).
  • a step of forming a layer is performed by applying a surface treatment layer forming composition containing a resin to the surface of the skin layer.
  • the application of the composition for forming the surface treatment layer can be carried out by appropriately applying a known method.
  • the composition for forming the surface treatment layer is applied to the surface of the skin layer by appropriately selecting from methods such as coating by a gravure printing method, coating with a reverse coater, direct coater or other coating device. You can do that.
  • the composition for forming a surface treatment layer by a gravure printing method.
  • the details of the surface treatment layer are as described above.
  • the thickness thereof can be reduced, so that the surface-treated layer for improving the feel hardly affects the appearance of the skin layer, and therefore the skin layer. It is possible to suppress a reduction in the degree of freedom in design.
  • Step (IV) When the skin material obtained by the production method of the present disclosure has a foamed resin layer, that is, when the step (III) of forming a laminate of the skin layer and the foamed resin layer-forming composition layer is performed, the step (III ), a step (step (IV)) of forming a foamed resin layer by heating to foam the foaming agent in the composition for forming a foamed resin layer is performed.
  • Step (IV) is a step of foaming the foaming agent contained in the foamed resin layer forming composition by heating to form a foamed resin layer. It is preferable that the heating is performed by non-contact heating by transporting in a heating furnace adjusted to a predetermined temperature.
  • the heating temperature for expanding the thermal expansion beads is preferably in the range of 130°C to 230°C, and 190°C to 230°C. The range is more preferable.
  • the heating temperature is preferably 180°C to 250°C, more preferably 200°C to 230°C. Step (IV) may be performed after the step of adhering the base cloth and the skin layer (step (II)) and prior to the step of forming the surface treatment layer (step (VI)). You may go later.
  • the manufacturing method of the present disclosure can perform a step of imparting a design property for further improving the appearance, if necessary. After the steps (I) and (II) are completed, or in addition to the steps (I) and (II), the above-mentioned other steps optionally performed are completed, and then the design property is imparted.
  • the process can be performed.
  • a step of imparting a design property for example, an embossing roll in which a skin pattern or a surface treatment layer provided as desired is engraved with a textured pattern which is a fine uneven pattern like leather is used. There is a step of forming a squeezing pattern on the surface by pressing while heated.
  • the striation pattern may be applied after the step (II) and prior to the step (VI).
  • the foaming agent is foamed by heating the laminate having the foamed resin layer-forming composition layer and the skin layer on the base fabric to form the foamed resin layer having bubbles, and then the drawn shape is changed. It may be a step of pressing the engraved embossing roll in a state where the surface is heated to form a diaphragm pattern, and then forming a surface treatment layer if desired.
  • the heating temperature in embossing is preferably 100°C to 240°C.
  • the heating temperature is a value obtained by measuring the surface temperature of the embossing roll used for embossing.
  • the skin material of the present disclosure obtained by the production method of the present disclosure has, on the outermost surface, a skin layer having good wear resistance and flexibility, or a surface-treated layer having a good feel, and thus a molded article having a complicated shape. And is suitable for use in applications with excellent durability such as abrasion resistance.
  • the synthetic resin skin material of the present disclosure is formed by a simple method represented by the manufacturing method of the present disclosure described above, and has excellent appearance, durability, and flexibility. Therefore, the synthetic resin skin material of the present disclosure is suitable for various fields such as automobile interior materials, railway vehicle/aircraft interior parts, furniture, shoes/footwear/bags, interior/exterior members for construction, clothing surface/lining materials, etc. Can be used for
  • Example 1 As the resin contained in the composition for forming a vinyl chloride resin skin layer, polyvinyl chloride having an average degree of polymerization of 2800 (Tayo PVC Co., Ltd.: TH-2800) was used.
  • composition for forming foamed resin layer ⁇ Polyvinyl chloride resin (Tayo PVC Co., Ltd.: TH-1300: Average degree of polymerization 1300) 100 parts by mass, foaming agent (ADCA) 6 parts by mass, plasticizer (dialkyl phthalate) 75 parts by mass, stabilizer (Ba-Zn-based composite stabilizer) 4 parts by mass, filler (calcium bicarbonate) ) 15 parts by mass, colorant (pigment: Hihiro Vix Co., Ltd.: GB-91) 2 parts by mass
  • a calender device is used to form a laminate in which a skin layer and a foamed resin layer-forming composition layer are laminated using each of the above compositions.
  • the skin layer in the laminate had a thickness of 250 ⁇ m
  • the foamed resin layer-forming composition layer (before foaming) had a thickness of 500 ⁇ m.
  • About 15 g/m 2 of an adhesive (urethane emulsion adhesive) was applied to the surface of the foamed resin layer-forming composition of the obtained laminate, and a base cloth was attached.
  • a knitted fabric with improved knitting (fiber: polyester, thickness: 300 denier, basis weight: 155 g/m 2 , thickness: 0.55 mm) was used.
  • a composition for forming a surface treatment layer having the following formulation was applied by gravure printing to improve the feel, and dried to form a surface treatment layer having a thickness of 2 ⁇ m. Formed.
  • composition for forming surface treatment layer ⁇ Polyurethane resin composition 100 parts by mass ⁇ Solvent (methyl ethyl ketone: MEK) 900 parts by mass
  • the obtained laminated body was passed through a heating furnace at a temperature condition of 190° C. to 230° C. to foam the foaming agent, thereby forming a foamed resin layer containing bubbles.
  • a heating furnace at a temperature condition of 190° C. to 230° C. to foam the foaming agent, thereby forming a foamed resin layer containing bubbles.
  • an embossing roll in which a diaphragm shape is engraved is pressed while heating the surface to 130° C. to perform embossing.
  • the formed synthetic resin skin material of Example 1 having the structure shown in FIG. 2 was obtained.
  • Example 2 In the same manner as in Example 1 except that the content of the silicone/acrylic copolymer relative to 100 parts by mass of the vinyl chloride resin having a degree of polymerization of 2800 used in Example 1 was changed to the amount (10 parts by mass) described in Table 1. Thus, the skin material of Example 2 was obtained.
  • Example 3 Instead of the vinyl chloride resin having a degree of polymerization of 2800 used in Example 1, a vinyl chloride resin having a degree of polymerization of 1700 (manufactured by Taiyo PVC Co., Ltd.: TH-1700) was used, and the content of the silicone/acrylic copolymer was measured. A skin material of Example 3 was obtained in the same manner as in Example 1 except that the amount (10 parts by mass) described in 1 was changed.
  • Example 4 In the same manner as in Example 1 except that the content of the silicone/acrylic copolymer relative to 100 parts by mass of the vinyl chloride resin having a degree of polymerization of 2800 used in Example 1 was changed to the amount (20 parts by mass) described in Table 1. Thus, the skin material of Example 4 was obtained.
  • Comparative Example 1 A skin material of Comparative Example 1 was obtained in the same manner as in Example 1 except that a vinyl chloride resin having a polymerization degree of 1000 was used in place of the vinyl chloride resin having a polymerization degree of 2800 used in Example 1.
  • Comparative Example 2 A skin material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the vinyl chloride resin having a degree of polymerization of 2800 used in Example 1 was used and no silicone/acrylic copolymer was contained.
  • Example 3 Comparison was carried out in the same manner as in Example 1 except that the vinyl chloride resin having a degree of polymerization of 2800 used in Example 1 was used and the content of the silicone/acrylic copolymer was 2 parts by mass based on 100 parts by mass of the vinyl chloride resin. The skin material of Example 3 was obtained.
  • Example 4 A base fabric was prepared in the same manner as in Example 1 except that a vinyl chloride resin having a degree of polymerization of 1300 was used in place of the vinyl chloride resin having a degree of polymerization of 2800 used in Example 1 and no silicone/acrylic copolymer was contained. An adhesive layer, a foamed resin layer, and a skin layer were formed on this in this order. Further, a crosslinked polyurethane abrasion-resistant layer, which is a layer that imparts abrasion resistance, is formed on the surface of the skin layer so as to have a thickness of 8 ⁇ m, and a surface treatment layer is further formed on the abrasion-resistant layer to have a thickness of 2 ⁇ m. Then, a skin material of Comparative Example 4 was obtained.
  • a crosslinked polyurethane abrasion-resistant layer which is a layer that imparts abrasion resistance
  • Plane abrasion test- The test was carried out with reference to a planar wear tester (method B) of JASO M 403/48/sheet skin material. As described below, the test conditions were stricter than those of the JASO method. (Test conditions) Standard conditions in JASO method ⁇ Conditions of this test Pressing load: 9.81N ⁇ 19.6N Number of tests: 10,000 times ⁇ 40,000 times After the flat abrasion test, the central portion of the synthetic resin skin material test sample was visually observed and evaluated according to the following criteria. (Criteria) The judgment criteria are as shown below. Of the following evaluation results, Grade 5 to Grade 3 are levels that pose no practical problems.
  • the striation pattern formed on the skin layer does not disappear 4 Part of the striation pattern formed on the skin layer disappears, but the foamed resin layer located below the skin layer is not exposed 3 Formed on the skin layer The drawn striation pattern disappears, but the foamed resin layer located below the skin layer is not exposed. 2 The striation pattern of the skin layer disappears and a part of the foamed resin layer located below the skin layer is exposed. The squeezing pattern of the skin layer disappears and the entire foamed resin layer located below the skin layer is exposed when the number of tests is less than 1
  • the synthetic resin skin materials of Examples 1 to 4 showed a practically problem-free abrasion resistance even in the abrasion resistance test under severe conditions, and white blur was observed in the appearance evaluation. I was not able to admit. From this, it is understood that the synthetic resin skin materials of the examples have both wear resistance and good appearance, and can be suitably used for a molded body having complicated irregularities. Further, although the synthetic resin skin materials of Examples 1 to 4 have a surface treatment layer, the surface treatment layer is a thin layer, no white blur is observed, and the appearance of the skin layer is not impaired. You can expect a high degree of freedom.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

基布、及び、前記基布上に形成され、重合度が1600~3000の塩化ビニル樹脂と、前記塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層を有する合成樹脂表皮材及びその製造方法。

Description

合成樹脂表皮材及びその製造方法
 本開示は、合成樹脂表皮材及びその製造方法に関する。
 近年、自動車内装品(インストルメントパネル、ドアトリム、座席、天井など)、鉄道車輌内装部品、航空機内装部品(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・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。このような合成樹脂表皮材は、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ものである。
 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きている。
 図3は、従来の塩化ビニル樹脂を含む表皮層32を有する合成樹脂表皮材30の概略断面図である。公知の合成樹脂表皮材30は、基布14の表面に接着剤層20を介して、発泡樹脂層18としての塩化ビニル発泡層が接着され、発泡樹脂層18の表面に塩化ビニル樹脂を含む表皮層32と表面処理層16とを備える。発泡樹脂層18は、気泡を含む弾力性に富む層である。表面処理層16は、塩化ビニル樹脂を含む表皮層32表面に位置し、外観や感触を調製したり、合成樹脂表皮材に耐摩耗性を付与したりする機能を有している。
 車両の内装用表皮材は、天然皮革に劣らないしっとりした感触と柔らかな風合いを必要とする。通常は、柔らかな感触を付与するために、柔軟性及び寸法安定性に優れた塩化ビニル樹脂を含む層(表皮層)を表面近傍に用いることが行われている。しかし、柔軟性に優れた塩化ビニル樹脂を含む層を、表皮材の表面近傍に配置する場合、合成樹脂表皮材における表面の耐摩耗性が低下するという問題があった。
 日常、長期間使用される自動車用の内装部品、家具の表皮材等は耐久性を必要とするため、長期間に亘り、良好な外観と風合いとを維持しうることが重要である。
 耐摩耗性を向上する目的で、表面近傍に存在する塩化ビニル樹脂を含む表皮層の厚みを厚くする、表面処理層の厚みを厚くする、塩化ビニル樹脂を含む表皮層の形成に高強度の塩化ビニル樹脂を用いる等の対応をとることができる。しかし、既述の対応では、表皮材の風合いが損なわれたり、表皮材の柔軟性及び屈曲性が低下したりする場合がある。従って、既述の対応では、得られた表皮材は、自動車のシートなどの内装材として、複雑な凹凸を有する成型体に適用することが困難となる。
 耐摩耗性と風合いとを両立しうる合成樹脂表皮材として、塩化ビニル樹脂層と、水系架橋ポリウレタン層と、樹脂及び有機粒子を含有する表面処理層と、をこの順に備える合成樹脂表皮材が提案されている(特開2015-66889号公報参照)。
 また、塩化ビニル樹脂層に塩化ビニル樹脂に対し、特定量のシリコーン/アクリル共重合体を含有する塩化ビニル樹脂層と、ポリカーボネートポリウレタンとエステル系ポリウレタンとの混合物をカルボジシミド基含有の架橋剤で架橋してなる表面処理層とを備える合成樹脂レザーが提案されている(国際公開第2017/061611号参照)。
 しかしながら、特開2015-66889号公報に記載の合成樹脂表皮材は、耐久性は良好であるが、塩化ビニル樹脂層上に、表面の感触を向上させる表面処理層と、耐久性向上のための架橋ポリウレタン層との2層を有し、製造性の点で改良の余地がある。
 また、国際公開第2017/061611号に記載の如く、耐摩耗性向上を目的として、塩化ビニル樹脂表皮層の表面に厚みのある表面処理層、又は、架橋構造を含み、耐摩耗性を向上させた表面処理層等を設けた場合、塩化ビニル樹脂表皮層の柔軟な感触及び外観が損なわれる場合がある。特に表面処理層の厚みを厚くすると、表面処理層表面の光散乱などに起因して、白ボケ(white blur)と称される表皮材の表面が目視にて白く見える現象が生じることがあり、合成樹脂表皮材に良好な外観を付与するための意匠の自由度が低下するという問題があった。
 上記従来技術を考慮してなされた本発明の一実施形態の課題は、耐摩耗性に優れ、意匠の自由度が良好な合成樹脂表皮材を提供することである。
 また、本発明の別の実施形態の課題は、耐摩耗性に優れ、意匠の自由度が良好な合成樹脂表皮材の製造方法を提供することにある。
 上記課題を解決するための手段には、以下の態様が含まれる。
<1> 基布、基布上に形成され、重合度が1600~3000の塩化ビニル樹脂と、前記塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層を有す合成樹脂表皮材。
<2> 前記塩化ビニル樹脂表皮層の、基布側とは反対側の面に、架橋構造を含む耐摩耗性層を有さない<1>に記載の合成樹脂表皮材。
<3> 前記基布と前記塩化ビニル樹脂表皮層との間に、接着剤層の少なくとも1層を有する<1>又は<2>に記載の合成樹脂表皮材。
<4> 前記基布と前記塩化ビニル樹脂表皮層との間に、発泡樹脂層を有する<1>~<3>のいずれか1つに記載の合成樹脂表皮材。
<5> 前記基布と前記塩化ビニル樹脂表皮層との間に、前記基布側から接着剤層及び発泡樹脂層をこの順に有する<1>又は<2>に記載の合成樹脂表皮材。
<6> 前記発泡樹脂層は、塩化ビニル樹脂を含む<4>又は<5>に記載の合成樹脂表皮材。
<7> 重合度が1600~3000の塩化ビニル樹脂と、前記塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層形成用組成物を用いて、塩化ビニル樹脂表皮層を形成する工程と、前記塩化ビニル樹脂表皮層の片面に、基布を接着する工程と、を有する合成樹脂表皮材の製造方法。
<8> さらに、前記塩化ビニル樹脂表皮層の、基布と接着させる側に、発泡剤と樹脂とを含有する発泡樹脂層形成用組成物層を形成し、前記塩化ビニル樹脂表皮層と発泡樹脂層形成用組成物層との積層体を形成する工程と、加熱により、前記発泡樹脂層形成用組成物中の発泡剤を発泡させ、発泡樹脂層を形成する工程と、を有する<7>に記載の合成樹脂表皮材の製造方法。
<9>前記基布を接着する工程が、前記塩化ビニル発泡樹脂層形成用組成物層と基布との間に接着剤層を設ける工程を含む<8>に記載の合成樹脂表皮材。
 本開示の合成樹脂表皮材の作用機構は明確ではないが、以下のように考えている。
 本開示の合成樹脂表皮材は、塩化ビニル樹脂表皮層の形成に用いる塩化ビニル樹脂として、重合度が1600~3000の塩化ビニル樹脂を含むことにより、重合度のより低い塩化ビニル樹脂を含む場合に比較して、シート状に成形した際の塩化ビニル樹脂表皮層の耐摩耗性が向上する。さらに、塩化ビニル樹脂表皮層がシリコーン/アクリル共重合体を含むことで、表皮層の色相などに影響を与えることなく、表面エネルギーを下げることができ、耐摩耗性がより向上すると考えられる。
 このため、塩化ビニル樹脂表皮層は、厚みを厚くしなくても十分な耐摩耗性などの耐久性を発現し、塩化ビニル樹脂が本来有する柔軟性を生かした合成樹脂表皮材を提供できる。
 また、塩化ビニル樹脂表皮層の耐摩耗性が良好であることにより、特に耐摩耗性付与のための表面処理層をさらに設ける必要はなく、表皮層の意匠に応じた外観を呈することにより、意匠の自由度が良好となる。
 なお、合成樹脂表皮材の外観を損なわない限りにおいて、塩化ビニル樹脂表皮層の面上に、例えば、表面の感触を改良するための薄層の表面処理層などの任意の層をさらに有することは妨げない。
 本開示の合成樹脂表皮材に使用される基布には特に制限はないが、基布として、弾力性と伸縮性が良好な編布、例えば、メリヤス編み地等の編布を選択することで、合成樹脂表皮材の伸縮性、柔軟性がより向上するという利点を有する。
 本開示の合成樹脂表皮材は、既述のように、表面の耐摩耗性、耐久性に優れ、且つ、柔軟で意匠の自由度に優れることから、車輌用シートなどの車両用内装材や椅子の表面材として好適に使用され、製品に任意の意匠を付与することができる。
 本発明の一実施形態によれば、耐摩耗性に優れ、意匠の自由度が良好な合成樹脂表皮材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、耐摩耗性に優れ、意匠の自由度が良好な合成樹脂表皮材の製造方法を提供することができる。
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。 塩化ビニル樹脂表皮層に加え、さらに、表面処理層、発泡樹脂層などの任意の層を有する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。 従来の合成樹脂表皮材の一態様を示す概略断面図である。
 以下、本開示の好ましい実施の形態について説明する。
 以下に記載する実施の形態における構成要件の説明は、本開示の代表的な実施の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の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。
 本開示中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、本開示中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。
 本開示における「意匠の自由度が良好」とは、「合成樹脂表皮材表面の光散乱などに起因する白ボケと称される現象が生じることが抑制される」ことを指す。即ち、表皮材の表面が、光散乱などに起因して白く見えることで、本来表皮材が有する色相、天然皮革を模したシボ模様などが見え難くなり、良好な外観を付与する意匠が損なわれる。しかし、本開示の合成樹脂表皮材によれば、白ボケに起因する意匠の自由度の低下が抑制され、良好な外観を付与する意匠の自由度が達成される。
<合成樹脂表皮材>
 まず、本開示の合成樹脂表皮材について、図1及び図2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。図1に示す態様は、本開示の合成樹脂表皮材の最も簡易な構成を示している。
 図1に示す態様では、合成樹脂表皮材10は、基布14上に、塩化ビニル樹脂表皮層12を有する。
 なお、各図面において同一の符号を用いて示される構成要素は、同一の構成要素であることを意味する。
 本開示の合成樹脂表皮材における塩化ビニル樹脂表皮層(以下、「表皮層」とも称する)は、重合度が1600~3000の塩化ビニル樹脂(以下、「特定塩化ビニル樹脂」とも称する)と、特定塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む。この組成に起因して、塩化ビニル樹脂表皮層は、塩化ビニル樹脂特有の柔軟性及び良好な感触を備え、且つ、耐摩耗性に優れる。このため、特に、塩化ビニル樹脂表皮層の基布とは反対側の面に、耐摩耗性を向上させる目的で別異の層をさらに設ける必要はない。
 このため、合成樹脂表皮材は、塩化ビニル樹脂が有する感触と、良好な外観とを備え、塩化ビニル樹脂表皮層の形成時に付与した種々の意匠を生かした外観となる。このため、本開示の合成樹脂表皮材は意匠の自由度が良好となる。
 本開示の合成樹脂表皮材は、以下に詳述する基布と、塩化ビニル樹脂表皮層とを有すれば特に制限はない。なお、基布と塩化ビニル樹脂表皮層とに加え、効果を損なわない範囲で、合成樹脂表皮材に通常備えられるその他の層を有していてもよい。その他の層については後述する。
 以下、本開示の合成樹脂表皮材(以下、単に「表皮材」と称することがある)を、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.基布)
 本開示の表皮材の基布としては、必要な強度、耐久性を有するものであれば、特に制限はなく、公知の基布から目的に応じて適宜選択して用いることができる。基布は、編物、織物、及び不織布のいずれであってもよい。
 表皮材を凹凸のある成型体に適用する場合には、ある程度の伸縮性を有する編物や織物を用いることが好ましい。表皮材の感触及び形状追従性がより良好であるという観点からは、タテとヨコの伸びの比率が均等で厚みが比較的厚い基布を使用することが好ましい。
 基布としては、例えば、車両用シートの表皮材として用いる場合には、伸縮性、厚み制御の容易性の観点から、メリヤス編み地、変成メリヤス編み地などの編布が好ましい。
 また、基布として、三次元不織布なども厚みの調整が容易という観点から好適に使用される。
 基布の編成、織成に使用される繊維(糸)の材質は、ポリエステル、ポリアミド、レーヨン等からなる糸、及び、ポリエステル、ポリアミド、レーヨン等を含む混紡糸などが挙げられる。
 基布としては、メリヤス編み地の他、例えば、特開2013-72141号公報に記載のポンチローマ編みを用いた合成皮革用基布などを用いることもできる。
 基布の厚みは表皮材の使用目的に応じて適宜選択される。なかでも、感触に優れ、表皮材の柔軟性を低下させない範囲、例えば、0.15mm~0.6mmの範囲が好ましく、0.3mm~0.5mmの範囲がより好ましい。
 基布の表皮層側の面には、必要に応じて起毛加工を施してもよい。また、基布は、基布の表皮層側の面にパイルが形成されたパイル編み地を用いてもよい。基布の表面に起毛又はパイルを有することで、隣接する層、例えば、表皮層、接着剤層等との接着性がより向上する。
(2.塩化ビニル樹脂表皮層)
 本開示の表皮材における表皮層は、重合度が1600~3000の特定塩化ビニル樹脂及び、特定塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体を含み、所望によりその他の成分を含んでもよい。
 表皮層は、少なくとも、特定塩化ビニル樹脂と、シリコーン/アクリル共重合体と、好ましくは可塑剤とを含む塩化ビニル樹脂表皮層形成用組成物を用いて形成される。
(2-1.重合度が1600~3000の塩化ビニル樹脂)
 特定塩化ビニル樹脂は、塩化ビニルモノマー(CH=CHCl)を付加重合させて得られる樹脂である。塩化ビニル樹脂は、重合度1000~1300程度の樹脂が汎用されている。しかし、本開示の表皮材における表皮層は、重合度が1600~3000の特定塩化ビニル樹脂を用い、さらに後述のシリコーン/アクリル共重合体を含有することで、強度、耐摩耗性が改良されている。
 特定塩化ビニル樹脂の重合度は、1600~3000であり、1700~2900が好ましく、1700~2800がより好ましい。
 本開示における塩化ビニル樹脂の重合度は、市販品の場合、カタログ値を参照することができる。
 表皮層に含まれる特定塩化ビニル樹脂としては、重合度が上記範囲であれば、いずれも用いることができる。
 特定塩化ビニル樹脂は市販品を用いてもよく、例えば、大洋塩ビ(株)製のTH-2800等が挙げられる。
 表皮層は、特定塩化ビニル樹脂は1種のみを含んでいてもよく、2種以上を含んでいてもよい。2種以上含む場合、上記重合度の範囲であれば、互いに重合度の異なる2種以上の塩化ビニル樹脂の混合物を用いてもよい。
 表皮層は、塩化ビニル樹脂以外の樹脂を含んでいてもよい。表皮層が含む全樹脂に対する塩化ビニル樹脂の含有量は、30質量%~80質量%であることが好ましく、40質量%~50質量%であることがより好ましい。
 得られた表皮層の柔軟性向上のため、表皮層は、可塑剤を含むことが好ましい。
(2-2.シリコーン/アクリル共重合体)
 表皮層は、シリコーン/アクリル共重合体の少なくとも1種を含む。
 シリコーン/アクリル共重合体は、以下に示すシロキサン構造単位とアクリル系モノマー由来の構造単位とを含む共重合体である。
Figure JPOXMLDOC01-appb-C000001

 
 シリコーン/アクリル共重合体は、例えば、末端にラジカル重合性基を有するポリオルガノシロキサンと(メタ)アクリル酸エステルとを、常法により共重合させて得ることができる。シロキサン構造単位とアクリル系モノマー由来の構造単位との共重合比には特に制限はないが、シロキサン構造単位:アクリル系モノマー由来の構造単位の共重合比はモル比で60:40~90:10とすることができる。なかでも、形成された表皮層の耐摩耗性をより向上させるという観点からは、シロキサン構造単位:アクリル系モノマー由来の構造単位の共重合比は65:35~75:25が好ましく、70:30~75:25がより好ましい。
 表皮層は、シリコーン/アクリル共重合体を1種のみ含んでもよく2種以上含んでいてもよい。
 表皮層におけるシリコーン/アクリル共重合体の含有量は、表皮層に含まれる塩化ビニル樹脂100質量部に対して、3質量部~20質量部であり、5質量部~15質量部の範囲が好ましく、7質量部~13質量の範囲がより好ましい。
 シリコーン/アクリル共重合体の含有量が上記範囲において、表皮材の表面耐摩耗性及び柔軟性が好適な範囲となる。
(2-3.表皮層に含まれるその他の成分)
 表皮層は、特定塩化ビニル樹脂及びシリコーン/アクリル共重合体に加え、その他の成分を含んでいてもよい。
 その他の成分としては、上記以外の合成樹脂、可塑剤、安定剤、充填剤、着色剤、難燃剤、ゲル化促進剤、可塑剤相溶剤などが挙げられる。
(可塑剤)
 塩化ビニル樹脂の柔軟性を向上させるため、表皮層は可塑剤を含むことが好ましい。
 可塑剤としては、公知の塩化ビニル樹脂用可塑剤を制限なく使用することができる。
 可塑剤としては、例えば、ジイソデシルフタレート、ジ-2-エチルヘキシルフタレート、ジイソノニルフタレート等のフタル酸エステル系可塑剤、アジピン酸ジオクチル、セバシン酸ジオクチル等の脂肪酸エステル系可塑剤、トリメリット酸トリオクチル等のトリメリット酸エステル系可塑剤、トリクレジルホスフェート、トリキシリルホスフェート等のトリアリールリン酸エステル系可塑剤、エポキシ化大豆油等のエポキシ系可塑剤、ポリプロピレンアジペート等のポリエステル系可塑剤等が挙げられる。
 表皮層は、可塑剤を1種のみ含んでもよく、2種以上含んでいてもよい。
(着色剤)
 表皮層は着色剤を含んでもよい。表皮層が着色剤を含むことで、表皮材に所望の色相を付与することができ、意匠性に優れた表皮材とすることができる。
 表皮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。耐久性、及び耐光性により良好であるという観点からは、着色剤は顔料が好ましい。
 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。
 表皮層は、着色剤を1種のみ含んでもよく、2種以上含んでもよい。
 着色剤として顔料を用いる場合には、界面活性剤、高分子分散剤などの顔料分散剤を併用してもよい。
(その他の成分)
 表皮層は、充填剤を含有してもよい。充填剤としては、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)、マイカ(雲母)、タルク、硫酸バリウム等の無機充填剤が挙げられる。
 表皮層は、充填剤を1種のみ含んでもよく、2種以上含んでもよい。
 表皮層は、安定化剤を含有してもよい。安定化剤を含有することで、表皮層の耐熱性が向上する。
 安定化剤としては、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸バリウム、ステアリン酸亜鉛、ラウリン酸カルシウム、ラウリン酸バリウム、ラウリン酸亜鉛などの脂肪酸金属塩、フェノール、ナフトール等のナトリウム化合物、亜鉛、バリウム等の金属塩、ジブチルスズジラウレート、ジブチルスズジマレートなどの有機スズ化合物、ジエチルホスファイト、ジブチルホスファイト、ジオクチルホスファイト、ジフェニルイソデシルホスファイト、トリクレジルホスファイト、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリイソオクチルホスファイトなどの亜リン酸エステル類等が挙げられる。表皮層は、安定化剤を1種のみ含んでもよく、2種以上含んでもよい。
 表皮層は、難燃剤を含有してもよい。表皮層が難燃剤を含むことで、表皮材に難燃性を付与することができる。難燃剤としては、公知の無機系又は有機系の難燃剤を適宜選択して用いることができる。表皮層は、難燃剤を1種のみ含んでもよく、2種以上含んでもよい。
 表皮層は、膜物性改良などの目的で、塩化ビニル樹脂及びシリコーン/アクリル共重合体以外の、他の合成樹脂を含んでいてもよい。他の合成樹脂としては、熱可塑性ポリウレタン樹脂(TPU)などが挙げられる。他の樹脂を含む場合、他の樹脂の含有量は、表皮層の全固形分100質量部に対し、10質量部以下であることが好ましい。
(2-4.表皮層の形成)
 表皮層の形成方法には特に制限はない。表皮層の形成方法としては、上記した各成分を含む表皮層形成用組成物を調製し、カレンダー法、ペースト加工法、溶融押出し法等によりシート状に成形することで表皮層を形成する方法が挙げられる。また、基布上に直接、又は、後述の接着剤層等を介して表皮層形成用組成物を塗布して表皮層形成用組成物層を形成し、これを硬化して基布上に表皮層を形成する方法をとることもできる。
 なかでも、表皮層の均一性がより良好となり、着色剤を含んだ表皮層形成後の装置内の清掃が簡易である点から、表皮層の形成をカレンダー法で行うことが好ましい。
 表皮層の厚みには特に制限はないが、本開示における表皮層は、薄層でも耐摩耗性、及び強度が良好であるため、強度向上のために厚みを向上させることは必ずしも必要ではない。
 表皮層の厚みは、170μm~650μmの範囲が好ましく、200μm~300μmの範囲がより好ましい。
 本開示の表皮材は、基布及び表皮層のみで構成されていてもよいが、他の公知の層を有していてもよい。
 図2は、本開示の表皮材の別の一例を示す概略断面図である。
 図2に示す表皮材22は、基布14上に任意の層である接着剤層20を介して、任意の層である発泡樹脂層18と、既述の表皮層12と、任意の層である表面処理層16とを、この順に有する。
 表皮材22が、接着剤層20を有することで隣接する層が接着剤層20を介してより安定に、且つ強固に接着される。
 また、表皮材22が、発泡樹脂層18を有することで、表皮材22がより柔軟となり、適度な弾力性を表皮材22に付与することができる。
 表皮材22が、表面処理層16を有することで、表皮材22に任意の良好な感触を付与することができる。なお、本開示における表皮層12は耐摩耗性が良好であるため、公知の表面処理層16の如く、耐摩耗性などの強度向上を目的とした、架橋構造など有する厚みの厚い表面処理層、架橋構造を有する耐摩耗性層などを形成する必要はない。
 以下、本開示の表皮材が有してもよい任意の層について説明する。
(3.接着剤層)
 本開示の表皮材は、接着剤層を有していてもよい。接着剤層は、例えば、基布と表皮層など隣接する層同士の接着性を向上させる等の目的で設けられる。
 接着剤層は、例えば、基布表面に接着剤を積層し、乾燥することで形成することができる。接着剤の積層は、転写法により行っても、塗布法により行ってもよい。
 所望により設けられる接着剤層の形成に使用される接着剤としては特に制限はなく、目的に応じて適宜選択されるが、例えば(1)ウレタン系エマルジョン接着剤、(2)塩化ビニル系接着剤、(3)2液硬化型ポリエステル系接着剤、(4)2液硬化型ウレタン接着剤などが好適に使用される。
 基布と表皮層との積層体を形成して表皮材を形成する際には、通常は、基布の表面に接着剤を付与することで、接着剤層を形成することができる。
 また、図2に示す態様では、基布14と表皮層12との間に任意の層である接着剤層20と発泡樹脂層18とを形成する。この場合、まず、表皮層12を形成するための表皮層形成用組成物層を形成し、表皮層形成用組成物層の表面に後述の発泡樹脂層形成用組成物層を形成し、発泡樹脂層形成用組成物層に接着剤を付与することで接着剤層20を形成することができる。
 表皮材は、接着剤層を1層のみ有してもよく、必要に応じて2層以上を有してもよい。
 既述のように、接着剤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が、均一な厚みの接着剤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。
 また、接着剤層を転写法で形成する場合には、予め作製された接着剤層の表面保護のため、接着剤層表面に保護シートを有していてもよい。接着剤層表面の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。
(4.発泡樹脂層)
 本開示の表皮材は、発泡樹脂層を有していてもよい。
 発泡樹脂層は、表皮材に弾力を付与し、より感触を向上させる目的で設けられる。発泡樹脂層に含まれる樹脂としては、発泡が容易という観点から、塩化ビニル樹脂、ウレタン樹脂などが挙げられ、表皮層との親和性に優れるという観点からは、塩化ビニル樹脂を含む発泡樹脂層が好ましい。
 発泡樹脂層は、発泡剤及び樹脂を含む発泡樹脂層形成用組成物層を形成し、その後、加熱により発泡剤を発泡させて、樹脂層内に微細な気泡を発生させることで形成される。上記方法により、微細な気泡を内包する発泡樹脂層が形成される。
 発泡樹脂層が塩化ビニル樹脂を含む場合、塩化ビニル樹脂としては、既述の表皮層に含まれる塩化ビニル樹脂の例を同様に挙げることができる。発泡樹脂層に含まれる塩化ビニル樹脂は表皮層に含まれる塩化ビニル樹脂と同じであっても異なっていてもよい。
 発泡剤としては、発泡樹脂層に必要な弾力性と厚みを与える微細な気泡を形成しうるものであれば特に制限はない。発泡剤としては、加熱により発泡するアゾジカルボンアミド(ADCA)、p,p’-オキシビスベンゼンスルホニルヒドラジド(OBSH)などの化学的発泡剤;熱膨張ビーズなどが挙げられる。
 発泡樹脂層形成用組成物の調製に用いる熱膨張ビーズとは、中空の熱可塑性樹脂粒子中に炭化水素系溶剤などの有機溶剤等を内包してなる粒子であり、加熱による有機溶剤の体積膨張により粒子の体積が増加し、結果として樹脂マトリックス(分散媒)中に気泡が内在された発泡樹脂層が形成される。
 本開示に使用される熱膨張ビーズは、加熱により膨張して前記樹脂マトリックスに気泡が形成され、形成された気泡の状態を維持しうるものであれば、いずれのものを用いてもよい。
 熱膨張ビーズは市販品としても入手可能であり、例えば、日本フェライト社製のエクスパンセルシリーズ(商品名)などが挙げられ、いずれも本開示に使用しうる。
 発泡剤として熱膨張ビーズを用いる場合の、熱膨張ビーズの添加量としては、発泡樹脂層に含まれる樹脂100質量部に対して、0.5質量部~10質量部であることが好ましく、1質量部~7質量部であることがより好ましい。
 本開示における発泡樹脂層形成用組成物は、乾燥を効率よく行う観点から、溶媒として水ではなく、有機溶剤を用いることが好ましい。発泡剤として熱膨張ビーズを用いる場合には、有機溶剤は熱膨張ビーズを構成する樹脂を溶解しないものを選択することが好ましい。熱膨張ビーズを構成する樹脂が有機溶剤によって溶けた場合には、中空部分が維持できなくなり、所望の気泡を内在する発泡樹脂層が形成し難くなるためである。
 熱膨張ビーズを構成する樹脂を溶解しない溶剤の選択方法としては、評価する有機溶剤(単体及び混合物を含む)に、使用する熱膨張ビーズを室温(25℃)で3日間浸漬した後、目視判定により発泡の形跡がない有機溶剤を選択する方法が挙げられる。熱膨張ビーズを構成する樹脂が有機溶剤に溶解した場合、樹脂ビーズの外皮が損傷し、熱膨張ビーズ中に内包される気体や炭化水素系溶剤が浸漬した有機溶剤中に流出して気泡が観察され、このような有機溶剤は本開示における「熱膨張ビーズを構成する樹脂を溶解しない溶剤」には包含されない。
 例えば、熱膨張ビーズとして、日本フェライト社製のエクスパンセルを用いた場合、使用し得る溶剤としては、メチルアルコール、エチルアルコール、イソプロピルアルコール(IPA)、トルエン、スチレン、アセトン、酢酸エチル、エチレングリコール、n-ヘキサン、シクロヘキサン、メチルエチルケトン(MEK)、及びプロピレングリコールモノメチルエーテル(PGME)が挙げられ、これら溶剤から1種以上を適宜選択して用いればよい。
 なお、発泡樹脂層形成用組成物層に含まれる熱膨張ビーズを膨張させるための加熱温度は、130℃~230℃の範囲であることが好ましく、190℃~230℃の範囲であることがより好ましい。
 発泡樹脂層の膜厚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、強度及び触感の観点から、発泡樹脂層の膜厚は、発泡前の膜厚として、150μm~700μmの範囲であることが好ましく、170μm~450μmの範囲であることがさらに好ましい。また、発泡後の気泡を内在した発泡樹脂層の膜厚は、220μm~1300μmの範囲であることが好ましく、400μm~900μmの範囲であることがさらに好ましい。
 なお、図2に示すように、合成樹脂表皮材22において、基布14と発泡樹脂層18との間に接着剤層20を有することが、表皮材22の耐久性及び形状追従性がより向上するという観点から好ましい。
(5.表面処理層)
 表皮材は、既述のように、外観と感触向上を目的として表面処理層を有してもよい。
 表面処理層は、感触をより向上させる目的で設けられ、少なくとも樹脂を含み、所望により、感触向上剤として、フィラーである有機粒子、意匠性向上を目的とする着色剤などを含んでもよい。
 また、表皮材の最表面に位置して所望により形成される表面処理層は、目的に応じて着色されたり、印刷が施されたり、絞模様に代表される天然皮革様の凹凸が形成されたりしてもよい。
 表面処理層に含まれ得る樹脂としては、ポリウレタン、アクリル樹脂、フッ素樹脂、塩化ビニル樹脂等が挙げられ、感触が良好であるという点からは、ポリウレタンを主材として用いることが好ましい。ここで「主材」とは、樹脂を複数種併用する場合に、含有比率の最も高い樹脂を意味する。
 表面処理層に使用されるポリウレタンとしては、水系ポリウレタンが好ましいものとして挙げられる。
 また、表面処理層に使用されるアクリル樹脂としては、例えば、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る。
 表面処理層にフィラーとしての有機粒子を含むことで、従来、つや消し剤として使用されていた不定形無機フィラーを使用した場合に比較して、表皮材にしっとりとした温か味の有る触感を付与することができる。
 有機粒子としては、ウレタンビーズ、アクリルビーズなどの有機樹脂粒子、コラーゲン粒子などのタンパク質系フィラーなどが挙げられる。
 有機粒子の形状は、感触がより良好になるという観点からは、真球状か或は真球状に近い球形が好ましい。有機粒子の形状は、例えば、長径と短径との比が1.5以下であることが好ましい。
 有機粒子の平均粒子径としては、1μm~20μmの範囲であることが好ましく、5μm~10μmの範囲であることがより好ましい。粒子径が上記範囲において、表面処理層からの粒子の脱落や外観への悪影響が抑制され、良好な外観と優れた風合いを長期間維持しうる。
 なお、有機粒子の平均粒子径は、堀場製作所製の自動粒径測定装置(型番:CAPA-300)を用い、分散媒を水とした光透過遠心沈殿法によりディスク回転速度3000rpm(回転/分)で測定し、容積基準のメディアン径を測定する方法により測定した値を用いている。
 表面処理層は、有機粒子を1種のみを含んでもよく、2種以上を含んでもよい。
 表面処理層は、必要に応じて意匠性を付与するために着色剤を含んでいてもよい。着色剤としては、表皮層において挙げた汎用の着色剤を同様に用いることができ、好ましい含有量も同様である。
 表面処理層の厚みは、1μm~5μmの範囲であることが好ましく、2μm~3μmの範囲がより好ましい。
 本開示の表皮材は、特定塩化ビニル樹脂と特定量のシリコーン/アクリル共重合体とを含む表皮層を有しているため、表皮層の、基布側とは反対側の面、即ち、表皮材の最表面に、架橋構造を含む耐摩耗性層を有さなくても、良好な耐摩耗性が得られる。
〔合成樹脂表皮材の製造方法〕
 本開示の合成樹脂表皮材の製造方法には特に制限はない。本開示の合成樹脂表皮材は、以下に示す本開示の合成樹脂表皮材の製造方法(以下、本開示の製造方法と称することがある)により製造されることが好ましい。
 本開示の製造方法は、重合度が1600~3000の塩化ビニル樹脂(特定塩化ビニル樹脂)と、特定塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層形成用組成物を用いて、塩化ビニル樹脂表皮層を形成する工程(工程(I))と、塩化ビニル樹脂表皮層の片面に、基布を接着する工程(工程(II))と、を有する。
 また、本開示の製造方法は、工程(I)及び工程(II)に加え、所望により、さらに、塩化ビニル樹脂表皮層の、基布と接着させる側に、発泡剤と樹脂とを含有する発泡樹脂層形成用組成物層を形成し、塩化ビニル樹脂表皮層と発泡樹脂層形成用組成物層との積層体を形成する工程(工程(III))と、加熱により、前記発泡樹脂層形成用組成物に含まれる発泡剤を発泡させ、発泡樹脂層を形成する工程(工程(IV))と、を有していてもよい。
 なお、塩化ビニル樹脂表皮層の片面に、基布を接着する工程(工程(II))は、発泡樹脂層形成用組成物層と基布との間に接着剤層を設ける工程(工程(V))を含んでいてもよい。
 また、任意の層である表面処理層を設ける場合には、表皮層の基布側とは反対側の面に、表面処理層を形成する工程(工程(VI))を行ってもよい。
 本開示の製造方法について工程毎に詳細を説明する。
(工程(I))
 工程(I)は、重合度が1600~3000の特定塩化ビニル樹脂と、特定塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層形成用組成物を用いて、表皮層を形成する工程であり、重合度が1600~3000の特定塩化ビニル樹脂と、特定塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、さらに、所望により含有させる可塑剤、着色剤などの任意の成分を含む塩化ビニル樹脂表皮層形成用組成物をまず調製し、得られた組成物を用いて、表皮層を形成する。
 表皮層を形成する方法は任意であるが、既述のように、調製した塩化ビニル樹脂表皮層形成用組成物を、カレンダー法、ペースト加工法、溶融押出し法等によりシート状に成形して表皮層とする方法が挙げられ、好ましくはカレンダー法により、前記組成物をシート状に成形して表皮層とする方法が挙げられる。
(工程(III))
 なお、任意の層としての発泡樹脂層を形成する場合には、表皮層を形成する工程に引き続き、発泡剤と樹脂とを含有する組成物からなる発泡樹脂層形成用組成物層を形成し、表皮層と発泡樹脂層形成用組成物層との積層体を形成する工程(工程(III))を行ってもよい。
 工程(III)を行う場合、積層体は、表皮層と、発泡樹脂層形成用組成物層と、を同時にカレンダー加工、或は、同時押し出し加工により形成してもよい。
 また、まず、発泡樹脂層形成用組成物層を形成し、その表面にペースト加工機や押し出し機で表皮層(又は表皮層形成用組成物層)を形成して、発泡樹脂層形成用組成物層と表皮層との積層体を形成してもよい。
(工程(II))
 工程(II)は、工程(I)で予め形成された表皮層、又は、工程(I)と工程(III)とを実施して形成した表皮層と発泡樹脂層形成用組成物層との積層体を、基布に接着する工程である。工程(II)に代えて、又は、工程(II)に加えて、前記発泡樹脂層形成用組成物層と基布との間に接着剤層を設ける工程(工程(V))を行ってもよい。
 積層体と基布とを接着する場合(工程(V))、積層体の発泡樹脂層形成用組成物層側の表面に基布を接着すればよい。
 基布は、表皮層又は発泡樹脂層形成用組成物層と接する側には常法により起毛処理を行った基布を用いてもよい。
 接着は、表皮層又は発泡樹脂層形成用組成物層の表面、或は基布の表面に接着剤層を形成した後、両者を、接着剤層を介して貼り合わせることで行ってもよい。
 また、積層体と基布とを接着させる場合には、例えば、発泡樹脂層形成用組成物層の硬化前に、基布と合わせてラミネートした後、接着剤層及び発泡樹脂層を硬化させて接着させてもよい。
 接着剤層は、例えば、表皮層又は発泡樹脂層形成用組成物層の表面或は基布の表面に、接着剤を積層し、乾燥して形成することができる。
 所望により設けられる接着剤層の形成に使用される接着剤は、接着剤層の欄で述べた通りである。
 通常は、接着剤層を形成する層又は基布の表面に接着剤を付与することで接着剤層が形成される。接着剤を付与する方法としては、転写法、塗布法などが挙げられ、均一な厚みの接着剤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。
 工程(I)又は工程(III)と、工程(II)又は工程(V)とは、同時に行ってもよく、或いは、逐次行ってもよい。即ち、表皮層又は積層体をカレンダー法などにより形成し、搬送しながら、表皮層又は積層体の発泡樹脂層形成用組成物層側の表面に、基布をニップロールなどで、加熱、押圧しながら接着してもよい。
 また、接着剤層を介して基布と所望の層とを接着する場合には、所望の層の表面に、接着剤層を形成し、その後、接着剤層と基布とを合わせて押圧接着してもよい。
 接着剤層を加熱、及び乾燥させることで、表皮層上に所望の層と接着剤層とが形成される。
(工程(VI))
 工程(VI)は、表皮層の表面の感触及び外観をより優れたものとするために、表皮層の表面(表皮層の基布側とは反対側の面)に、表面処理層(感触向上層)を形成する工程である。
 工程(VI)は、樹脂を含む表面処理層形成用組成物を、表皮層の表面に付与することにより行われる。
 表面処理層形成用組成物の付与は、公知の方法を適宜適用して行うことができる。
 表面処理層の形成は、表面処理層形成用組成物を表皮層の表面に、例えば、グラビアプリント法による塗布、リバースコーター、ダイレクトコーター等のコーティング装置による塗布などの方法から適宜選択して適用することで行えばよい。なかでも、より均一な層を形成しうるという観点からは、グラビアプリント法により表面処理層形成用組成物を付与することが好ましい。
 表面処理層の詳細は既述の通りである。本開示の製造方法では、表面処理層を形成する場合も、その厚みを薄くすることができるため、感触向上用の表面処理層は、表皮層の外観に殆ど影響を与えず、従って、表皮層における意匠の自由度を低下が抑制できる。
(工程(IV))
 本開示の製造方法により得られる表皮材が発泡樹脂層を有する場合、即ち、表皮層と発泡樹脂層形成用組成物層との積層体を形成する工程(III)を行った場合、工程(III)の後に、加熱により、発泡樹脂層形成用組成物中の発泡剤を発泡させ、発泡樹脂層を形成する工程(工程(IV))を行う。
 工程(IV)は、加熱により、発泡樹脂層形成用組成物に含まれるの発泡剤を発泡させ、発泡樹脂層を形成する工程である。加熱は、所定の温度に調整された加熱炉内を搬送させることで非接触加熱により行うことが好ましい。
 発泡樹脂層形成用組成物層に発泡剤として熱膨張ビーズを含む場合、熱膨張ビーズを膨張させるための加熱温度は、130℃~230℃の範囲であることが好ましく、190℃~230℃の範囲であることがより好ましい。また、発泡剤としてADCAを用いた場合には、加熱温度は、180℃~250℃の範囲であることが好ましく、200℃~230℃の範囲であることがより好ましい。
 工程(IV)は、基布と表皮層とを接着する工程(工程(II))の後、表面処理層の形成工程(工程(VI))に先立って行ってもよく、工程(VI)の後に行ってもよい。
(その他の工程)
 本開示の製造方法は、必要に応じて、さらに外観を向上させるための意匠性を付与する工程を行うことができる。
 上記工程(I)及び工程(II)を完了した後、又は、上記工程(I)及び工程(II)に加え、所望により行われる既述のその他の工程を完了した後、意匠性を付与する工程を行うことができる。
 意匠性を付与する工程としては、例えば、表皮層又は所望により設けられた表面処理層に、例えば、皮革様の微細な凹凸模様である絞(シボ)模様が彫刻されているエンボスロールを、表面が加熱されている状態で押し当てることにより、表面に絞模様を形成する工程が挙げられる。
 絞模様の付与は、工程(II)の後、工程(VI)に先立って行ってもよい。この場合、基布上に、発泡樹脂層形成用組成物層と表皮層とを有する積層体を加熱することで発泡剤を発泡させ、気泡を有する発泡樹脂層を形成させた後、絞形状が彫刻されているエンボスロールを、表面が加熱されている状態で押し当てて、絞模様を形成し、その後、所望により表面処理層を形成する工程であってもよい。
 絞ロールに予め天然皮革様の凹凸を形成することで、これを用いてエンボス加工することにより、表面に天然皮革様の凹凸が転写され、合成樹脂表皮材は天然皮革様の優れた外観を有することになる。
 エンボス加工における加熱温度は、100℃~240℃が好適である。前記加熱温度は、エンボス加工に用いるエンボスロールの表面温度を測定して得られる値である。
 本開示の製造方法により得られる本開示の表皮材は最表面に、耐摩耗性と柔軟性が良好な表皮層、又は、感触が良好な表面処理層を有することから、複雑な形状の成型体の表皮材であって、耐摩耗性などの耐久性に優れた用途に好適に使用される。
 本開示の合成樹脂表皮材は、既述の本開示の製造方法に代表される簡易な方法で形成され、外観、耐久性に優れ、柔軟である。このため、本開示の合成樹脂表皮材は、自動車用内装材、鉄道車輌・航空機内装部品、家具、靴・履物・鞄、建装用内外装部材、衣類表装材・裏地、など種々の分野に好適に使用しうる。
 以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに制限されるものではない。
〔実施例1〕
 塩化ビニル樹脂表皮層形成用組成物に含まれる樹脂としては、平均重合度2800のポリ塩化ビニル(大洋塩ビ(株):TH-2800)を用いた。
(表皮層形成用組成物)
・ポリ塩化ビニル樹脂(平均重合度2800)      100質量部
・シリコーン/アクリル共重合体              3質量部
 〔シロキサン構造単位:アクリル系モノマー由来の構造単位の共重合比=70:30~75:25の範囲内〕
・可塑剤(フタル酸ジアルキル)             85質量部
・安定剤(Ba-Zn系複合安定剤)            2質量部
・充填剤(重炭酸カルシウム)              20質量部
・着色剤(顔料:日弘ビックス(株):GB-91)      5質量部
(発泡樹脂層形成用組成物)
・ポリ塩化ビニル樹脂(大洋塩ビ(株):TH-1300:
  平均重合度1300)               100質量部
・発泡剤(ADCA)                   6質量部
・可塑剤(フタル酸ジアルキル)             75質量部
・安定剤(Ba-Zn系複合安定剤)            4質量部
・充填剤(重炭酸カルシウム)              15質量部
・着色剤(顔料:日弘ビックス(株):GB-91)      2質量部
 カレンダー装置にて、上記各組成物を用いて表皮層と発泡樹脂層形成用組成物層とが積層された積層体を形成する。積層体における表皮層の厚みは250μmであり、発泡樹脂層形成用組成物層(発泡前)の厚みは500μmであった。
 得られた積層体の発泡樹脂層形成用組成物側表面に接着剤(ウレタン系エマルジョン接着剤)を約15g/m塗布し、基布を貼り合せた。
 基布として、メリヤス編みを改良した編物(繊維:ポリエステル、太さ:300デニール、目付:155g/m、厚み:0.55mm)を使用した。
 その後、基布と貼り合わせた積層体の表皮層表面に、触感向上のため、下記処方の表面処理層形成用組成物をグラビアプリントにて塗布し、乾燥させて、厚み2μmの表面処理層を形成した。
(表面処理層形成用組成物)
・ポリウレタン樹脂組成物               100質量部
・溶剤(メチルエチルケトン:MEK)         900質量部
 表面処理層を形成した後、得られた積層体を温度条件190℃~230℃の加熱炉内を通過させることで、発泡剤を発泡させ、気泡が内在する発泡樹脂層を形成した。
 発泡樹脂層が形成された積層体の表面処理層側の面に、絞形状が彫刻されているエンボスロールを、表面を130℃に加熱しながら押し当ててエンボス加工を行い、表面に絞模様が形成された、図2に示す構成の実施例1の合成樹脂表皮材を得た。
〔実施例2〕
 実施例1で用いた重合度2800の塩化ビニル樹脂100質量部に対するシリコーン/アクリル共重合体の含有量を表1に記載の量(10質量部)に代えた以外は、実施例1と同様にして、実施例2の表皮材を得た。
〔実施例3〕
 実施例1で用いた重合度2800の塩化ビニル樹脂に代えて重合度1700の塩化ビニル樹脂(大洋塩ビ(株):TH-1700)を用い、且つ、シリコーン/アクリル共重合体の含有量を表1に記載の量(10質量部)に代えた以外は、実施例1と同様にして、実施例3の表皮材を得た。
〔実施例4〕
 実施例1で用いた重合度2800の塩化ビニル樹脂100質量部に対するシリコーン/アクリル共重合体の含有量を表1に記載の量(20質量部)に代えた以外は、実施例1と同様にして、実施例4の表皮材を得た。
〔比較例1〕
 実施例1で用いた重合度2800の塩化ビニル樹脂に代えて重合度1000の塩化ビニル樹脂を用いた以外は、実施例1と同様にして、比較例1の表皮材を得た。
〔比較例2〕
 実施例1で用いた重合度2800の塩化ビニル樹脂を用い、シリコーン/アクリル共重合体を含有しなかった以外は、実施例1と同様にして、比較例2の表皮材を得た。
〔比較例3〕
 実施例1で用いた重合度2800の塩化ビニル樹脂を用い、シリコーン/アクリル共重合体の塩化ビニル樹脂100質量部に対する含有量を2質量部とした以外は、実施例1と同様にして、比較例3の表皮材を得た。
〔比較例4〕
 実施例1で用いた重合度2800の塩化ビニル樹脂に代えて重合度1300の塩化ビニル樹脂を用い、シリコーン/アクリル共重合体を含有しなかった以外は、実施例1と同様にして、基布上に接着剤層、発泡樹脂層、表皮層を、この順に形成した。さらに、表皮層の表面に耐摩耗性を付与する層である架橋ポリウレタン耐摩耗性層を膜厚8μmとなるように形成し、耐摩耗性層上に、さらに表面処理層を厚み2μmとなるように形成し、比較例4の表皮材を得た。
〔合成樹脂表皮材の評価〕
 得られた実施例及び比較例の各合成樹脂表皮材を以下の基準にて評価した。結果を下記表1に示す。
-耐摩耗性:平面摩耗性試験-
 JASO M 403/88/シート表皮用布材料の平面摩耗試験機(B法)を参考に試験を行った。
 以下のように、試験条件をJASO法の条件よりも厳しい条件で行った。
(試験条件)
 JASO法における標準の条件→本試験の条件
 押圧荷重:9.81N    →19.6N
 試験回数:10,000回  →40,000回
 平面摩耗性試験後に、合成樹脂表皮材試験サンプルの中央部を目視で観察し、以下の判定基準で評価した。
(判定基準)
 判定基準は以下に示す通りである。下記評価結果のうち、等級5~等級3が実用上問題のないレベルである。
等級 判定基準
5  表皮層に形成された絞模様が消失しない
4  表皮層に形成された絞模様の一部が消失するが、表皮層の下層に位置する発泡樹脂層は露出しない
3  表皮層に形成された絞模様が消失するが、表皮層の下層に位置する発泡樹脂層は露出しない
2  表皮層の絞模様が消失し、且つ、表皮層の下層に位置する発泡樹脂層の一部が露出する
1  試験回数未満で表皮層の絞模様が消失し、且つ、表皮層の下層に位置する発泡樹脂層全体が露出する
-外観評価-
 得られた合成樹脂表皮材試験サンプルを目視により観察し、表皮材表面の白ボケの有無及び白ボケ発生領域の広さを以下の基準で評価した。以下の基準で「表面の広い領域」とは、合成樹脂表皮材における観察対象表面の「全面積における50%以上の領域」を示す。
(判定基準)
 判定基準は以下に示す通りである。下記評価結果のうち、等級5及び等級4が実用上問題のないレベルである。
等級 判定基準
5  白ボケは、全く認められない
4  白ボケが、表面の一部の領域にわずかに認められる
3  白ボケが、表面の一部の領域に明らかに認められる
2  白ボケが、表面の広い領域に亘り明らかに認められる
1  表面の広い領域に亘り白ボケが著しい
-総合評価-
S  耐摩耗性及び外観評価のいずれもが等級4以上
A  耐摩耗性評価が等級3以上であり、且つ、外観評価が等級4以上であるか、又は、外観評価が等級3以上であり、耐摩耗性評価が等級4以上
B  耐摩耗性及び外観評価の少なくとも一方が等級2以下
Figure JPOXMLDOC01-appb-T000002
 表1の結果より、実施例1~実施例4の合成樹脂表皮材は、厳しい条件の耐摩耗性試験においても、実用上問題のないレベルの耐摩耗性を示し、外観評価においても白ボケは認められなかった。このことから、実施例の合成樹脂表皮材は、いずれも耐摩耗性と良好な外観が両立され、複雑な凹凸を有する成型体に好適に使用しうることがわかる。また、実施例1~実施例4の合成樹脂表皮材は表面処理層を有するが、表面処理層が薄層であり、白ボケの発生が認められず、表皮層の外観を損なわないため、意匠の自由度が高いことが期待できる。
 他方、シリコーン/アクリル共重合体を含有しても、塩化ビニル樹脂の重合度が低い比較例1では、十分な耐摩耗性が得られなかった。重合度がより高い塩化ビニル樹脂を用いても、シリコーン/アクリル共重合体を含有しないか、又は含有量が少ない比較例2及び比較例3では、十分な耐摩耗性が得られなかった。耐摩耗性向上を目的として、架橋構造を有する厚み8μmの架橋ポリウレタン耐摩耗性層を形成した比較例4では、耐摩耗性は向上したが、耐摩耗性層に起因して白ボケが発生し、外観は実用上問題となるレベルであった。
〔符号の説明〕
 10、22   合成樹脂表皮材
 14      基布
 12      塩化ビニル樹脂表皮層(表皮層)
 16      表面処理層
 18      発泡樹脂層
 20      接着剤層
 30      従来の合成樹脂表皮材
 32      従来の合成樹脂表皮材の表皮層
 2019年1月16日に出願された日本国特許出願2019-005477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。

Claims (9)

  1.  基布、及び、
     基布上に形成され、重合度が1600~3000の塩化ビニル樹脂と、前記塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層を有する合成樹脂表皮材。
  2.  前記塩化ビニル樹脂表皮層の、基布側とは反対側の面に、架橋構造を含む耐摩耗性層を有さない請求項1に記載の合成樹脂表皮材。
  3.  前記基布と前記塩化ビニル樹脂表皮層との間に、接着剤層の少なくとも1層を有する請求項1又は請求項2に記載の合成樹脂表皮材。
  4.  前記基布と前記塩化ビニル樹脂表皮層との間に、発泡樹脂層を有する請求項1~請求項3のいずれか1項に記載の合成樹脂表皮材。
  5.  前記基布と前記塩化ビニル樹脂表皮層との間に、前記基布側から接着剤層及び発泡樹脂層をこの順に有する、請求項1又は請求項2に記載の合成樹脂表皮材。
  6.  前記発泡樹脂層は、塩化ビニル樹脂を含む請求項4又は請求項5に記載の合成樹脂表皮材。
  7.  重合度が1600~3000の塩化ビニル樹脂と、前記塩化ビニル樹脂100質量部に対し、3質量部~20質量部のシリコーン/アクリル共重合体と、を含む塩化ビニル樹脂表皮層形成用組成物を用いて、塩化ビニル樹脂表皮層を形成する工程と、
     前記塩化ビニル樹脂表皮層の片面に、基布を接着する工程と、
     を有する合成樹脂表皮材の製造方法。
  8.  さらに、前記塩化ビニル樹脂表皮層の、基布と接着させる側に、発泡剤と樹脂とを含有する発泡樹脂層形成用組成物層を形成し、前記塩化ビニル樹脂表皮層と発泡樹脂層形成用組成物層との積層体を形成する工程と、
     加熱により、前記発泡樹脂層形成用組成物中の発泡剤を発泡させ、発泡樹脂層を形成する工程と、を有する請求項7に記載の合成樹脂表皮材の製造方法。
  9.  前記基布を接着する工程が、前記発泡樹脂層形成用組成物層と基布との間に接着剤層を設ける工程を含む、請求項8に記載の合成樹脂表皮材の製造方法。
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