WO2023127223A1 - Synthetic leather - Google Patents
Synthetic leather Download PDFInfo
- Publication number
- WO2023127223A1 WO2023127223A1 PCT/JP2022/037430 JP2022037430W WO2023127223A1 WO 2023127223 A1 WO2023127223 A1 WO 2023127223A1 JP 2022037430 W JP2022037430 W JP 2022037430W WO 2023127223 A1 WO2023127223 A1 WO 2023127223A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- plasticizer
- mass
- resin
- synthetic leather
- Prior art date
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 70
- 239000004014 plasticizer Substances 0.000 claims abstract description 137
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- 239000011347 resin Substances 0.000 claims abstract description 103
- 229920000728 polyester Polymers 0.000 claims abstract description 87
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- 229920005749 polyurethane resin Polymers 0.000 claims description 39
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 32
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- 239000012790 adhesive layer Substances 0.000 claims description 19
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- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 3
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- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
Definitions
- the present invention relates to synthetic leather.
- synthetic leathers that have a film whose main component is vinyl chloride resin have high flexibility such as flexibility and flexibility, as well as strength.
- the strength includes, for example, wear resistance against repeated rubbing.
- Synthetic leather is used in various fields such as vehicle interior material applications such as vehicle seats and door linings, interior material applications such as furniture and chairs, and fashion applications such as bags and shoes. These applications require a high degree of durability because they are placed under severe conditions of use.
- vehicle interior material applications such as vehicle seats and door linings
- interior material applications such as furniture and chairs
- fashion applications such as bags and shoes.
- Patent Document 1 a surface treatment agent obtained by cross-linking a mixture of polycarbonate urethane and ester urethane with a carbodiimide group-containing cross-linking agent is applied to the surface side of a film containing vinyl chloride resin as a main component. Forming a treated layer is described.
- Patent Document 1 by forming the surface treatment layer, in addition to high flexibility and good strength, abrasion resistance against repeated rubbing phenomena and chemical resistance against contact with the human body are obtained. It is described that the property (resistance to oleic acid) can be improved.
- the synthetic resin leather of Patent Document 1 has good chemical resistance (oleic acid resistance), but higher oil resistance is required.
- synthetic leather is required to have a structure that is easy to make, that is, workability (or manufacturability) from the viewpoint of cost reduction and ensuring a certain level of quality.
- the present invention has been made in view of such circumstances, and its purpose is to provide a synthetic leather with excellent oil resistance and workability.
- the synthetic leather according to the embodiment of the present invention includes a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer in this order.
- a fibrous base material a foamed layer containing a vinyl chloride resin and a plasticizer
- a non-foamed layer containing a vinyl chloride resin and a plasticizer in this order.
- the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin
- the plasticizer is a phthalate plasticizer.
- a polyester-based plasticizer is included, and the mass ratio of the phthalate-based plasticizer and the polyester-based plasticizer is 73:27 to 87:13.
- synthetic leather with excellent oil resistance and workability can be provided.
- the synthetic leather according to this embodiment has a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer.
- the foamed layer and the non-foamed layer contain 60 to 100 parts by mass of plasticizer with respect to 100 parts by mass of vinyl chloride resin.
- the plasticizers used in the foaming layer and the non-foaming layer are a phthalate plasticizer and a polyester plasticizer, and the mass ratio of the phthalate plasticizer and the polyester plasticizer is 73:27 to 87: 13.
- FIG. 1 schematically shows the cross-sectional structure of synthetic leather 1 according to one embodiment.
- this synthetic leather 1 a foam layer 3 and a non-foam layer 4 are laminated in this order on one side of a fibrous base material 2. As shown in FIG.
- FIG. 2 schematically shows a cross-sectional structure of synthetic leather 10 according to another embodiment.
- the foam layer 3 is provided on the fibrous base material 2 via the adhesive layer 5, and the protective layer 6 is provided on the non-foam layer 4.
- Synthetic leather 1 is different. Therefore, in the example of FIG. 2, the adhesive layer 5, the foam layer 3, the non-foam layer 4, and the protective layer 6 are laminated in this order on one surface of the fibrous base material 2. As shown in FIG.
- FIG. 3 schematically shows a cross-sectional structure of synthetic leather 100 according to another embodiment.
- This synthetic leather 100 differs from the synthetic leather 10 of FIG. 2 in that a protective layer 6 is provided on the non-foamed layer 4 via an undercoat layer 7 . Therefore, in the example of FIG. 3, the adhesive layer 5, the foam layer 3, the non-foam layer 4, the undercoat layer 7, and the protective layer 6 are laminated in this order on one surface of the fibrous base material 2.
- the front surface of the synthetic leather is provided with unevenness such as a grain pattern in consideration of the design, but it may be flat.
- the front surface of the synthetic leather refers to the surface (design surface) of the front and back surfaces of the synthetic leather that is visible during use.
- the front surface is the surface of the non-foamed layer or protective layer.
- the fibrous base material is not particularly limited, and for example, fiber fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics, natural leather (including split leather), and the like can be used.
- the fiber fabric one obtained by applying or impregnating a conventionally known solvent-based or solvent-free polymer compound and then dry-coagulating or wet-coagulating it may be used.
- the solventless systems referred to herein include aqueous systems.
- examples of the polymer compound include polyurethane resins and vinyl chloride resins.
- knitted fabrics are preferable as the fibrous base material, and circular knitted fabrics are more preferable, from the viewpoint of leather-like properties (specifically, the texture, thickness, and texture of natural leather), strength, and elongation properties. preferable.
- the type of fiber in the fiber fabric is not particularly limited, and conventionally known fibers such as natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers can be mentioned. good.
- synthetic fibers are preferable, and polyester fibers are more preferable, from the viewpoint of strength and workability.
- the shape of the fibers is also not particularly limited, and may be either long fibers or short fibers.
- the form of the yarn constituting the fibrous base material may be short fiber yarn such as spun yarn, long fiber yarn such as multifilament yarn or monofilament yarn, or long and short composite spun yarn combining long fibers and short fibers. good. From the viewpoint that flexibility can be imparted to the fibrous base material to be obtained, short fibers that have been pre-crimped may be used as the yarn, and the yarn is subjected to false twisting, fluid agitation treatment, or the like. It may be processed.
- the fibrous base material may be colored with dyes or pigments.
- the synthetic leather according to this embodiment includes a foam layer and a non-foam layer as resin layers containing a vinyl chloride resin and a plasticizer.
- the foam layer is a resin layer having cells, and may be a porous layer.
- the non-foamed layer is a resin layer having no air bubbles, unlike the foamed layer.
- the non-foamed layer is a resin layer laminated on the surface of the foamed layer, and is also called a skin layer.
- the vinyl chloride resin that constitutes the non-foamed layer is a polymer composed of vinyl chloride and/or vinylidene chloride as a monomer component.
- the vinyl chloride resin is not particularly limited, and conventionally known vinyl chloride resins can be used. Examples thereof include vinyl chloride resin and/or vinylidene chloride resin.
- vinyl chloride resins include polyvinyl chloride, which is a homopolymer of vinyl chloride, and copolymers of vinyl chloride and other monomers.
- Vinylidene chloride resins include, for example, polyvinylidene chloride, which is a homopolymer of vinylidene chloride, and copolymers of vinylidene chloride with other monomers.
- vinyl chloride or vinylidene chloride examples include, for example, vinyl acetate, ethylene, propylene, styrene, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, maleic acid, maleic acid, Examples include acid esters and higher vinyl ethers, and vinyl chloride and vinylidene chloride may be copolymerized.
- the resin component constituting the non-foamed layer is mainly composed of vinyl chloride resin. Specifically, it is preferable that more than 50% by mass of the resin component is a vinyl chloride resin, more preferably 80% by mass or more of the resin component is a vinyl chloride resin, and 100% by mass of the resin component is a vinyl chloride resin. Resin may be used.
- the resin component refers to a polymer component, excluding additives such as plasticizers and heat stabilizers, among the components constituting the resin layer.
- the non-foaming layer contains a phthalate plasticizer and a polyester plasticizer as plasticizers.
- a phthalate plasticizer and the polyester plasticizer together, the viscosity of the resin composition liquid for the non-foaming layer can be kept low. Therefore, it is possible to suppress the generation of bubbles and processing streaks, and to form a uniform coating. Therefore, the workability, particularly the workability of the casting method, is improved.
- the processing streak refers to a streak-like defect that occurs along the application direction when the resin composition liquid is applied.
- a polyester plasticizer has a larger molecular weight than other plasticizers.
- the diffusion rate of the plasticizer is reduced, and the plasticizer is less likely to migrate from the inside of the non-foamed layer to the outside of the non-foamed layer. Therefore, the oil resistance of the obtained synthetic leather can be improved.
- a phthalate plasticizer is a phthalate that acts as a plasticizer for vinyl chloride resin.
- phthalate plasticizers include dibutyl phthalate (DBP), dioctyl phthalate (DOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), diundecyl phthalate (DUP), benzylbutyl phthalate (BBP), nonylundecyl phthalate (NUP), dialkyl phthalate (C9-C11), and the like. These can be used individually by 1 type or in combination of 2 or more types. Since these are esters of phthalic acid and monohydric alcohol, the phthalate-based polyester as a polyester-based plasticizer described later is not included in the phthalate-based plasticizer.
- the phthalate ester plasticizer is preferably a dialkyl phthalate, which is an ester of phthalic acid and at least one monohydric alcohol selected from the group consisting of alcohols having 4 to 20 carbon atoms.
- dialkyl phthalate (C9 to C11) is preferable from the viewpoint of bleeding resistance, cold resistance and heat resistance.
- the dialkyl phthalate (C9-C11) is an ester of a mixture of alcohols having 9-11 carbon atoms and phthalic acid.
- a polyester plasticizer is a polyester that acts as a plasticizer for vinyl chloride resin.
- Polyester plasticizers include those obtained by polycondensation of dicarboxylic acids and dihydric alcohols, such as adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters. These can be used individually by 1 type or in combination of 2 or more types.
- Dihydric alcohols include, for example, ethylene glycol, propylene glycol, butanediol (eg 1,3-butanediol, 1,4-butanediol), and hexanediol (eg 1,6-hexanediol). These can be used individually by 1 type or in combination of 2 or more types.
- adipic acid-based polyester is preferable from the viewpoint of versatility.
- the number average molecular weight (Mn) of the polyester plasticizer is not particularly limited, and is preferably 500-2500, more preferably 1200-2000. When the number average molecular weight is 2500 or less, the viscosity of the resin composition liquid for the non-foaming layer can be kept low, and the processability, particularly the processability of the casting method, can be further improved. When the number average molecular weight is 500 or more, good oil resistance can be obtained.
- the number average molecular weight of the polyester plasticizer is calculated as a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.
- the viscosity of the polyester plasticizer is not particularly limited, and is preferably 150 to 5000 mPa ⁇ s, more preferably 2000 to 5000 mPa ⁇ s.
- the viscosity is 150 mPa ⁇ s or more, the resulting synthetic leather has good oil resistance.
- the viscosity is 5000 mPa ⁇ s or less, the viscosity of the resin composition liquid for the non-foaming layer can be kept low, and the processability, particularly the processability of the casting method, can be further improved.
- the viscosity of the polyester plasticizer is the viscosity at 25 ° C.
- Brookfield viscometer and more specifically, a BII viscometer (BHII type, manufactured by Toki Sangyo Co., Ltd., rotor No. 3) at 10 rpm and a liquid temperature of 25°C.
- the blending ratio of the phthalate plasticizer is 73% by mass or more (that is, the blending ratio of the polyester plasticizer is 27% by mass or less)
- the viscosity of the resin composition liquid for the non-foaming layer can be kept low.
- the workability, especially the workability by the casting method is improved.
- Good oil resistance is obtained when the blending ratio of the phthalate plasticizer is 87% by mass or less (that is, the blending ratio of the polyester plasticizer is 13% by mass or more).
- the mass ratio of the phthalate ester plasticizer and the polyester plasticizer is obtained by rounding off the decimal point when the ratio of each has a fraction after the decimal point when the total of both is 100. It is an integer ratio.
- solid content refers to components other than volatile substances such as organic solvents and water, and is also referred to as evaporation residue or non-volatile content. Therefore, liquids that do not evaporate at ordinary drying temperatures, such as plasticizers, are also included in the solid content.
- the content of the plasticizer in the non-foaming layer (the total content of the phthalate plasticizer and the polyester plasticizer) is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, preferably 65 to 85 parts by mass.
- the amount of the plasticizer is 60 parts by mass or more, a soft texture can be obtained.
- the viscosity of the resin composition liquid for the non-foaming layer can be kept low, and the processability, particularly the processability by the casting method, is improved.
- the amount of the plasticizer is 100 parts by mass or less, the strength can be improved. Moreover, since the bleeding of the plasticizer can be suppressed, the designability can be improved.
- the non-foaming layer can contain conventionally known additives as needed within a range that does not impair its physical properties.
- additives include plasticizers other than phthalate plasticizers and polyester plasticizers, thermoplastic resins and thermosetting resins other than vinyl chloride resins, heat stabilizers, fillers, pigments, Amine-resistant agents, flame retardants, conductivity-imparting agents, antistatic agents, ultraviolet absorbers, light stabilizers, antioxidants, pigment dispersants, cross-linking agents, thickeners, etc., may be used alone or in combination of two. The above can be used in combination.
- heat stabilizer examples include metal soaps such as calcium stearate, magnesium stearate, aluminum stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, and zinc laurate; sodium phenol and/or naphthol; Salts, metal salts such as zinc salts and barium salts, organotin compounds such as dibutyltin dilaurate and dibutyltin dimalate, and phosphites such as triphenylphosphite, tricresylphosphite and triisooctylphosphite. be done. These can be used individually by 1 type or in combination of 2 or more types.
- an organic acid calcium salt and/or an organic acid zinc salt may be used as a thermal stabilizer.
- the content of the heat stabilizer is not particularly limited, and may be, for example, 0.1 to 10 parts by mass or 0.5 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- amine-resistant agents examples include perchlorates such as sodium perchlorate and potassium perchlorate. These can be used individually by 1 type or in combination of 2 or more types.
- the content of the amine-resistant agent is not particularly limited, and may be, for example, 0.05 to 5 parts by mass or 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- the thickness of the non-foamed layer is not particularly limited, it is preferably 100-300 ⁇ m, more preferably 130-250 ⁇ m. Good strength is obtained when the thickness of the non-foamed layer is 100 ⁇ m or more. When the thickness of the non-foamed layer is 300 ⁇ m or less, the thickness of the non-foamed layer of the obtained synthetic leather can be made uniform.
- the vinyl chloride resin that constitutes the foam layer is a polymer composed of vinyl chloride and/or vinylidene chloride as a monomer component.
- the vinyl chloride-based resin is not particularly limited, and the same vinyl chloride-based resin as that used for the non-foamed layer can be used, so the description thereof is omitted.
- the vinyl chloride resin contained in the foam layer and the vinyl chloride resin contained in the non-foam layer may be the same or different.
- the resin component constituting the foam layer is mainly composed of vinyl chloride resin. Specifically, it is preferable that more than 50% by mass of the resin component is a vinyl chloride resin, more preferably 80% by mass or more of the resin component is a vinyl chloride resin, and 100% by mass of the resin component is a vinyl chloride resin. Resin may be used.
- the foam layer contains a phthalate plasticizer and a polyester plasticizer as plasticizers.
- a phthalate plasticizer and a polyester plasticizer in combination, the viscosity of the resin composition liquid for the foam layer can be kept low. Therefore, it is possible to suppress the generation of bubbles and processing streaks, and to form a uniform coating. Therefore, the workability, particularly the workability of the casting method, is improved.
- a polyester plasticizer has a larger molecular weight than other plasticizers. Therefore, by using a polyester-based plasticizer, the diffusion speed of the plasticizer to other resin layers is reduced, and the plasticizer is less likely to migrate from the inside of the foam layer to the outside of the foam layer. Therefore, good oil resistance is obtained.
- the phthalate ester plasticizer and polyester plasticizer in the foam layer are not particularly limited, and the same phthalate ester plasticizer and polyester plasticizer as in the non-foam layer can be used. Therefore, dialkyl phthalate (C9-C11) is preferable as the phthalate plasticizer, adipic acid polyester is preferable as the polyester plasticizer, and the number average molecular weight of the polyester plasticizer is preferably 500 to 2500 (more It is preferably 1200 to 2000), and the viscosity of the polyester plasticizer is preferably 150 to 5000 mPa s (more preferably 2000 to 5000 mPa s). .
- the phthalate ester plasticizer and polyester plasticizer contained in the foam layer and the phthalate ester plasticizer and polyester plasticizer contained in the non-foam layer may be the same or different.
- the blending ratio of the phthalate plasticizer is 73% by mass or more (that is, the blending ratio of the polyester plasticizer is 27% by mass or less)
- the viscosity of the resin composition liquid for the foam layer can be kept low. Workability, especially workability by casting method, is improved.
- the mass ratio of the phthalate-based plasticizer and the polyester-based plasticizer may be the same or different between the foaming layer and the non-foaming layer.
- the content of the plasticizer in the foam layer (the total content of the phthalate plasticizer and the polyester plasticizer) is 60 to 100 parts by mass, preferably 65 parts by mass, based on 100 parts by mass of the vinyl chloride resin. ⁇ 85 parts by mass.
- the blending amount of the plasticizer is 60 parts by mass or more, a soft texture can be obtained.
- the viscosity of the resin composition liquid for the foam layer can be kept low, and workability, particularly workability by a casting method, is improved.
- the amount of the plasticizer By setting the amount of the plasticizer to be 100 parts by mass or less, the strength can be improved. Moreover, since the bleeding of the plasticizer can be suppressed, the designability can be improved.
- the content of the plasticizer may be the same or different between the foamed layer and the non-foamed layer.
- the foam layer can be formed, for example, by adding a foaming agent to the resin composition liquid for the foam layer, and can improve the tactile feel and texture.
- the foaming agent is not particularly limited, and any known foaming agent can be used. From the viewpoint of foamability, it is preferable to use an organic foaming agent.
- organic blowing agents include azodicarbonamide (ADCA), 2,2′-azodiisobutyronitrile (AIBN), benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 4,4′-oxybis[benzenesulfonylhydrazide]. (OBSH), N,N'-dinitrosopentamethylenetetramine (DPT) and the like. These can be used individually by 1 type or in combination of 2 or more types.
- the expansion ratio of the foamed layer is not particularly limited, but is preferably 2 times or less, more preferably 1.1 times or more and 2 times or less, and still more preferably 1.2 times or more and 1.7 times or less. .
- the expansion ratio of the foam layer is 2 or less, independent pores are easily formed, and wear resistance, flex resistance, and peel strength can be improved.
- the thickness of the foam layer is not particularly limited, and may be, for example, 150 to 370 ⁇ m, preferably 190 to 370 ⁇ m, more preferably 200 to 300 ⁇ m.
- the foam layer has a thickness of 190 ⁇ m or more, a soft texture can be obtained.
- the thickness of the foam layer is 370 ⁇ m or less, it is easy to adjust the diameter of the foam cells.
- additives can be blended into the foam layer as needed within a range that does not impair its physical properties.
- additives include plasticizers other than phthalate plasticizers and polyester plasticizers, thermoplastic resins and thermosetting resins other than vinyl chloride resins, heat stabilizers, fillers, pigments, Amine-resistant agents, flame retardants, conductivity-imparting agents, antistatic agents, ultraviolet absorbers, light stabilizers, antioxidants, pigment dispersants, cross-linking agents, thickeners, etc., may be used alone or in combination of two. The above can be used in combination. Specific examples and contents of the heat stabilizer and the amine-resistant agent in the foam layer are the same as those of the non-foam layer described above.
- an adhesive layer may be interposed between the foam layer and the fibrous base material, or the foam layer may be directly laminated on the fibrous base material.
- the adhesive layer may be a non-foamed resin layer having no air bubbles.
- the resin that constitutes the adhesive layer is not particularly limited, and resins commonly used for ordinary vinyl chloride leather can be used. Examples thereof include polyurethane resins and vinyl chloride resins.
- the thickness of the adhesive layer is not particularly limited, and may be, for example, 20-200 ⁇ m or 50-150 ⁇ m.
- a protective layer may be further provided on the non-foamed layer.
- the protective layer preferably contains polyurethane resin.
- the polyurethane resin for the protective layer is not particularly limited, and examples thereof include polyether-based polyurethane resins, polyester-based polyurethane resins, and polycarbonate-based polyurethane resins. These polyurethane resins can be used singly or in combination of two or more. Among them, polycarbonate-based polyurethane resin is preferable as the polyurethane resin for the protective layer from the viewpoint of abrasion resistance.
- the form of the polyurethane resin for the protective layer is not particularly limited, and may be appropriately selected according to the application.
- it may be solvent-based or water-based, and may be one-component or two-component curable.
- the form of the polyurethane resin is preferably water-based.
- the protective layer resin composition liquid used to form the protective layer can optionally contain optional components within a range that does not impair the physical properties of the polyurethane resin.
- optional components include cross-linking agents, lubricants, leveling agents, thickeners, antifoaming agents, light stabilizers, conductivity imparting agents, antistatic agents, water repellent agents, oil repellent agents, antiblocking agents, antibacterial agents, and the like. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
- the thickness of the protective layer is not particularly limited, and is preferably 2 to 30 ⁇ m, more preferably 5 to 20 ⁇ m, for example. Abrasion resistance can be improved if the thickness is 2 ⁇ m or more. If the thickness is 30 ⁇ m or less, a soft texture can be obtained.
- an undercoat layer when providing the protective layer, an undercoat layer may be interposed between the protective layer and the non-foamed layer, or the protective layer may be laminated directly on the non-foamed layer.
- the undercoat layer preferably contains a polyurethane resin.
- the polyurethane resin for such an undercoat layer is not particularly limited, and examples thereof include polyether-based polyurethane resins, polyester-based polyurethane resins, and polycarbonate-based polyurethane resins. These polyurethane resins can be used singly or in combination of two or more. Among them, polyester-based polyurethane resins are preferable as the polyurethane resin for the undercoat layer from the viewpoint of heat resistance to yellowing and oil resistance.
- the form of the polyurethane resin for the undercoat layer is not particularly limited, and may be appropriately selected according to the application.
- it may be solvent-based or water-based, and may be one-component or two-component curable.
- the polyurethane resin is preferably water-based.
- the undercoat layer resin composition liquid used to form the undercoat layer may optionally contain optional components within a range that does not impair the physical properties of the polyurethane resin.
- optional components include resins other than polyurethane resins (for example, acrylic resins), cross-linking agents, leveling agents, antifoaming agents, and thickening agents. These can be used individually by 1 type or in combination of 2 or more types.
- the thickness of the undercoat layer is not particularly limited, and may be, for example, 1 to 20 ⁇ m or 2 to 10 ⁇ m.
- the manufacturing method is not particularly limited, and the same manufacturing method as that for conventionally known synthetic leather can be employed, and examples thereof include a calendering method and a casting method.
- the synthetic leather of the embodiment can be manufactured by performing the following steps in order.
- the production method is (1) a step of applying a non-foaming layer resin composition liquid onto a release substrate to form a non-foaming layer; (2) a step of applying a foamed layer resin composition liquid onto the non-foamed layer to form a foamed layer; (3) a step of laminating the foam layer and the fibrous base material, and (4) a step of peeling off the releasable substrate; includes.
- a method for applying the resin composition liquid for the non-foaming layer onto the releasable base material conventionally known various methods can be employed, and there is no particular limitation. Examples thereof include methods using a knife coater, comma coater, roll coater, die coater, and the like. Among them, application by a knife coater or a comma coater is preferable in that a uniform thin film layer can be formed.
- the releasable base material is not particularly limited as long as it has releasability with respect to vinyl chloride resin or a base material that has undergone a releasable treatment.
- examples thereof include release paper, release-treated cloth, water-repellent treated cloth, olefin sheet or film made of polyethylene resin or polypropylene resin, fluororesin sheet or film, and plastic film with release paper.
- the release substrate may have an uneven pattern, and by using such a release substrate, an uneven pattern such as a textured pattern is formed on the surface of the synthetic leather to impart a design property. can be done.
- the resin composition liquid for foaming layer is applied onto the non-foaming layer.
- a method for applying the resin composition liquid for the foaming layer the same method as the method for applying the resin composition liquid for the non-foaming layer can be adopted.
- Lamination methods include, for example, conventionally known methods such as a transfer method, heat fusion bonding, thermocompression bonding, and adhesion using an adhesive.
- a fibrous base material may be laminated after the adhesive layer resin composition liquid is applied onto the foam layer.
- a method of applying the adhesive layer resin composition liquid the same method as the method of applying the non-foaming layer resin composition liquid can be employed.
- the release base material is peeled off from the non-foamed layer.
- a laminate of the non-foamed layer, the foamed layer, and the fibrous base is obtained by peeling off the releasable base.
- the protective layer When the protective layer is formed on the non-foamed layer, the protective layer may be formed on the surface of the laminate after the release substrate is peeled off as described above.
- the protective layer may be provided on the non-foamed layer via an undercoat layer, or may be laminated directly on the non-foamed layer.
- the method for applying the resin composition liquid for the undercoat layer to the surface of the non-foaming layer is not particularly limited, and the same method as the method for applying the resin composition liquid for the non-foaming layer can be used.
- the same method as the method for applying the non-foaming layer resin composition liquid can be employed.
- a coating method using a device such as a spray coater, a gravure coater, a gravure direct printer, a gravure offset printer, or a screen printer can also be employed.
- heat treatment is performed if necessary.
- the heat treatment is performed to evaporate the solvent in the protective layer resin composition liquid and dry the resin.
- the heat treatment is performed to promote the reaction and form a film having sufficient strength. .
- the non-foamed layer (protective layer if a protective layer is formed) is formed with an uneven pattern such as a embossed pattern.
- various conventionally known methods can be employed, and there is no particular limitation. Examples thereof include methods using embossing, vacuum embossing, welding, and pinsonic processing.
- a synthetic leather according to one embodiment is obtained.
- the method for producing the synthetic leather of this embodiment is not limited to the above method.
- a glass plate having a width of 150 mm, a length of 200 mm and a thickness of 3 mm was placed on 100% cotton gauze. This was left for 72 hours in a blower constant temperature dryer (“DRM620DD” manufactured by ADVANTEC) adjusted to 80°C. Thereafter, the glass plate and 100% cotton gauze were removed, and wiper paper (“Kimwipe S-200” manufactured by Nippon Paper Crecia Co., Ltd.) was pressed against the glass plate to remove excess oleic acid.
- DRM620DD blower constant temperature dryer
- wiper paper Karlwipe S-200 manufactured by Nippon Paper Crecia Co., Ltd.
- test pieces each having a width of 30 mm and a length of 120 mm were taken from the central portion of the obtained sample after the oil resistance test in the vertical direction (longitudinal direction) and the horizontal direction (width direction).
- the test pieces collected from the same direction are superimposed so that the resin layer surface faces inside, and the Scott type kneading tester (Scott rubbing resistance tester "CV-10N", manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) is gripped at intervals. Sandwiched with 30 mm. Gradually the gap between the grips was reduced so that the two specimens were separated from each other. After lightly touching the resin layer surface of the test piece, a load of 9.8 N was applied.
- a test piece having a width of 70 mm and a length of 300 mm was taken from each of the vertical and horizontal directions, and a urethane foam having a width of 70 mm, a length of 300 mm and a thickness of 10 mm was attached to the back surface.
- a wire with a diameter of 4.5 mm was installed in the center of the lower surface of the urethane foam, and it was fixed to a flat abrasion tester "T-TYPE" (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), and an abrading element covered with cotton cloth was placed on the wire.
- a wear test was performed by applying a load of 9.8 N to the friction element so that the friction element reciprocated in parallel with the wire.
- the friction element was reciprocated 10,000 times at a speed of 60 reciprocations/minute over a distance of 140 mm above the surface of the test piece.
- the surface condition of the test piece was observed and evaluated according to the following criteria. (criterion) 5: No change in appearance (no cracks or breaks) 4: Slight but inconspicuous wear 3: Clear wear 2: Exposed fibrous base material 1: Exposed fibrous base material (tears observed)
- Example 1 ⁇ Fibrous base material> A circular knitted fabric (polyester fiber, thickness 580 ⁇ m, mass per unit area 120 g/m 2 ) was prepared as a base material.
- ⁇ Prescription 1 Resin composition liquid for non-foaming layer> ⁇ Vinyl chloride resin (polyvinyl chloride, paste resin with an average degree of polymerization of 1300, solid content 100% by mass): 100 parts by mass ⁇ Phthalic acid ester plasticizer (dialkyl phthalate (C9-C11), solid content 100% by mass ): 65 parts by mass Polyester plasticizer (adipic acid polyester obtained by polycondensation of adipic acid and 1,3-butanediol and 1,4-butanediol, number average molecular weight 1800, viscosity (25°C) 3000 mPa s, solid content 100% by mass): 10 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Pigment (carbon black, solid content minute 100% by mass): 7 parts by mass Amine-resistant agent (sodium perchlorate, solid content 100% by mass): 0.5 parts by
- ⁇ Prescription 2 Resin composition liquid for foam layer> ⁇ Vinyl chloride resin (polyvinyl chloride, paste resin with an average degree of polymerization of 1300, solid content 100% by mass): 100 parts by mass ⁇ Phthalic acid ester plasticizer (dialkyl phthalate (C9-C11), solid content 100% by mass ): 65 parts by mass Polyester plasticizer (adipic acid polyester obtained by polycondensation of adipic acid and 1,3-butanediol and 1,4-butanediol, number average molecular weight 1800, viscosity (25°C) 3000 mPa s, solid content 100% by mass): 10 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Pigment (carbon black, solid content minute 100% by mass): 3 parts Amine-resistant agent (sodium perchlorate, solid content 100% by mass): 1 part Organic blowing agent (azodicarbon
- ⁇ Prescription 3 Resin composition liquid for adhesive layer> ⁇ Vinyl chloride resin (hydroxyl group-containing polyvinyl chloride resin obtained by copolymerizing a monomer having a hydroxyl group, average polymerization degree 1300, solid content 100% by mass): 100 parts by mass ⁇ Plasticizer (dialkyl phthalate (C9 to C11) , solid content 100% by mass): 100 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Flame retardant (antimony trioxide, solid content 100% by mass): 8 parts by mass Cross-linking agent (isocyanate-based cross-linking agent, solid content 100% by mass): 6.5 parts by mass Preparation method: After mixing vinyl chloride resin and plasticizer, Ca-Zn-based heat stabilization A resin composition liquid for an adhesive layer was obtained by adding and mixing an agent and a flame retardant, and then adding and mixing a cross-linking agent. The viscosity of the adhesive layer resin composition
- ⁇ Prescription 4 Resin composition liquid for undercoat layer> ⁇ Polyurethane resin (aqueous dispersion of polyester polyurethane resin, solid content 20.5% by mass): 100 parts ⁇ Crosslinking agent (aqueous dispersion of isocyanate-based crosslinker, solid content 50% by mass): 2 parts by mass Preparation method : A cross-linking agent was added to a polyurethane resin and mixed to obtain a resin composition liquid for an undercoat layer. The viscosity of the undercoat layer resin composition liquid was 3000 mPa ⁇ s (BII type viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23° C.).
- Resin composition liquid for protective layer Polyurethane resin (aqueous dispersion of polycarbonate-based polyurethane resin, solid content 30% by mass): 100 parts by mass Crosslinking agent (aqueous dispersion of carbodiimide-based cross-linking agent, solid content 49.5% by mass): 2 parts by mass Lubricant (Aqueous dispersion of silicone resin, solid content: 40 parts by mass): 6 parts by mass Preparation method: After mixing a lubricant with a polyurethane resin, a cross-linking agent was added and mixed to obtain a protective layer resin composition liquid.
- the viscosity of the protective layer resin composition liquid was 1000 mPa ⁇ s (BII viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23° C.).
- the non-foaming layer resin composition liquid prepared according to the above recipe 1 is coated on a flat release paper (trade name “VX-12”, manufactured by Lintec Corporation) with a comma coater so that the thickness is 160 ⁇ m. and heat-treated in a dryer at 180° C. for 2 minutes and 30 seconds to form a non-foaming layer.
- a flat release paper trade name “VX-12”, manufactured by Lintec Corporation
- the foamed layer resin composition liquid prepared according to Formulation 2 above is coated on the non-foamed layer formed on the release paper with a comma coater so that the coating thickness becomes 140 ⁇ m in a sheet form, and dried.
- a foam layer was formed by heat-treating at 200° C. for 2 minutes and 30 seconds using a machine.
- the adhesive layer resin composition liquid prepared according to Formulation 3 above was coated on the foam layer in a sheet form with a knife coater so that the coating thickness was 90 ⁇ m.
- the fibrous base material was superimposed and treated in a dryer at 180° C. for 2 minutes and 30 seconds to form an adhesive layer and bond with the fibrous base material.
- the release paper was peeled off to obtain a laminate composed of a non-foamed layer, a foamed layer, an adhesive layer, and a fibrous base material.
- the undercoat layer resin composition liquid prepared according to Formulation 4 above was coated on the surface of the non-foamed layer after peeling off the release paper in a sheet form with a gravure coater so that the coating thickness was 12 ⁇ m. and heat-treated at 130° C. for 2 minutes in a dryer to form an undercoat layer.
- the protective layer resin composition solution prepared according to Formulation 5 above was applied to the surface of the undercoat layer in the form of a sheet using a gravure coater so that the coating thickness was 15 ⁇ m. A heat treatment was performed for 1 minute to form a protective layer.
- a grain pattern was formed on the front surface of the protective layer with a vacuum embossing machine to obtain the synthetic leather of Example 1.
- the non-foamed layer had a thickness of 160 ⁇ m
- the foamed layer had an expansion ratio of 1.5
- the foamed layer had a thickness of 210 ⁇ m.
- each resin layer is obtained by observing the vertical cross section of the synthetic leather with a microscope (manufactured by Keyence Corporation, Digital HF Microscope VH-8000), measuring the thickness at any 10 points, and averaging these It is a value obtained by calculating the value.
- the expansion ratio of the foam layer was determined by coating the resin composition liquid for the foam layer on release paper with a comma coater in the form of a sheet to a coating thickness of 140 ⁇ m, followed by drying at 200° C. for 2 minutes and 30 seconds.
- Examples 2 to 14, Comparative Examples 1 to 6 A synthetic leather was obtained in the same manner as in Example 1, except that the formulation of the resin composition for each resin layer was changed as shown in Tables 1 to 4. "%" for the solid content in Tables 1 to 4 is mass%.
- the polyester plasticizer the viscosity and number average molecular weight of the adipic acid-based polyester in Tables 1-4 are as shown in Tables 1-4. Specifically, the adipic acid-based polyesters in Tables 1 to 4 are all obtained by polycondensing adipic acid with 1,3-butanediol and 1,4-butanediol.
- Example 7 an adipic acid-based polyester having a number average molecular weight of 800 and a viscosity (25° C.) of 200 mPa ⁇ s was used.
- Example 8 an adipic acid-based polyester having a number average molecular weight of 2,200 and a viscosity (25° C.) of 5,000 mPa ⁇ s was used.
- the adipic acid-based polyesters used in other examples and comparative examples are the same as in Example 1, as described above.
- Example 1 The evaluation results for Examples 1-14 and Comparative Examples 1-6 are shown in Tables 1-4.
- Comparative Example 1 the mass ratio of the phthalate ester plasticizer and the polyester plasticizer contained in the non-foamed layer and the foamed layer was 93:7, and the amount of the phthalate ester plasticizer was large. was inferior.
- Comparative Examples 3 to 5 the non-foamed layer and/or the foamed layer contained only the phthalate ester plasticizer, so the oil resistance was poor.
- Comparative Example 2 the mass ratio of the phthalate plasticizer and the polyester plasticizer contained in the non-foamed layer and the foamed layer was 67:33, and the content of the polyester plasticizer was large, so oil resistance was improved. Although it was excellent, foam entrapment occurred and the workability was poor.
- Comparative Example 6 the content of the plasticizer was small and the workability was poor.
- Examples 1 to 14 were excellent in oil resistance and workability.
- a synthetic leather comprising, in this order, a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer,
- the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin
- the plasticizer is a phthalate plasticizer and a polyester synthetic leather, wherein the mass ratio of the phthalate plasticizer and the polyester plasticizer is 73:27 to 87:13 (preferably 77:23 to 83:17).
- the polyester-based plasticizer in the foamed layer and the non-foamed layer is at least one selected from the group consisting of adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters, preferably adipic acid-based plasticizers.
- the phthalate ester plasticizer in the foam layer and the non-foam layer is dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, phthalate.
- the foamed layer and the non-foamed layer each further contain a heat stabilizer (preferably a calcium salt of an organic acid and/or a zinc salt of an organic acid), and preferably the content of the heat stabilizer is the vinyl chloride resin.
- the synthetic leather according to any one of [1] to [6] which is 0.1 to 10 parts by mass (preferably 0.5 to 5 parts by mass) per 100 parts by mass.
- the foamed layer and the non-foamed layer each further contain an amine-resistant agent (preferably perchlorate), and preferably the content of the amine-resistant agent is 0 with respect to 100 parts by mass of the vinyl chloride resin. 05 to 5 parts by mass (preferably 0.1 to 2 parts by mass), the synthetic leather according to any one of [1] to [7].
- an amine-resistant agent preferably perchlorate
- a protective layer containing a polyurethane resin (preferably a polycarbonate-based polyurethane resin) on the non-foamed layer.
- the protective layer has a thickness of 2 to 30 ⁇ m (preferably 5 to 20 ⁇ m).
- an undercoat layer containing a polyurethane resin preferably a polyester polyurethane resin
- the non-foamed layer is a resin layer formed by applying a non-foamed layer resin composition liquid onto a releasable substrate, and the foamed layer is formed on the releasable substrate.
- the synthetic leather according to any one of [1] to [16] which has an uneven pattern (preferably a embossed pattern) on the front side.
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Abstract
A synthetic leather according to an embodiment of the present invention comprises a fibrous substrate, a foam layer that contains a vinyl chloride resin and a plasticizer, and a non-foam layer that contains a vinyl chloride resin and a plasticizer. In the foam layer and the non-foam layer, the content of the plasticizer is 60-100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, the plasticizer contains a phthalic acid ester plasticizer and a polyester plasticizer, and the mass ratio of the phthalic acid ester plasticizer and the polyester plasticizer is 73:27 to 87:13.
Description
本発明は、合成皮革に関する。
The present invention relates to synthetic leather.
合成皮革のうち、塩化ビニル系樹脂を主成分とする皮膜を有する合成皮革は、高い屈曲性や柔軟性などの可撓性や、強度を有する。強度としては、例えば、繰り返し受ける擦れ現象に対しての耐摩耗性が挙げられる。合成皮革は、車両シート、ドア内張り等の車両内装材用途、家具、椅子等のインテリア資材用途、鞄、靴などのファッション用途等、様々な分野で用いられている。これらの用途は過酷な使用状況に置かれることから、高度な耐久性が求められている。なかでも、人体に直接又は間接的に触れる機会の多いところに用いられる合成皮革の場合、人体から分泌される皮脂や化粧品に含まれる油性成分に対する耐油性が求められる。特には、皮脂の主成分であるオレイン酸などの高級脂肪酸類に対する耐久性が強く求められている。
Among synthetic leathers, synthetic leathers that have a film whose main component is vinyl chloride resin have high flexibility such as flexibility and flexibility, as well as strength. The strength includes, for example, wear resistance against repeated rubbing. Synthetic leather is used in various fields such as vehicle interior material applications such as vehicle seats and door linings, interior material applications such as furniture and chairs, and fashion applications such as bags and shoes. These applications require a high degree of durability because they are placed under severe conditions of use. In particular, in the case of synthetic leather, which is used where there are many chances of direct or indirect contact with the human body, oil resistance against sebum secreted from the human body and oily ingredients contained in cosmetics is required. In particular, there is a strong demand for durability against higher fatty acids such as oleic acid, which is the main component of sebum.
例えば、特許文献1には、塩化ビニル樹脂を主成分とする皮膜の表面側に、ポリカーボネートウレタンとエステルウレタンの混合物をカルボジイミド基含有の架橋剤で架橋してなる表面処理剤を塗布することにより表面処理層を形成することが記載されている。特許文献1には、該表面処理層を形成することにより、高い可撓性や良好な強度に加えて、繰り返し受ける擦れ現象に対しての耐摩耗性と、人体の接触に対しての耐薬品性(耐オレイン酸性)の向上が図れることが記載されている。
For example, in Patent Document 1, a surface treatment agent obtained by cross-linking a mixture of polycarbonate urethane and ester urethane with a carbodiimide group-containing cross-linking agent is applied to the surface side of a film containing vinyl chloride resin as a main component. Forming a treated layer is described. In Patent Document 1, by forming the surface treatment layer, in addition to high flexibility and good strength, abrasion resistance against repeated rubbing phenomena and chemical resistance against contact with the human body are obtained. It is described that the property (resistance to oleic acid) can be improved.
特許文献1の合成樹脂レザーでは、耐薬品性(耐オレイン酸性)が良好であるが、より高い耐油性が求められている。
The synthetic resin leather of Patent Document 1 has good chemical resistance (oleic acid resistance), but higher oil resistance is required.
一方、低コスト化や一定の品質確保等の観点から、合成皮革には作りやすい構成を持つこと、即ち加工性(ないし製造性)が求められる。
On the other hand, synthetic leather is required to have a structure that is easy to make, that is, workability (or manufacturability) from the viewpoint of cost reduction and ensuring a certain level of quality.
本発明は、このような現状に鑑みてなされたものであり、その目的は、耐油性及び加工性に優れた合成皮革を提供することである。
The present invention has been made in view of such circumstances, and its purpose is to provide a synthetic leather with excellent oil resistance and workability.
本発明の実施形態に係る合成皮革は、繊維質基材と、塩化ビニル系樹脂と可塑剤とを含む発泡層と、塩化ビニル系樹脂と可塑剤とを含む非発泡層とを、この順で含む合成皮革である。前記発泡層及び前記非発泡層のそれぞれにおいて、前記可塑剤の含有量が前記塩化ビニル系樹脂100質量部に対して60~100質量部であり、また前記可塑剤がフタル酸エステル系可塑剤とポリエステル系可塑剤を含み、更に前記フタル酸エステル系可塑剤と前記ポリエステル系可塑剤の質量比が73:27~87:13である。
The synthetic leather according to the embodiment of the present invention includes a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer in this order. Contains synthetic leather. In each of the foamed layer and the non-foamed layer, the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the plasticizer is a phthalate plasticizer. A polyester-based plasticizer is included, and the mass ratio of the phthalate-based plasticizer and the polyester-based plasticizer is 73:27 to 87:13.
本発明の実施形態によれば、耐油性及び加工性に優れた合成皮革を提供することができる。
According to the embodiment of the present invention, synthetic leather with excellent oil resistance and workability can be provided.
本実施形態に係る合成皮革は、繊維質基材と、塩化ビニル系樹脂と可塑剤とを含む発泡層と、塩化ビニル系樹脂と可塑剤とを含む非発泡層と、を有する。発泡層及び非発泡層は、塩化ビニル系樹脂100質量部に対して可塑剤を60~100質量部含む。発泡層及び非発泡層に用いられる可塑剤は、フタル酸エステル系可塑剤及びポリエステル系可塑剤であり、且つ、フタル酸エステル系可塑剤とポリエステル系可塑剤の質量比は73:27~87:13である。このような構成を採用することにより、耐油性が良好でありながら、キャスティング工法での加工性が良好であり、風合いが柔軟な合成皮革とすることができる。
The synthetic leather according to this embodiment has a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer. The foamed layer and the non-foamed layer contain 60 to 100 parts by mass of plasticizer with respect to 100 parts by mass of vinyl chloride resin. The plasticizers used in the foaming layer and the non-foaming layer are a phthalate plasticizer and a polyester plasticizer, and the mass ratio of the phthalate plasticizer and the polyester plasticizer is 73:27 to 87: 13. By adopting such a configuration, it is possible to obtain a synthetic leather having good oil resistance, good workability in a casting method, and a soft texture.
図1は、一実施形態に係る合成皮革1の断面構造を模式的に示したものである。この合成皮革1では、繊維質基材2の一方の面に、発泡層3と、非発泡層4がこの順に積層されている。
FIG. 1 schematically shows the cross-sectional structure of synthetic leather 1 according to one embodiment. In this synthetic leather 1, a foam layer 3 and a non-foam layer 4 are laminated in this order on one side of a fibrous base material 2. As shown in FIG.
図2は、他の実施形態に係る合成皮革10の断面構造を模式的に示したものである。この合成皮革10では、繊維質基材2の上に接着層5を介して発泡層3が設けられている点と、非発泡層4の上に保護層6が設けられている点で図1の合成皮革1とは異なる。従って、図2の例では、繊維質基材2の一方の面に、接着層5と、発泡層3と、非発泡層4と、保護層6がこの順に積層されている。
FIG. 2 schematically shows a cross-sectional structure of synthetic leather 10 according to another embodiment. In this synthetic leather 10, the foam layer 3 is provided on the fibrous base material 2 via the adhesive layer 5, and the protective layer 6 is provided on the non-foam layer 4. Synthetic leather 1 is different. Therefore, in the example of FIG. 2, the adhesive layer 5, the foam layer 3, the non-foam layer 4, and the protective layer 6 are laminated in this order on one surface of the fibrous base material 2. As shown in FIG.
図3は、他の実施形態に係る合成皮革100の断面構造を模式的に示したものである。この合成皮革100では、非発泡層4の上に、アンダーコート層7を介して保護層6が設けられている点で図2の合成皮革10とは異なる。従って、図3の例では、繊維質基材2の一方の面に、接着層5と、発泡層3と、非発泡層4と、アンダーコート層7と、保護層6がこの順に積層されている。
FIG. 3 schematically shows a cross-sectional structure of synthetic leather 100 according to another embodiment. This synthetic leather 100 differs from the synthetic leather 10 of FIG. 2 in that a protective layer 6 is provided on the non-foamed layer 4 via an undercoat layer 7 . Therefore, in the example of FIG. 3, the adhesive layer 5, the foam layer 3, the non-foam layer 4, the undercoat layer 7, and the protective layer 6 are laminated in this order on one surface of the fibrous base material 2. there is
図1~3の例では、合成皮革のオモテ面には、意匠を考慮して、例えばシボ模様などの凹凸が設けられているが、平坦であってもよい。ここで、合成皮革のオモテ面とは、合成皮革の表裏のうち、使用時に目に見える面(意匠面)をいう。具体的には、オモテ面は、上記の非発泡層又は保護層の表面である。
In the examples of Figures 1 to 3, the front surface of the synthetic leather is provided with unevenness such as a grain pattern in consideration of the design, but it may be flat. Here, the front surface of the synthetic leather refers to the surface (design surface) of the front and back surfaces of the synthetic leather that is visible during use. Specifically, the front surface is the surface of the non-foamed layer or protective layer.
上記繊維質基材としては、特に限定されるものでなく、例えば、織物、編物、不織布などの繊維布帛や、天然皮革(床革を含む)等を用いることができる。繊維布帛としては、従来公知の溶剤系又は無溶剤系の高分子化合物を塗布又は含浸し、乾式凝固又は湿式凝固させたものを用いてもよい。ここでいう無溶剤系には水系が含まれる。また、高分子化合物としては、例えばポリウレタン樹脂や塩化ビニル系樹脂が挙げられる。なかでも、レザーライク性(具体的には、天然皮革のようなシボ感、厚み感、風合い)と強度や伸び特性などの観点から、繊維質基材としては編物が好ましく、丸編地がより好ましい。
The fibrous base material is not particularly limited, and for example, fiber fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics, natural leather (including split leather), and the like can be used. As the fiber fabric, one obtained by applying or impregnating a conventionally known solvent-based or solvent-free polymer compound and then dry-coagulating or wet-coagulating it may be used. The solventless systems referred to herein include aqueous systems. Further, examples of the polymer compound include polyurethane resins and vinyl chloride resins. Among them, knitted fabrics are preferable as the fibrous base material, and circular knitted fabrics are more preferable, from the viewpoint of leather-like properties (specifically, the texture, thickness, and texture of natural leather), strength, and elongation properties. preferable.
繊維布帛において繊維の種類は、特に限定されるものでなく、天然繊維、再生繊維、半合成繊維、合成繊維等、従来公知の繊維を挙げることができ、これらが2種以上組み合わされていてもよい。なかでも強度や加工性の点から、繊維としては合成繊維が好ましく、ポリエステル繊維がより好ましい。
The type of fiber in the fiber fabric is not particularly limited, and conventionally known fibers such as natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers can be mentioned. good. Among these fibers, synthetic fibers are preferable, and polyester fibers are more preferable, from the viewpoint of strength and workability.
繊維の形状も特に限定されず、長繊維、短繊維のいずれであってもよい。繊維質基材を構成する糸条の形態は、紡績糸などの短繊維糸でもよく、マルチフィラメント糸、モノフィラメント糸などの長繊維糸でもよく、長繊維と短繊維を組み合わせた長短複合紡績糸でもよい。得られる繊維質基材に柔軟性を付与できるという観点から、糸条としては、予め捲縮加工を施した短繊維を用いてもよく、糸条の状態で仮撚り加工や流体撹乱処理などの加工を施してもよい。
The shape of the fibers is also not particularly limited, and may be either long fibers or short fibers. The form of the yarn constituting the fibrous base material may be short fiber yarn such as spun yarn, long fiber yarn such as multifilament yarn or monofilament yarn, or long and short composite spun yarn combining long fibers and short fibers. good. From the viewpoint that flexibility can be imparted to the fibrous base material to be obtained, short fibers that have been pre-crimped may be used as the yarn, and the yarn is subjected to false twisting, fluid agitation treatment, or the like. It may be processed.
繊維質基材は、染料又は顔料により着色されたものでもよい。
The fibrous base material may be colored with dyes or pigments.
本実施形態に係る合成皮革は、塩化ビニル系樹脂と可塑剤を含む樹脂層として、発泡層と非発泡層とを備える。発泡層は、気泡を持つ樹脂層であり、多孔質層であってもよい。非発泡層は、発泡層とは異なり、気泡を持たない樹脂層である。非発泡層は、発泡層の表面に積層された樹脂層であり、表皮層とも称される。
The synthetic leather according to this embodiment includes a foam layer and a non-foam layer as resin layers containing a vinyl chloride resin and a plasticizer. The foam layer is a resin layer having cells, and may be a porous layer. The non-foamed layer is a resin layer having no air bubbles, unlike the foamed layer. The non-foamed layer is a resin layer laminated on the surface of the foamed layer, and is also called a skin layer.
非発泡層を構成する塩化ビニル系樹脂は、塩化ビニル及び/又は塩化ビニリデンを単量体成分として構成される重合体である。塩化ビニル系樹脂としては、特に限定されるものではなく、従来公知の塩化ビニル系樹脂を用いることができ、例えば、塩化ビニル樹脂及び/又は塩化ビニリデン樹脂が挙げられる。塩化ビニル樹脂としては、例えば、塩化ビニルの単独重合体であるポリ塩化ビニル、塩化ビニルと他の単量体との共重合体などが挙げられる。塩化ビニリデン樹脂としては、例えば、塩化ビニリデンの単独重合体であるポリ塩化ビニリデン、塩化ビニリデンと他の単量体との共重合体などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。ここで、塩化ビニル又は塩化ビニリデンと共重合される他の単量体としては、例えば、酢酸ビニル、エチレン、プロピレン、スチレン、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、マレイン酸、マレイン酸エステル、高級ビニルエーテルなどが挙げられ、塩化ビニルと塩化ビニリデンを共重合してもよい。
The vinyl chloride resin that constitutes the non-foamed layer is a polymer composed of vinyl chloride and/or vinylidene chloride as a monomer component. The vinyl chloride resin is not particularly limited, and conventionally known vinyl chloride resins can be used. Examples thereof include vinyl chloride resin and/or vinylidene chloride resin. Examples of vinyl chloride resins include polyvinyl chloride, which is a homopolymer of vinyl chloride, and copolymers of vinyl chloride and other monomers. Vinylidene chloride resins include, for example, polyvinylidene chloride, which is a homopolymer of vinylidene chloride, and copolymers of vinylidene chloride with other monomers. These can be used individually by 1 type or in combination of 2 or more types. Other monomers to be copolymerized with vinyl chloride or vinylidene chloride include, for example, vinyl acetate, ethylene, propylene, styrene, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, maleic acid, maleic acid, Examples include acid esters and higher vinyl ethers, and vinyl chloride and vinylidene chloride may be copolymerized.
非発泡層を構成する樹脂成分は塩化ビニル系樹脂を主成分とすることが好ましい。詳細には、樹脂成分の50質量%超が塩化ビニル系樹脂であることが好ましく、より好ましくは樹脂成分の80質量%以上が塩化ビニル系樹脂であり、樹脂成分の100質量%が塩化ビニル系樹脂でもよい。本明細書において、樹脂成分とは、樹脂層を構成する成分のうち、可塑剤や熱安定剤などの添加剤を除くポリマー成分をいう。
It is preferable that the resin component constituting the non-foamed layer is mainly composed of vinyl chloride resin. Specifically, it is preferable that more than 50% by mass of the resin component is a vinyl chloride resin, more preferably 80% by mass or more of the resin component is a vinyl chloride resin, and 100% by mass of the resin component is a vinyl chloride resin. Resin may be used. In the present specification, the resin component refers to a polymer component, excluding additives such as plasticizers and heat stabilizers, among the components constituting the resin layer.
非発泡層は、可塑剤として、フタル酸エステル系可塑剤とポリエステル系可塑剤とを含む。フタル酸エステル系可塑剤とポリエステル系可塑剤とを併用することで、非発泡層用樹脂組成液の粘度を低く抑えることができる。そのため、泡かみ、加工筋の発生を抑制することができ、均一な皮膜を形成することができる。よって、加工性、特にはキャスティング工法の加工性が良好となる。ここで、加工筋とは、樹脂組成液を塗布した際に塗布方向に沿って生じる筋状の欠陥をいう。ポリエステル系可塑剤は、他の可塑剤と比べて分子量が大きい。そのため、ポリエステル系可塑剤を用いることにより、可塑剤の拡散速度が小さくなり、非発泡層内部から非発泡層外部へ可塑剤が移行しにくい。よって、得られる合成皮革の耐油性を向上することができる。
The non-foaming layer contains a phthalate plasticizer and a polyester plasticizer as plasticizers. By using the phthalate plasticizer and the polyester plasticizer together, the viscosity of the resin composition liquid for the non-foaming layer can be kept low. Therefore, it is possible to suppress the generation of bubbles and processing streaks, and to form a uniform coating. Therefore, the workability, particularly the workability of the casting method, is improved. Here, the processing streak refers to a streak-like defect that occurs along the application direction when the resin composition liquid is applied. A polyester plasticizer has a larger molecular weight than other plasticizers. Therefore, by using a polyester-based plasticizer, the diffusion rate of the plasticizer is reduced, and the plasticizer is less likely to migrate from the inside of the non-foamed layer to the outside of the non-foamed layer. Therefore, the oil resistance of the obtained synthetic leather can be improved.
フタル酸エステル系可塑剤とは、塩化ビニル系樹脂に対して可塑剤として作用するフタル酸エステルをいう。フタル酸エステル系可塑剤としては、例えば、フタル酸ジブチル(DBP)、フタル酸ジオクチル(DOP)、フタル酸ジノニル(DNP)、フタル酸ジイソノニル(DINP)、フタル酸ジイソデシル(DIDP)、フタル酸ジトリデシル(DTDP)、フタル酸ジウンデシル(DUP)、フタル酸ベンジルブチル(BBP)、フタル酸ノニルウンデシル(NUP)、フタル酸ジアルキル(C9~C11)などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。これらはフタル酸と一価アルコールとのエステルであるため、後述するポリエステル系可塑剤としてのフタル酸系ポリエステルはフタル酸エステル系可塑剤には含まれない。
A phthalate plasticizer is a phthalate that acts as a plasticizer for vinyl chloride resin. Examples of phthalate plasticizers include dibutyl phthalate (DBP), dioctyl phthalate (DOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate ( DTDP), diundecyl phthalate (DUP), benzylbutyl phthalate (BBP), nonylundecyl phthalate (NUP), dialkyl phthalate (C9-C11), and the like. These can be used individually by 1 type or in combination of 2 or more types. Since these are esters of phthalic acid and monohydric alcohol, the phthalate-based polyester as a polyester-based plasticizer described later is not included in the phthalate-based plasticizer.
一実施形態において、フタル酸エステル可塑剤としては、炭素数4以上20以下のアルコールからなる群から選択される少なくとも1種の一価アルコールとフタル酸とのエステルであるフタル酸ジアルキルが好ましい。なかでも、耐ブリード性、耐寒性、耐熱性の観点から、フタル酸ジアルキル(C9~C11)が好ましい。ここで、フタル酸ジアルキル(C9~C11)とは、炭素数9~11のアルコールの混合物とフタル酸とのエステルである。
In one embodiment, the phthalate ester plasticizer is preferably a dialkyl phthalate, which is an ester of phthalic acid and at least one monohydric alcohol selected from the group consisting of alcohols having 4 to 20 carbon atoms. Among them, dialkyl phthalate (C9 to C11) is preferable from the viewpoint of bleeding resistance, cold resistance and heat resistance. Here, the dialkyl phthalate (C9-C11) is an ester of a mixture of alcohols having 9-11 carbon atoms and phthalic acid.
ポリエステル系可塑剤とは、塩化ビニル系樹脂に対して可塑剤として作用するポリエステルをいう。ポリエステル系可塑剤としては、ジカルボン酸と二価アルコールを重縮合させて得られるものが挙げられ、例えば、アジピン酸系ポリエステル、セバシン酸系ポリエステル、フタル酸系ポリエステルなどが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。二価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール(例えば1,3-ブタンジオール、1,4-ブタンジオール)、及びヘキサンジオール(例えば1,6-ヘキサンジオール)などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。ポリエステル系可塑剤としては、汎用性の観点から、アジピン酸系ポリエステルが好ましい。
A polyester plasticizer is a polyester that acts as a plasticizer for vinyl chloride resin. Polyester plasticizers include those obtained by polycondensation of dicarboxylic acids and dihydric alcohols, such as adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters. These can be used individually by 1 type or in combination of 2 or more types. Dihydric alcohols include, for example, ethylene glycol, propylene glycol, butanediol (eg 1,3-butanediol, 1,4-butanediol), and hexanediol (eg 1,6-hexanediol). These can be used individually by 1 type or in combination of 2 or more types. As the polyester-based plasticizer, adipic acid-based polyester is preferable from the viewpoint of versatility.
ポリエステル系可塑剤の数平均分子量(Mn)は、特に限定されず、500~2500であることが好ましく、より好ましくは1200~2000である。数平均分子量が2500以下であることにより、非発泡層用樹脂組成液の粘度を低く抑えることができ、加工性、特にはキャスティング工法の加工性を更に向上することができる。数平均分子量が500以上であることにより、良好な耐油性が得られる。ここで、ポリエステル系可塑剤の数平均分子量は、ゲル浸透クロマトグラフィー(GPC)法で測定したポリスチレン換算値として算出される。
The number average molecular weight (Mn) of the polyester plasticizer is not particularly limited, and is preferably 500-2500, more preferably 1200-2000. When the number average molecular weight is 2500 or less, the viscosity of the resin composition liquid for the non-foaming layer can be kept low, and the processability, particularly the processability of the casting method, can be further improved. When the number average molecular weight is 500 or more, good oil resistance can be obtained. Here, the number average molecular weight of the polyester plasticizer is calculated as a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.
ポリエステル系可塑剤の粘度は、特に限定されず、150~5000mPa・sであることが好ましく、より好ましくは2000~5000mPa・sである。粘度が150mPa・s以上であることにより、得られる合成皮革の耐油性が良好なものとなる。粘度が5000mPa・s以下であることにより、非発泡層用樹脂組成液の粘度を低く抑えることができ、加工性、特にはキャスティング工法の加工性を更に向上することができる。ここで、ポリエステル系可塑剤の粘度は、ブルックフィールド型粘度計を用いて測定される25℃での粘度であり、より詳細にはBII形粘度計(BHII型、東機産業株式会社製、ローターNo.3)を用いて、10rpm、液温25℃で測定される。
The viscosity of the polyester plasticizer is not particularly limited, and is preferably 150 to 5000 mPa·s, more preferably 2000 to 5000 mPa·s. When the viscosity is 150 mPa·s or more, the resulting synthetic leather has good oil resistance. When the viscosity is 5000 mPa·s or less, the viscosity of the resin composition liquid for the non-foaming layer can be kept low, and the processability, particularly the processability of the casting method, can be further improved. Here, the viscosity of the polyester plasticizer is the viscosity at 25 ° C. measured using a Brookfield viscometer, and more specifically, a BII viscometer (BHII type, manufactured by Toki Sangyo Co., Ltd., rotor No. 3) at 10 rpm and a liquid temperature of 25°C.
非発泡層において、フタル酸エステル系可塑剤とポリエステル系可塑剤との質量比(固形分としての配合比)は、(フタル酸エステル系可塑剤の量):(ポリエステル系可塑剤の量)=73:27~87:13であり、好ましくは77:23~83:17である。フタル酸エステル系可塑剤の配合比が73質量%以上(即ち、ポリエステル系可塑剤の配合比が27質量%以下)であることにより、非発泡層用樹脂組成液の粘度を低く抑えることができ、加工性、特にはキャスティング工法による加工性が良好となる。フタル酸エステル系可塑剤の配合比が87質量%以下(すなわち、ポリエステル系可塑剤の配合比が13質量%以上)であることにより、良好な耐油性が得られる。
In the non-foaming layer, the mass ratio of the phthalate plasticizer and the polyester plasticizer (blending ratio as solid content) is (amount of phthalate plasticizer):(amount of polyester plasticizer) = 73:27 to 87:13, preferably 77:23 to 83:17. When the blending ratio of the phthalate plasticizer is 73% by mass or more (that is, the blending ratio of the polyester plasticizer is 27% by mass or less), the viscosity of the resin composition liquid for the non-foaming layer can be kept low. , the workability, especially the workability by the casting method is improved. Good oil resistance is obtained when the blending ratio of the phthalate plasticizer is 87% by mass or less (that is, the blending ratio of the polyester plasticizer is 13% by mass or more).
本明細書において、フタル酸エステル系可塑剤とポリエステル系可塑剤の質量比は、両者の合計を100としたときのそれぞれの割合が小数点以下の端数を持つ場合、小数点以下を四捨五入して得られる整数比である。
In the present specification, the mass ratio of the phthalate ester plasticizer and the polyester plasticizer is obtained by rounding off the decimal point when the ratio of each has a fraction after the decimal point when the total of both is 100. It is an integer ratio.
本明細書において、固形分とは、有機溶剤や水などの揮発する物質以外の成分をいい、蒸発残分ないし不揮発分とも称される。そのため、可塑剤のように通常の乾燥温度で蒸発しない液体も固形分に含まれる。
In this specification, solid content refers to components other than volatile substances such as organic solvents and water, and is also referred to as evaporation residue or non-volatile content. Therefore, liquids that do not evaporate at ordinary drying temperatures, such as plasticizers, are also included in the solid content.
非発泡層中における可塑剤の含有量(フタル酸エステル系可塑剤とポリエステル系可塑剤の含有量の合計)は、塩化ビニル系樹脂100質量部に対し、60~100質量部であり、好ましくは65~85質量部である。可塑剤の量が60質量部以上であることにより、柔軟な風合いが得られる。また、非発泡層用樹脂組成液の粘度を低く抑えることができ、加工性、特にはキャスティング工法による加工性が良好となる。可塑剤の量が100質量部以下であることにより、強度を向上することができる。また、可塑剤のブリードを抑制することができるため意匠性を向上することができる。
The content of the plasticizer in the non-foaming layer (the total content of the phthalate plasticizer and the polyester plasticizer) is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, preferably 65 to 85 parts by mass. When the amount of the plasticizer is 60 parts by mass or more, a soft texture can be obtained. In addition, the viscosity of the resin composition liquid for the non-foaming layer can be kept low, and the processability, particularly the processability by the casting method, is improved. When the amount of the plasticizer is 100 parts by mass or less, the strength can be improved. Moreover, since the bleeding of the plasticizer can be suppressed, the designability can be improved.
非発泡層には、必要に応じて、その物性を損なわない範囲内で、従来公知の添加剤を配合することができる。そのような添加剤としては、例えば、フタル酸エステル系可塑剤やポリエステル系可塑剤以外の可塑剤、塩化ビニル系樹脂以外の熱可塑性樹脂や熱硬化性樹脂、熱安定剤、充填剤、顔料、耐アミン剤、難燃剤、導電性付与剤、帯電防止剤、紫外線吸収剤、光安定剤、酸化防止剤、顔料分散剤、架橋剤、増粘剤などが挙げられ、1種単独で又は2種以上組み合わせて用いることができる。
The non-foaming layer can contain conventionally known additives as needed within a range that does not impair its physical properties. Examples of such additives include plasticizers other than phthalate plasticizers and polyester plasticizers, thermoplastic resins and thermosetting resins other than vinyl chloride resins, heat stabilizers, fillers, pigments, Amine-resistant agents, flame retardants, conductivity-imparting agents, antistatic agents, ultraviolet absorbers, light stabilizers, antioxidants, pigment dispersants, cross-linking agents, thickeners, etc., may be used alone or in combination of two. The above can be used in combination.
上記熱安定剤としては、例えば、ステアリン酸カルシウム、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金属石鹸、フェノール及び/又はナフトールのナトリウム塩、亜鉛塩、バリウム塩などの金属塩、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、トリフェニルホスファイト、トリクレジルホスファイト、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などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。一実施形態において、熱安定剤としては、有機酸カルシウム塩及び/又は有機酸亜鉛塩を用いてもよい。熱安定剤の含有量は特に限定されず、例えば塩化ビニル系樹脂100質量部に対して0.1~10質量部でもよく、0.5~5質量部でもよい。
Examples of the heat stabilizer include metal soaps such as calcium stearate, magnesium stearate, aluminum stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, and zinc laurate; sodium phenol and/or naphthol; Salts, metal salts such as zinc salts and barium salts, organotin compounds such as dibutyltin dilaurate and dibutyltin dimalate, and phosphites such as triphenylphosphite, tricresylphosphite and triisooctylphosphite. be done. These can be used individually by 1 type or in combination of 2 or more types. In one embodiment, an organic acid calcium salt and/or an organic acid zinc salt may be used as a thermal stabilizer. The content of the heat stabilizer is not particularly limited, and may be, for example, 0.1 to 10 parts by mass or 0.5 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
上記耐アミン剤としては、例えば、過塩素酸ナトリウム、過塩素酸カリウムなどの過塩素酸塩などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。耐アミン剤の含有量は特に限定されず、例えば塩化ビニル系樹脂100質量部に対して0.05~5質量部でもよく、0.1~2質量部でもよい。
Examples of the amine-resistant agents include perchlorates such as sodium perchlorate and potassium perchlorate. These can be used individually by 1 type or in combination of 2 or more types. The content of the amine-resistant agent is not particularly limited, and may be, for example, 0.05 to 5 parts by mass or 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
非発泡層の厚さは、特に限定されないが、100~300μmであることが好ましく、より好ましくは130~250μmである。非発泡層の厚さが100μm以上であると、良好な強度が得られる。非発泡層の厚さが300μm以下であると、得られる合成皮革の非発泡層の膜厚を均一化できる。
Although the thickness of the non-foamed layer is not particularly limited, it is preferably 100-300 μm, more preferably 130-250 μm. Good strength is obtained when the thickness of the non-foamed layer is 100 μm or more. When the thickness of the non-foamed layer is 300 μm or less, the thickness of the non-foamed layer of the obtained synthetic leather can be made uniform.
発泡層を構成する塩化ビニル系樹脂は、塩化ビニル及び/又は塩化ビニリデンを単量体成分として構成される重合体である。当該塩化ビニル系樹脂としては、特に限定されるものではなく、上述の非発泡層と同様の塩化ビニル系樹脂を用いることができるので、説明は省略する。発泡層に含まれる塩化ビニル系樹脂と非発泡層に含まれる塩化ビニル系樹脂とは、同一でも異なってもよい。
The vinyl chloride resin that constitutes the foam layer is a polymer composed of vinyl chloride and/or vinylidene chloride as a monomer component. The vinyl chloride-based resin is not particularly limited, and the same vinyl chloride-based resin as that used for the non-foamed layer can be used, so the description thereof is omitted. The vinyl chloride resin contained in the foam layer and the vinyl chloride resin contained in the non-foam layer may be the same or different.
発泡層を構成する樹脂成分は塩化ビニル系樹脂を主成分とすることが好ましい。詳細には、樹脂成分の50質量%超が塩化ビニル系樹脂であることが好ましく、より好ましくは樹脂成分の80質量%以上が塩化ビニル系樹脂であり、樹脂成分の100質量%が塩化ビニル系樹脂でもよい。
It is preferable that the resin component constituting the foam layer is mainly composed of vinyl chloride resin. Specifically, it is preferable that more than 50% by mass of the resin component is a vinyl chloride resin, more preferably 80% by mass or more of the resin component is a vinyl chloride resin, and 100% by mass of the resin component is a vinyl chloride resin. Resin may be used.
発泡層は、可塑剤として、フタル酸エステル系可塑剤とポリエステル系可塑剤とを含む。フタル酸エステル系可塑剤とポリエステル系可塑剤とを併用することで、発泡層用樹脂組成液の粘度を低く抑えることができる。そのため、泡かみ、加工筋の発生を抑制することができ、均一な皮膜を形成することができる。よって、加工性、特にはキャスティング工法の加工性が良好となる。ポリエステル系可塑剤は、他の可塑剤と比べて分子量が大きい。そのため、ポリエステル系可塑剤を用いることにより、他の樹脂層への可塑剤の拡散速度が小さくなり、発泡層内部から発泡層外部へ可塑剤が移行しにくい。よって、良好な耐油性が得られる。
The foam layer contains a phthalate plasticizer and a polyester plasticizer as plasticizers. By using a phthalate plasticizer and a polyester plasticizer in combination, the viscosity of the resin composition liquid for the foam layer can be kept low. Therefore, it is possible to suppress the generation of bubbles and processing streaks, and to form a uniform coating. Therefore, the workability, particularly the workability of the casting method, is improved. A polyester plasticizer has a larger molecular weight than other plasticizers. Therefore, by using a polyester-based plasticizer, the diffusion speed of the plasticizer to other resin layers is reduced, and the plasticizer is less likely to migrate from the inside of the foam layer to the outside of the foam layer. Therefore, good oil resistance is obtained.
発泡層におけるフタル酸エステル系可塑剤とポリエステル系可塑剤としては、特に限定されるものでなく、上述の非発泡層と同様のフタル酸エステル系可塑剤とポリエステル系可塑剤を用いることができる。そのため、フタル酸エステル系可塑剤としてフタル酸ジアルキル(C9~C11)が好ましいこと、ポリエステル系可塑剤としてアジピン酸系ポリエステルが好ましいこと、ポリエステル系可塑剤の数平均分子量が好ましくは500~2500(より好ましくは1200~2000)であること、及び、ポリエステル系可塑剤の粘度が好ましくは150~5000mPa・s(より好ましくは2000~5000mPa・s)であることについても、上記非発泡層と同様である。発泡層に含まれるフタル酸エステル系可塑剤及びポリエステル系可塑剤と非発泡層に含まれるフタル酸エステル系可塑剤及びポリエステル系可塑剤とは、それぞれ同一でも異なってもよい。
The phthalate ester plasticizer and polyester plasticizer in the foam layer are not particularly limited, and the same phthalate ester plasticizer and polyester plasticizer as in the non-foam layer can be used. Therefore, dialkyl phthalate (C9-C11) is preferable as the phthalate plasticizer, adipic acid polyester is preferable as the polyester plasticizer, and the number average molecular weight of the polyester plasticizer is preferably 500 to 2500 (more It is preferably 1200 to 2000), and the viscosity of the polyester plasticizer is preferably 150 to 5000 mPa s (more preferably 2000 to 5000 mPa s). . The phthalate ester plasticizer and polyester plasticizer contained in the foam layer and the phthalate ester plasticizer and polyester plasticizer contained in the non-foam layer may be the same or different.
発泡層において、フタル酸エステル系可塑剤とポリエステル系可塑剤との質量比(固形分としての配合比)は、(フタル酸エステル系可塑剤の量):(ポリエステル系可塑剤の量)=73:27~87:13であり、好ましくは77:23~83:17である。フタル酸エステル系可塑剤の配合比が73質量%以上(即ち、ポリエステル系可塑剤の配合比が27質量%以下)であることにより、発泡層用樹脂組成液の粘度を低く抑えることができ、加工性、特にはキャスティング工法による加工性が良好となる。フタル酸エステル系可塑剤の配合比が87質量%以下(すなわち、ポリエステル系可塑剤の配合比が13質量%以上)であることにより、良好な耐油性が得られる。フタル酸エステル系可塑剤とポリエステル系可塑剤との質量比は、発泡層と非発泡層とで同一でも異なってもよい。
In the foam layer, the mass ratio of the phthalate-based plasticizer and the polyester-based plasticizer (blending ratio as a solid content) is (amount of phthalate-based plasticizer):(amount of polyester-based plasticizer) = 73. :27-87:13, preferably 77:23-83:17. When the blending ratio of the phthalate plasticizer is 73% by mass or more (that is, the blending ratio of the polyester plasticizer is 27% by mass or less), the viscosity of the resin composition liquid for the foam layer can be kept low. Workability, especially workability by casting method, is improved. Good oil resistance is obtained when the blending ratio of the phthalate plasticizer is 87% by mass or less (that is, the blending ratio of the polyester plasticizer is 13% by mass or more). The mass ratio of the phthalate-based plasticizer and the polyester-based plasticizer may be the same or different between the foaming layer and the non-foaming layer.
発泡層中における可塑剤の含有量(フタル酸エステル系可塑剤とポリエステル系可塑剤の含有量の合計)は、塩化ビニル系樹脂100質量部に対し、60~100質量部であり、好ましくは65~85質量部である。可塑剤の配合量が60質量部以上であることにより、柔軟な風合いが得られる。また、発泡層用樹脂組成液の粘度を低く抑えることができ、加工性、特にはキャスティング工法による加工性が良好となる。可塑剤の配合量が100質量部以下であることにより、強度を向上することができる。また、可塑剤のブリードを抑制することができるため意匠性を向上することができる。可塑剤の含有量は、発泡層と非発泡層とで同一でも異なってもよい。
The content of the plasticizer in the foam layer (the total content of the phthalate plasticizer and the polyester plasticizer) is 60 to 100 parts by mass, preferably 65 parts by mass, based on 100 parts by mass of the vinyl chloride resin. ~85 parts by mass. When the blending amount of the plasticizer is 60 parts by mass or more, a soft texture can be obtained. In addition, the viscosity of the resin composition liquid for the foam layer can be kept low, and workability, particularly workability by a casting method, is improved. By setting the amount of the plasticizer to be 100 parts by mass or less, the strength can be improved. Moreover, since the bleeding of the plasticizer can be suppressed, the designability can be improved. The content of the plasticizer may be the same or different between the foamed layer and the non-foamed layer.
発泡層は、例えば、発泡層用樹脂組成液に発泡剤を添加することにより形成することができ、触感や風合いを良好にすることができる。発泡剤としては、特に限定されず、公知の発泡剤を用いることができ、発泡性の観点から、有機系発泡剤を用いることが好ましい。有機系発泡剤としては、例えば、アゾジカルボンアミド(ADCA)、2,2'-アゾジイソブチロニトリル(AIBN)、ベンゼンスルホニルヒドラジド、p-トルエンスルホニルヒドラジド、4,4’-オキシビス[ベンゼンスルホニルヒドラジド](OBSH)、N,N'-ジニトロソペンタメチレンテトラミン(DPT)などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。
The foam layer can be formed, for example, by adding a foaming agent to the resin composition liquid for the foam layer, and can improve the tactile feel and texture. The foaming agent is not particularly limited, and any known foaming agent can be used. From the viewpoint of foamability, it is preferable to use an organic foaming agent. Examples of organic blowing agents include azodicarbonamide (ADCA), 2,2′-azodiisobutyronitrile (AIBN), benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 4,4′-oxybis[benzenesulfonylhydrazide]. (OBSH), N,N'-dinitrosopentamethylenetetramine (DPT) and the like. These can be used individually by 1 type or in combination of 2 or more types.
発泡層の発泡倍率は、特に限定されないが、2倍以下であることが好ましく、より好ましくは1.1倍以上2倍以下であり、更に好ましくは1.2倍以上1.7倍以下である。発泡層の発泡倍率が2倍以下であることにより、独立孔が形成されやすくなり、耐摩耗性、耐屈曲性、剥離強度を向上することができる。
The expansion ratio of the foamed layer is not particularly limited, but is preferably 2 times or less, more preferably 1.1 times or more and 2 times or less, and still more preferably 1.2 times or more and 1.7 times or less. . When the expansion ratio of the foam layer is 2 or less, independent pores are easily formed, and wear resistance, flex resistance, and peel strength can be improved.
発泡層の厚さは、特に限定されず、例えば150~370μmでもよいが、190~370μmであることが好ましく、より好ましくは200~300μmである。発泡層の厚さが190μm以上であると、柔軟な風合いが得られる。発泡層の厚さが370μm以下であると、発泡セルの径の大きさの調整が容易である。
The thickness of the foam layer is not particularly limited, and may be, for example, 150 to 370 μm, preferably 190 to 370 μm, more preferably 200 to 300 μm. When the foam layer has a thickness of 190 µm or more, a soft texture can be obtained. When the thickness of the foam layer is 370 µm or less, it is easy to adjust the diameter of the foam cells.
発泡層には、必要に応じて、その物性を損なわない範囲内で、従来公知の添加剤を配合することができる。そのような添加剤としては、例えば、フタル酸エステル系可塑剤やポリエステル系可塑剤以外の可塑剤、塩化ビニル系樹脂以外の熱可塑性樹脂や熱硬化性樹脂、熱安定剤、充填剤、顔料、耐アミン剤、難燃剤、導電性付与剤、帯電防止剤、紫外線吸収剤、光安定剤、酸化防止剤、顔料分散剤、架橋剤、増粘剤などが挙げられ、1種単独で又は2種以上組み合わせて用いることができる。なお、発泡層における熱安定剤及び耐アミン剤についての具体例及び含有量については、上述した非発泡層と同様である。
Conventionally known additives can be blended into the foam layer as needed within a range that does not impair its physical properties. Examples of such additives include plasticizers other than phthalate plasticizers and polyester plasticizers, thermoplastic resins and thermosetting resins other than vinyl chloride resins, heat stabilizers, fillers, pigments, Amine-resistant agents, flame retardants, conductivity-imparting agents, antistatic agents, ultraviolet absorbers, light stabilizers, antioxidants, pigment dispersants, cross-linking agents, thickeners, etc., may be used alone or in combination of two. The above can be used in combination. Specific examples and contents of the heat stabilizer and the amine-resistant agent in the foam layer are the same as those of the non-foam layer described above.
本実施形態において、発泡層を設ける際、発泡層と繊維質基材との間に接着層を介してもよいし、繊維質基材に発泡層を直接積層してもよい。繊維質基材と発泡層の間に接着層を介在させることにより、繊維質基材と発泡層の接着性を向上させることができる。接着層は、気泡を持たない非発泡の樹脂層でもよい。
In this embodiment, when providing the foam layer, an adhesive layer may be interposed between the foam layer and the fibrous base material, or the foam layer may be directly laminated on the fibrous base material. By interposing an adhesive layer between the fibrous base material and the foam layer, the adhesion between the fibrous base material and the foam layer can be improved. The adhesive layer may be a non-foamed resin layer having no air bubbles.
接着層を構成する樹脂としては、特に限定されず、通常の塩化ビニルレザーに一般に使用される樹脂を用いることができる。例えば、ポリウレタン樹脂や塩化ビニル系樹脂などが挙げられる。
The resin that constitutes the adhesive layer is not particularly limited, and resins commonly used for ordinary vinyl chloride leather can be used. Examples thereof include polyurethane resins and vinyl chloride resins.
接着層の厚さは、特に限定されず、例えば20~200μmでもよく、50~150μmでもよい。
The thickness of the adhesive layer is not particularly limited, and may be, for example, 20-200 μm or 50-150 μm.
本実施形態において、非発泡層上に、更に保護層を設けてもよい。非発泡層上に保護層を設けることにより、得られる合成皮革の物性、特には耐摩耗性及び耐油性を向上させることができる。
In this embodiment, a protective layer may be further provided on the non-foamed layer. By providing a protective layer on the non-foamed layer, the physical properties of the resulting synthetic leather, particularly abrasion resistance and oil resistance, can be improved.
保護層は、ポリウレタン樹脂を含むことが好ましい。かかる保護層用のポリウレタン樹脂は、特に限定されるものでなく、例えば、ポリエーテル系ポリウレタン樹脂、ポリエステル系ポリウレタン樹脂、ポリカーボネート系ポリウレタン樹脂などを挙げることができる。これらのポリウレタン樹脂は1種単独で又は2種以上組み合わせて用いることができる。なかでも、耐摩耗性の観点から、保護層用のポリウレタン樹脂としては、ポリカーボネート系ポリウレタン樹脂が好ましい。
The protective layer preferably contains polyurethane resin. The polyurethane resin for the protective layer is not particularly limited, and examples thereof include polyether-based polyurethane resins, polyester-based polyurethane resins, and polycarbonate-based polyurethane resins. These polyurethane resins can be used singly or in combination of two or more. Among them, polycarbonate-based polyurethane resin is preferable as the polyurethane resin for the protective layer from the viewpoint of abrasion resistance.
保護層用のポリウレタン樹脂の形態は、特に限定されず、用途に応じて適宜選択すればよい。例えば、溶剤系又は水系であってよく、一液型、二液硬化型であってよい。環境保全の観点から、当該ポリウレタン樹脂の形態は水系であることが好ましい。
The form of the polyurethane resin for the protective layer is not particularly limited, and may be appropriately selected according to the application. For example, it may be solvent-based or water-based, and may be one-component or two-component curable. From the viewpoint of environmental protection, the form of the polyurethane resin is preferably water-based.
保護層を形成するために用いる保護層用樹脂組成液には、必要に応じて、ポリウレタン樹脂の物性を損なわない範囲内で、任意成分を配合することができる。任意成分としては、例えば、架橋剤、滑剤、レベリング剤、増粘剤、消泡剤、耐光安定剤、導電性付与剤、帯電防止剤、撥水剤、撥油剤、ブロッキング防止剤、抗菌剤などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。
The protective layer resin composition liquid used to form the protective layer can optionally contain optional components within a range that does not impair the physical properties of the polyurethane resin. Examples of optional components include cross-linking agents, lubricants, leveling agents, thickeners, antifoaming agents, light stabilizers, conductivity imparting agents, antistatic agents, water repellent agents, oil repellent agents, antiblocking agents, antibacterial agents, and the like. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
保護層の厚さは、特に限定されず、例えば2~30μmであることが好ましく、より好ましくは5~20μmである。厚さが2μm以上であれば、耐摩耗性を向上させることができる。厚さが30μm以下であれば、柔軟な風合いが得られる。
The thickness of the protective layer is not particularly limited, and is preferably 2 to 30 μm, more preferably 5 to 20 μm, for example. Abrasion resistance can be improved if the thickness is 2 μm or more. If the thickness is 30 μm or less, a soft texture can be obtained.
本実施形態において、保護層を設ける際、保護層と非発泡層との間にアンダーコート層を介してもよいし、非発泡層に保護層を直接積層してもよい。表層と保護層の間にアンダーコート層を介在させることにより、得られる合成皮革の物性、特には耐摩耗性、耐熱黄変性及び耐油性を向上させることができる。
In this embodiment, when providing the protective layer, an undercoat layer may be interposed between the protective layer and the non-foamed layer, or the protective layer may be laminated directly on the non-foamed layer. By interposing an undercoat layer between the surface layer and the protective layer, the physical properties of the resulting synthetic leather, particularly abrasion resistance, heat yellowing resistance and oil resistance, can be improved.
アンダーコート層は、ポリウレタン樹脂を含むことが好ましい。かかるアンダーコート層用のポリウレタン樹脂は、特に限定されるものでなく、例えば、ポリエーテル系ポリウレタン樹脂、ポリエステル系ポリウレタン樹脂、ポリカーボネート系ポリウレタン樹脂などを挙げることができる。これらのポリウレタン樹脂は1種単独で又は2種以上組み合わせて用いることができる。なかでも、耐熱黄変性及び耐油性の観点から、アンダーコート層用のポリウレタン樹脂としては、ポリエステル系ポリウレタン樹脂が好ましい。
The undercoat layer preferably contains a polyurethane resin. The polyurethane resin for such an undercoat layer is not particularly limited, and examples thereof include polyether-based polyurethane resins, polyester-based polyurethane resins, and polycarbonate-based polyurethane resins. These polyurethane resins can be used singly or in combination of two or more. Among them, polyester-based polyurethane resins are preferable as the polyurethane resin for the undercoat layer from the viewpoint of heat resistance to yellowing and oil resistance.
アンダーコート層用のポリウレタン樹脂の形態は、特に限定されず、用途に応じて適宜選択すればよい。例えば、溶剤系又は水系であってよく、一液型、二液硬化型であってよい。環境保全の観点から、当該ポリウレタン樹脂は水系であることが好ましい。
The form of the polyurethane resin for the undercoat layer is not particularly limited, and may be appropriately selected according to the application. For example, it may be solvent-based or water-based, and may be one-component or two-component curable. From the viewpoint of environmental conservation, the polyurethane resin is preferably water-based.
アンダーコート層を形成するために用いるアンダーコート層用樹脂組成液には、必要に応じて、ポリウレタン樹脂の物性を損なわない範囲内で、任意成分を配合することができる。任意成分としては、例えば、ポリウレタン樹脂以外の樹脂(例えば、アクリル樹脂)、架橋剤、レベリング剤、消泡剤、増粘剤などが挙げられる。これらは1種単独で又は2種以上組み合わせて用いることができる。
The undercoat layer resin composition liquid used to form the undercoat layer may optionally contain optional components within a range that does not impair the physical properties of the polyurethane resin. Examples of optional components include resins other than polyurethane resins (for example, acrylic resins), cross-linking agents, leveling agents, antifoaming agents, and thickening agents. These can be used individually by 1 type or in combination of 2 or more types.
アンダーコート層の厚さは、特に限定されず、例えば1~20μmでもよく、2~10μmでもよい。
The thickness of the undercoat layer is not particularly limited, and may be, for example, 1 to 20 μm or 2 to 10 μm.
次に、本実施形態に係る合成皮革の製造方法について説明する。該製造方法は、特に限定されるものではなく、従来公知の合成皮革と同様の製造方法を採用することができ、カレンダー工法やキャスティング工法が挙げられる。一実施形態において、キャスティング工法による場合、以下のような工程を順に行うことにより実施形態の合成皮革が製造できる。すなわち、該製造方法は、
(1)非発泡層用樹脂組成液を離型性基材上に塗布して、非発泡層を形成する工程、
(2)非発泡層上に発泡層用樹脂組成液を塗布して、発泡層を形成する工程、
(3)発泡層と繊維質基材とを貼り合せる工程、及び、
(4)離型性基材を剥離する工程、
を含むものである。 Next, a method for manufacturing synthetic leather according to the present embodiment will be described. The manufacturing method is not particularly limited, and the same manufacturing method as that for conventionally known synthetic leather can be employed, and examples thereof include a calendering method and a casting method. In one embodiment, when the casting method is used, the synthetic leather of the embodiment can be manufactured by performing the following steps in order. That is, the production method is
(1) a step of applying a non-foaming layer resin composition liquid onto a release substrate to form a non-foaming layer;
(2) a step of applying a foamed layer resin composition liquid onto the non-foamed layer to form a foamed layer;
(3) a step of laminating the foam layer and the fibrous base material, and
(4) a step of peeling off the releasable substrate;
includes.
(1)非発泡層用樹脂組成液を離型性基材上に塗布して、非発泡層を形成する工程、
(2)非発泡層上に発泡層用樹脂組成液を塗布して、発泡層を形成する工程、
(3)発泡層と繊維質基材とを貼り合せる工程、及び、
(4)離型性基材を剥離する工程、
を含むものである。 Next, a method for manufacturing synthetic leather according to the present embodiment will be described. The manufacturing method is not particularly limited, and the same manufacturing method as that for conventionally known synthetic leather can be employed, and examples thereof include a calendering method and a casting method. In one embodiment, when the casting method is used, the synthetic leather of the embodiment can be manufactured by performing the following steps in order. That is, the production method is
(1) a step of applying a non-foaming layer resin composition liquid onto a release substrate to form a non-foaming layer;
(2) a step of applying a foamed layer resin composition liquid onto the non-foamed layer to form a foamed layer;
(3) a step of laminating the foam layer and the fibrous base material, and
(4) a step of peeling off the releasable substrate;
includes.
離型性基材上に非発泡層用樹脂組成液を塗布する方法としては、従来公知の種々の方法を採用することができ、特に限定されるものではない。例えば、ナイフコーター、コンマコーター、ロールコーター、ダイコーターなどを用いた方法を挙げることができる。なかでも均一な薄膜層の形成が可能であるという点で、ナイフコーター、又は、コンマコーターによる塗布が好ましい。
As a method for applying the resin composition liquid for the non-foaming layer onto the releasable base material, conventionally known various methods can be employed, and there is no particular limitation. Examples thereof include methods using a knife coater, comma coater, roll coater, die coater, and the like. Among them, application by a knife coater or a comma coater is preferable in that a uniform thin film layer can be formed.
離型性基材は特に限定されず、塩化ビニル系樹脂に対して離型性を有する基材、あるいは離型処理を施した基材であればよい。例えば、離型紙、離型処理布、撥水処理布、ポリエチレン樹脂又はポリプロピレン樹脂などからなるオレフィンシート又はフィルム、フッ素樹脂シート又はフィルム、離型紙付きプラスチックフィルムなどを挙げることができる。離型性基材は凹凸模様を有していてもよく、このような離型性基材を用いることにより、合成皮革の表面にシボ模様などの凹凸模様を形成して意匠性を付与することができる。
The releasable base material is not particularly limited as long as it has releasability with respect to vinyl chloride resin or a base material that has undergone a releasable treatment. Examples thereof include release paper, release-treated cloth, water-repellent treated cloth, olefin sheet or film made of polyethylene resin or polypropylene resin, fluororesin sheet or film, and plastic film with release paper. The release substrate may have an uneven pattern, and by using such a release substrate, an uneven pattern such as a textured pattern is formed on the surface of the synthetic leather to impart a design property. can be done.
非発泡層用樹脂組成液を離型性基材に塗布したのち、必要により熱処理を行う。熱処理は、ゲル化を促進するために行われる。
After applying the resin composition liquid for the non-foaming layer to the releasable base material, heat treatment is performed as necessary. Heat treatment is performed to promote gelation.
次いで、非発泡層上に発泡層用樹脂組成液を塗布する。発泡層用樹脂組成液を塗布する方法としては、非発泡層用樹脂組成液を塗布する方法と同様の方法を採用することができる。
Next, the resin composition liquid for foaming layer is applied onto the non-foaming layer. As a method for applying the resin composition liquid for the foaming layer, the same method as the method for applying the resin composition liquid for the non-foaming layer can be adopted.
次いで、発泡層と繊維質基材とを積層する。積層方法としては、例えば、転写法、熱融着、熱圧着、接着剤を用いた貼着など、従来公知の方法が挙げられる。接着剤を用いる場合は、発泡層上に接着層用樹脂組成液を塗布した後、繊維質基材を積層すればよい。接着層用樹脂組成液を塗布する方法としては、非発泡層用樹脂組成液を塗布する方法と同様の方法を採用することができる。
Next, the foam layer and the fibrous base material are laminated. Lamination methods include, for example, conventionally known methods such as a transfer method, heat fusion bonding, thermocompression bonding, and adhesion using an adhesive. When an adhesive is used, a fibrous base material may be laminated after the adhesive layer resin composition liquid is applied onto the foam layer. As a method of applying the adhesive layer resin composition liquid, the same method as the method of applying the non-foaming layer resin composition liquid can be employed.
次いで、非発泡層から離型性基材を剥離する。離型性基材を剥離することで、非発泡層と発泡層と繊維質基材との積層体が得られる。
Then, the release base material is peeled off from the non-foamed layer. A laminate of the non-foamed layer, the foamed layer, and the fibrous base is obtained by peeling off the releasable base.
非発泡層上に保護層を形成する場合、上記のように離型性基材を剥離した後、積層体の表面に保護層を形成してもよい。保護層は、非発泡層上にアンダーコート層を介して設けてもよいもいいし、非発泡層上に直接積層してもよい。アンダーコート層用樹脂組成液を非発泡層の表面に塗布する方法は、特に限定されず、非発泡層用樹脂組成液を塗布する方法と同様の方法を用いることができる。
When the protective layer is formed on the non-foamed layer, the protective layer may be formed on the surface of the laminate after the release substrate is peeled off as described above. The protective layer may be provided on the non-foamed layer via an undercoat layer, or may be laminated directly on the non-foamed layer. The method for applying the resin composition liquid for the undercoat layer to the surface of the non-foaming layer is not particularly limited, and the same method as the method for applying the resin composition liquid for the non-foaming layer can be used.
保護層を形成するために、保護層用樹脂組成液を非発泡層又はアンダーコート層に塗布する方法としては、非発泡層用樹脂組成液を塗布する方法と同様の方法を採用することができる。このほかに、スプレーコーター、グラビアコーター、グラビアダイレクト印刷機、グラビアオフセット印刷機、スクリーン印刷機などの装置を用いて塗布する方法を採用することもできる。
As a method for applying the protective layer resin composition liquid to the non-foaming layer or the undercoat layer in order to form the protective layer, the same method as the method for applying the non-foaming layer resin composition liquid can be employed. . In addition, a coating method using a device such as a spray coater, a gravure coater, a gravure direct printer, a gravure offset printer, or a screen printer can also be employed.
次いで、必要により熱処理を行う。熱処理は、保護層用樹脂組成液中の溶媒を蒸発させ、樹脂を乾燥させるために行われる。また、熱処理によって架橋反応を起こす架橋剤を用いる場合や、二液硬化型の樹脂を用いる場合にあっては、熱処理は、反応を促進し、十分な強度を有する皮膜を形成するために行われる。
Next, heat treatment is performed if necessary. The heat treatment is performed to evaporate the solvent in the protective layer resin composition liquid and dry the resin. In addition, when using a cross-linking agent that causes a cross-linking reaction by heat treatment, or when using a two-component curing resin, the heat treatment is performed to promote the reaction and form a film having sufficient strength. .
次いで、必要により、非発泡層(保護層が形成されている場合は保護層)に、シボ模様などの凹凸模様を形成する。このように離型性基材の剥離後に凹凸模様を形成する方法としては、従来公知の種々の方法を採用することができ、特に限定されるものではない。例えば、エンボス加工、真空エンボス加工、ウエルダー加工、ピンソニック加工などを用いた方法を挙げることができる。
Next, if necessary, the non-foamed layer (protective layer if a protective layer is formed) is formed with an uneven pattern such as a embossed pattern. As a method for forming the concave-convex pattern after peeling off the releasable base material in this manner, various conventionally known methods can be employed, and there is no particular limitation. Examples thereof include methods using embossing, vacuum embossing, welding, and pinsonic processing.
かくして、一実施形態に係る合成皮革が得られる。ただし、本実施形態の合成皮革を製造するための方法は、上記方法に限定されるものではない。
Thus, a synthetic leather according to one embodiment is obtained. However, the method for producing the synthetic leather of this embodiment is not limited to the above method.
以下、実施例により本発明を更に詳しく説明するが、本発明は以下の実施例に限定されるものではない。
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.
各評価項目は、以下の方法に従った。
Each evaluation item was in accordance with the following method.
[耐油性]
幅25cm、長さ35cmの大きさでサンプルを採取した。水平に置いた幅150mm、長さ200mm、厚さ3mmのガラス板の上に、サンプルを載せた。幅20cm、長さ25cmの大きさの綿100%ガーゼ(株式会社大和工場製「ベスケア ガーゼ10m 300-10M」)を試験片の樹脂層(非発泡層又は保護層)の表面に4枚重ね、オレイン酸(ナカライテスク株式会社製「15745-55」)を綿100%ガーゼ越しに60mL滴下した。綿100%ガーゼ上に、幅150mm、長さ200mm、厚さ3mmのガラス板を載せた。これを80℃に調整された送風定温乾燥機(ADVANTEC社製「DRM620DD」)で72時間放置した。その後、ガラス板、綿100%ガーゼを取り除き、ワイパー紙(日本製紙クレシア株式会社製「キムワイプS-200」)を押し当て、余分なオレイン酸を除去した。 [Oil resistance]
Samples were taken at a size of 25 cm wide and 35 cm long. A sample was placed on a horizontally placed glass plate having a width of 150 mm, a length of 200 mm, and a thickness of 3 mm. Four sheets of 100% cotton gauze (“Bescare Gauze 10m 300-10M” manufactured by Yamato Factory Co., Ltd.) with a width of 20 cm and a length of 25 cm are stacked on the surface of the resin layer (non-foamed layer or protective layer) of the test piece, 60 mL of oleic acid (“15745-55” manufactured by Nacalai Tesque Co., Ltd.) was dropped through a 100% cotton gauze. A glass plate having a width of 150 mm, a length of 200 mm and a thickness of 3 mm was placed on 100% cotton gauze. This was left for 72 hours in a blower constant temperature dryer (“DRM620DD” manufactured by ADVANTEC) adjusted to 80°C. Thereafter, the glass plate and 100% cotton gauze were removed, and wiper paper (“Kimwipe S-200” manufactured by Nippon Paper Crecia Co., Ltd.) was pressed against the glass plate to remove excess oleic acid.
幅25cm、長さ35cmの大きさでサンプルを採取した。水平に置いた幅150mm、長さ200mm、厚さ3mmのガラス板の上に、サンプルを載せた。幅20cm、長さ25cmの大きさの綿100%ガーゼ(株式会社大和工場製「ベスケア ガーゼ10m 300-10M」)を試験片の樹脂層(非発泡層又は保護層)の表面に4枚重ね、オレイン酸(ナカライテスク株式会社製「15745-55」)を綿100%ガーゼ越しに60mL滴下した。綿100%ガーゼ上に、幅150mm、長さ200mm、厚さ3mmのガラス板を載せた。これを80℃に調整された送風定温乾燥機(ADVANTEC社製「DRM620DD」)で72時間放置した。その後、ガラス板、綿100%ガーゼを取り除き、ワイパー紙(日本製紙クレシア株式会社製「キムワイプS-200」)を押し当て、余分なオレイン酸を除去した。 [Oil resistance]
Samples were taken at a size of 25 cm wide and 35 cm long. A sample was placed on a horizontally placed glass plate having a width of 150 mm, a length of 200 mm, and a thickness of 3 mm. Four sheets of 100% cotton gauze (“Bescare Gauze 10m 300-10M” manufactured by Yamato Factory Co., Ltd.) with a width of 20 cm and a length of 25 cm are stacked on the surface of the resin layer (non-foamed layer or protective layer) of the test piece, 60 mL of oleic acid (“15745-55” manufactured by Nacalai Tesque Co., Ltd.) was dropped through a 100% cotton gauze. A glass plate having a width of 150 mm, a length of 200 mm and a thickness of 3 mm was placed on 100% cotton gauze. This was left for 72 hours in a blower constant temperature dryer (“DRM620DD” manufactured by ADVANTEC) adjusted to 80°C. Thereafter, the glass plate and 100% cotton gauze were removed, and wiper paper (“Kimwipe S-200” manufactured by Nippon Paper Crecia Co., Ltd.) was pressed against the glass plate to remove excess oleic acid.
得られた耐油性試験後のサンプルの中央部から、幅30mm、長さ120mmの大きさの試験片を、タテ方向(長手方向)及びヨコ方向(幅方向)それぞれ2枚を採取した。同方向から採取した試験片を樹脂層表面が内側になるようにして重ね合わせ、スコット式もみ試験機(スコット耐揉試験機「CV-10N」、株式会社大栄科学精器製作所製)につかみ間隔30mmではさんだ。2枚の試験片が互いに開いて分離した状態になるように、つかみ具の間隔を次第にせばめた。試験片の樹脂層表面が軽く触れてから、荷重9.8Nをかけた。試験機を動かし、荷重9.8N、つかみ間隔30mm、もみストローク50mmで、2000回、もみ試験を実施した後、試験片の状態を観察し、下記基準に従って判定をした。
(判定基準)
A:樹脂層の剥離、亀裂がない
B:樹脂層の剥離、亀裂のうち、いずれか一つ以上あり Two test pieces each having a width of 30 mm and a length of 120 mm were taken from the central portion of the obtained sample after the oil resistance test in the vertical direction (longitudinal direction) and the horizontal direction (width direction). The test pieces collected from the same direction are superimposed so that the resin layer surface faces inside, and the Scott type kneading tester (Scott rubbing resistance tester "CV-10N", manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) is gripped at intervals. Sandwiched with 30 mm. Gradually the gap between the grips was reduced so that the two specimens were separated from each other. After lightly touching the resin layer surface of the test piece, a load of 9.8 N was applied. The testing machine was moved, and the rubbing test was performed 2000 times with a load of 9.8N, a gripping distance of 30mm, and a rubbing stroke of 50mm.
(criterion)
A: No peeling or cracking of the resin layer B: At least one of peeling and cracking of the resin layer
(判定基準)
A:樹脂層の剥離、亀裂がない
B:樹脂層の剥離、亀裂のうち、いずれか一つ以上あり Two test pieces each having a width of 30 mm and a length of 120 mm were taken from the central portion of the obtained sample after the oil resistance test in the vertical direction (longitudinal direction) and the horizontal direction (width direction). The test pieces collected from the same direction are superimposed so that the resin layer surface faces inside, and the Scott type kneading tester (Scott rubbing resistance tester "CV-10N", manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) is gripped at intervals. Sandwiched with 30 mm. Gradually the gap between the grips was reduced so that the two specimens were separated from each other. After lightly touching the resin layer surface of the test piece, a load of 9.8 N was applied. The testing machine was moved, and the rubbing test was performed 2000 times with a load of 9.8N, a gripping distance of 30mm, and a rubbing stroke of 50mm.
(criterion)
A: No peeling or cracking of the resin layer B: At least one of peeling and cracking of the resin layer
[耐摩耗性]
幅70mm、長さ300mmの大きさの試験片をタテ、ヨコ各方向からそれぞれ1枚採取し、裏面に幅70mm、長さ300mm、厚さ10mmの大きさのウレタンフォームを添えた。ウレタンフォームの下面中央に直径4.5mmのワイヤーを設置した状態で、平面摩耗試験機「T-TYPE」(株式会社大栄科学精器製作所製)に固定し、綿布をかぶせた摩耗子がワイヤー上をワイヤーと平行に往復動するように、該摩擦子に荷重9.8Nを掛けて摩耗試験を行った。摩擦子は試験片の表面上140mmの間を60往復/分の速さで10,000回往復させた。摩耗試験後の試験片の表面状態を観察し、下記の基準に従って判定した。
(判定基準)
5:外観に変化なし(亀裂、破れがない)
4:わずかに摩耗が認められるが、目立たないもの
3:摩耗が明らかに認められるもの
2:繊維質基材の露出があるもの
1:繊維質基材の露出が著しいもの(破れが認められる) [Abrasion resistance]
A test piece having a width of 70 mm and a length of 300 mm was taken from each of the vertical and horizontal directions, and a urethane foam having a width of 70 mm, a length of 300 mm and a thickness of 10 mm was attached to the back surface. A wire with a diameter of 4.5 mm was installed in the center of the lower surface of the urethane foam, and it was fixed to a flat abrasion tester "T-TYPE" (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), and an abrading element covered with cotton cloth was placed on the wire. A wear test was performed by applying a load of 9.8 N to the friction element so that the friction element reciprocated in parallel with the wire. The friction element was reciprocated 10,000 times at a speed of 60 reciprocations/minute over a distance of 140 mm above the surface of the test piece. After the wear test, the surface condition of the test piece was observed and evaluated according to the following criteria.
(criterion)
5: No change in appearance (no cracks or breaks)
4: Slight but inconspicuous wear 3: Clear wear 2: Exposed fibrous base material 1: Exposed fibrous base material (tears observed)
幅70mm、長さ300mmの大きさの試験片をタテ、ヨコ各方向からそれぞれ1枚採取し、裏面に幅70mm、長さ300mm、厚さ10mmの大きさのウレタンフォームを添えた。ウレタンフォームの下面中央に直径4.5mmのワイヤーを設置した状態で、平面摩耗試験機「T-TYPE」(株式会社大栄科学精器製作所製)に固定し、綿布をかぶせた摩耗子がワイヤー上をワイヤーと平行に往復動するように、該摩擦子に荷重9.8Nを掛けて摩耗試験を行った。摩擦子は試験片の表面上140mmの間を60往復/分の速さで10,000回往復させた。摩耗試験後の試験片の表面状態を観察し、下記の基準に従って判定した。
(判定基準)
5:外観に変化なし(亀裂、破れがない)
4:わずかに摩耗が認められるが、目立たないもの
3:摩耗が明らかに認められるもの
2:繊維質基材の露出があるもの
1:繊維質基材の露出が著しいもの(破れが認められる) [Abrasion resistance]
A test piece having a width of 70 mm and a length of 300 mm was taken from each of the vertical and horizontal directions, and a urethane foam having a width of 70 mm, a length of 300 mm and a thickness of 10 mm was attached to the back surface. A wire with a diameter of 4.5 mm was installed in the center of the lower surface of the urethane foam, and it was fixed to a flat abrasion tester "T-TYPE" (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), and an abrading element covered with cotton cloth was placed on the wire. A wear test was performed by applying a load of 9.8 N to the friction element so that the friction element reciprocated in parallel with the wire. The friction element was reciprocated 10,000 times at a speed of 60 reciprocations/minute over a distance of 140 mm above the surface of the test piece. After the wear test, the surface condition of the test piece was observed and evaluated according to the following criteria.
(criterion)
5: No change in appearance (no cracks or breaks)
4: Slight but inconspicuous wear 3: Clear wear 2: Exposed fibrous base material 1: Exposed fibrous base material (tears observed)
[加工性]
非発泡層用樹脂組成液及び発泡層用樹脂組成液の粘度をBII形粘度計(BHII型、東機産業株式会社製、ローターNo.3、10rpm、23℃)で測定し、下記の基準に従って判定した。Aであれば加工性に優れる。
(判定基準)
A:2000~6000mPa・s
B:2000mPa・s未満又は6000mPa・s超え [Workability]
The viscosities of the resin composition liquid for the non-foaming layer and the resin composition liquid for the foaming layer are measured with a BII type viscometer (BHII type, manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23 ° C.), and are measured according to the following criteria. Judged. If it is A, it is excellent in workability.
(criterion)
A: 2000-6000 mPa·s
B: less than 2000 mPa s or more than 6000 mPa s
非発泡層用樹脂組成液及び発泡層用樹脂組成液の粘度をBII形粘度計(BHII型、東機産業株式会社製、ローターNo.3、10rpm、23℃)で測定し、下記の基準に従って判定した。Aであれば加工性に優れる。
(判定基準)
A:2000~6000mPa・s
B:2000mPa・s未満又は6000mPa・s超え [Workability]
The viscosities of the resin composition liquid for the non-foaming layer and the resin composition liquid for the foaming layer are measured with a BII type viscometer (BHII type, manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23 ° C.), and are measured according to the following criteria. Judged. If it is A, it is excellent in workability.
(criterion)
A: 2000-6000 mPa·s
B: less than 2000 mPa s or more than 6000 mPa s
[風合い]
パネラーによる官能評価を行い、下記の基準に従って判定した。B以上で合格である。
(判定基準)
A:風合いが柔軟
B:風合いがやや粗硬
C:風合いが粗硬 [Texture]
A sensory evaluation was conducted by a panelist, and judgment was made according to the following criteria. A score of B or higher is acceptable.
(criterion)
A: Soft texture B: Slightly rough texture C: Rough and hard texture
パネラーによる官能評価を行い、下記の基準に従って判定した。B以上で合格である。
(判定基準)
A:風合いが柔軟
B:風合いがやや粗硬
C:風合いが粗硬 [Texture]
A sensory evaluation was conducted by a panelist, and judgment was made according to the following criteria. A score of B or higher is acceptable.
(criterion)
A: Soft texture B: Slightly rough texture C: Rough and hard texture
[実施例1]
<繊維質基材>
基材として、丸編地(ポリエステル繊維、厚さ580μm、単位面積当たりの質量120g/m2)を準備した。 [Example 1]
<Fibrous base material>
A circular knitted fabric (polyester fiber, thickness 580 μm, mass per unit area 120 g/m 2 ) was prepared as a base material.
<繊維質基材>
基材として、丸編地(ポリエステル繊維、厚さ580μm、単位面積当たりの質量120g/m2)を準備した。 [Example 1]
<Fibrous base material>
A circular knitted fabric (polyester fiber, thickness 580 μm, mass per unit area 120 g/m 2 ) was prepared as a base material.
<処方1:非発泡層用樹脂組成液>
・塩化ビニル系樹脂(ポリ塩化ビニル、平均重合度1300のペーストレジン、固形分100質量%):100質量部
・フタル酸エステル系可塑剤(フタル酸ジアルキル(C9~C11)、固形分100質量%):65質量部
・ポリエステル系可塑剤(アジピン酸と1,3-ブタンジオール及び1,4-ブタンジオールとを重縮合させて得られるアジピン酸系ポリエステル、数平均分子量1800、粘度(25℃)3000mPa・s、固形分100質量%):10質量部
・Ca-Zn系熱安定剤(有機酸カルシウム塩/有機酸亜鉛塩、固形分100質量%):2質量部
・顔料(カーボンブラック、固形分100質量%):7質量部
・耐アミン剤(過塩素酸ナトリウム、固形分100質量%):0.5質量部
調製法:塩化ビニル系樹脂及び可塑剤を混合した後、Ca-Zn系熱安定剤、顔料、耐アミン剤を添加・混合して、非発泡層用樹脂組成液を得た。非発泡層用樹脂組成液の粘度(23℃)は4000mPa・sであった。 <Prescription 1: Resin composition liquid for non-foaming layer>
・Vinyl chloride resin (polyvinyl chloride, paste resin with an average degree of polymerization of 1300, solid content 100% by mass): 100 parts by mass ・Phthalic acid ester plasticizer (dialkyl phthalate (C9-C11), solid content 100% by mass ): 65 parts by mass Polyester plasticizer (adipic acid polyester obtained by polycondensation of adipic acid and 1,3-butanediol and 1,4-butanediol, number average molecular weight 1800, viscosity (25°C) 3000 mPa s, solid content 100% by mass): 10 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Pigment (carbon black, solid content minute 100% by mass): 7 parts by mass Amine-resistant agent (sodium perchlorate, solid content 100% by mass): 0.5 parts by mass Preparation method: After mixing vinyl chloride resin and plasticizer, Ca-Zn-based A heat stabilizer, a pigment, and an anti-amine agent were added and mixed to obtain a resin composition liquid for a non-foaming layer. The viscosity (23° C.) of the resin composition liquid for the non-foaming layer was 4000 mPa·s.
・塩化ビニル系樹脂(ポリ塩化ビニル、平均重合度1300のペーストレジン、固形分100質量%):100質量部
・フタル酸エステル系可塑剤(フタル酸ジアルキル(C9~C11)、固形分100質量%):65質量部
・ポリエステル系可塑剤(アジピン酸と1,3-ブタンジオール及び1,4-ブタンジオールとを重縮合させて得られるアジピン酸系ポリエステル、数平均分子量1800、粘度(25℃)3000mPa・s、固形分100質量%):10質量部
・Ca-Zn系熱安定剤(有機酸カルシウム塩/有機酸亜鉛塩、固形分100質量%):2質量部
・顔料(カーボンブラック、固形分100質量%):7質量部
・耐アミン剤(過塩素酸ナトリウム、固形分100質量%):0.5質量部
調製法:塩化ビニル系樹脂及び可塑剤を混合した後、Ca-Zn系熱安定剤、顔料、耐アミン剤を添加・混合して、非発泡層用樹脂組成液を得た。非発泡層用樹脂組成液の粘度(23℃)は4000mPa・sであった。 <Prescription 1: Resin composition liquid for non-foaming layer>
・Vinyl chloride resin (polyvinyl chloride, paste resin with an average degree of polymerization of 1300, solid content 100% by mass): 100 parts by mass ・Phthalic acid ester plasticizer (dialkyl phthalate (C9-C11), solid content 100% by mass ): 65 parts by mass Polyester plasticizer (adipic acid polyester obtained by polycondensation of adipic acid and 1,3-butanediol and 1,4-butanediol, number average molecular weight 1800, viscosity (25°C) 3000 mPa s, solid content 100% by mass): 10 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Pigment (carbon black, solid content minute 100% by mass): 7 parts by mass Amine-resistant agent (sodium perchlorate, solid content 100% by mass): 0.5 parts by mass Preparation method: After mixing vinyl chloride resin and plasticizer, Ca-Zn-based A heat stabilizer, a pigment, and an anti-amine agent were added and mixed to obtain a resin composition liquid for a non-foaming layer. The viscosity (23° C.) of the resin composition liquid for the non-foaming layer was 4000 mPa·s.
<処方2:発泡層用樹脂組成液>
・塩化ビニル系樹脂(ポリ塩化ビニル、平均重合度1300のペーストレジン、固形分100質量%):100質量部
・フタル酸エステル系可塑剤(フタル酸ジアルキル(C9~C11)、固形分100質量%):65質量部
・ポリエステル系可塑剤(アジピン酸と1,3-ブタンジオール及び1,4-ブタンジオールとを重縮合させて得られるアジピン酸系ポリエステル、数平均分子量1800、粘度(25℃)3000mPa・s、固形分100質量%):10質量部
・Ca-Zn系熱安定剤(有機酸カルシウム塩/有機酸亜鉛塩、固形分100質量%):2質量部
・顔料(カーボンブラック、固形分100質量%):3質量部
・耐アミン剤(過塩素酸ナトリウム、固形分100質量%):1質量部
・有機系発泡剤(アゾジカルボンアミド、固形分60質量%):1質量部
調製法:塩化ビニル系樹脂及び可塑剤を混合した後、Ca-Zn系熱安定剤、顔料、耐アミン剤、有機系発泡剤を添加・混合して、発泡層用樹脂組成液を得た。発泡層用樹脂組成液の粘度(23℃)は4000mPa・sであった。 <Prescription 2: Resin composition liquid for foam layer>
・Vinyl chloride resin (polyvinyl chloride, paste resin with an average degree of polymerization of 1300, solid content 100% by mass): 100 parts by mass ・Phthalic acid ester plasticizer (dialkyl phthalate (C9-C11), solid content 100% by mass ): 65 parts by mass Polyester plasticizer (adipic acid polyester obtained by polycondensation of adipic acid and 1,3-butanediol and 1,4-butanediol, number average molecular weight 1800, viscosity (25°C) 3000 mPa s, solid content 100% by mass): 10 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Pigment (carbon black, solid content minute 100% by mass): 3 parts Amine-resistant agent (sodium perchlorate, solid content 100% by mass): 1 part Organic blowing agent (azodicarbonamide, solid content 60% by mass): 1 part by mass Preparation Method: After mixing a vinyl chloride resin and a plasticizer, a Ca—Zn heat stabilizer, a pigment, an anti-amine agent, and an organic foaming agent were added and mixed to obtain a resin composition liquid for a foam layer. The viscosity (23° C.) of the resin composition liquid for the foam layer was 4000 mPa·s.
・塩化ビニル系樹脂(ポリ塩化ビニル、平均重合度1300のペーストレジン、固形分100質量%):100質量部
・フタル酸エステル系可塑剤(フタル酸ジアルキル(C9~C11)、固形分100質量%):65質量部
・ポリエステル系可塑剤(アジピン酸と1,3-ブタンジオール及び1,4-ブタンジオールとを重縮合させて得られるアジピン酸系ポリエステル、数平均分子量1800、粘度(25℃)3000mPa・s、固形分100質量%):10質量部
・Ca-Zn系熱安定剤(有機酸カルシウム塩/有機酸亜鉛塩、固形分100質量%):2質量部
・顔料(カーボンブラック、固形分100質量%):3質量部
・耐アミン剤(過塩素酸ナトリウム、固形分100質量%):1質量部
・有機系発泡剤(アゾジカルボンアミド、固形分60質量%):1質量部
調製法:塩化ビニル系樹脂及び可塑剤を混合した後、Ca-Zn系熱安定剤、顔料、耐アミン剤、有機系発泡剤を添加・混合して、発泡層用樹脂組成液を得た。発泡層用樹脂組成液の粘度(23℃)は4000mPa・sであった。 <Prescription 2: Resin composition liquid for foam layer>
・Vinyl chloride resin (polyvinyl chloride, paste resin with an average degree of polymerization of 1300, solid content 100% by mass): 100 parts by mass ・Phthalic acid ester plasticizer (dialkyl phthalate (C9-C11), solid content 100% by mass ): 65 parts by mass Polyester plasticizer (adipic acid polyester obtained by polycondensation of adipic acid and 1,3-butanediol and 1,4-butanediol, number average molecular weight 1800, viscosity (25°C) 3000 mPa s, solid content 100% by mass): 10 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Pigment (carbon black, solid content minute 100% by mass): 3 parts Amine-resistant agent (sodium perchlorate, solid content 100% by mass): 1 part Organic blowing agent (azodicarbonamide, solid content 60% by mass): 1 part by mass Preparation Method: After mixing a vinyl chloride resin and a plasticizer, a Ca—Zn heat stabilizer, a pigment, an anti-amine agent, and an organic foaming agent were added and mixed to obtain a resin composition liquid for a foam layer. The viscosity (23° C.) of the resin composition liquid for the foam layer was 4000 mPa·s.
<処方3:接着層用樹脂組成液>
・塩化ビニル系樹脂(水酸基を持つモノマーを共重合してなる水酸基含有ポリ塩化ビニル樹脂、平均重合度1300、固形分100質量%):100質量部
・可塑剤(フタル酸ジアルキル(C9~C11)、固形分100質量%):100質量部
・Ca-Zn系熱安定剤(有機酸カルシウム塩/有機酸亜鉛塩、固形分100質量%):2質量部
・難燃剤(三酸化アンチモン、固形分100質量%):8質量部
・架橋剤(イソシアネート系架橋剤、固形分100質量%):6.5質量部
調製法:塩化ビニル系樹脂及び可塑剤を混合した後、Ca-Zn系熱安定剤、難燃剤を添加・混合し、更に架橋剤を添加・混合して、接着層用樹脂組成液を得た。接着層用樹脂組成液の粘度は65000mPa・s(BII形粘度計(BHII型)、東機産業株式会社製、ローターNo.6、10rpm、23℃)であった。 <Prescription 3: Resin composition liquid for adhesive layer>
・ Vinyl chloride resin (hydroxyl group-containing polyvinyl chloride resin obtained by copolymerizing a monomer having a hydroxyl group, average polymerization degree 1300, solid content 100% by mass): 100 parts by mass ・ Plasticizer (dialkyl phthalate (C9 to C11) , solid content 100% by mass): 100 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Flame retardant (antimony trioxide, solid content 100% by mass): 8 parts by mass Cross-linking agent (isocyanate-based cross-linking agent, solid content 100% by mass): 6.5 parts by mass Preparation method: After mixing vinyl chloride resin and plasticizer, Ca-Zn-based heat stabilization A resin composition liquid for an adhesive layer was obtained by adding and mixing an agent and a flame retardant, and then adding and mixing a cross-linking agent. The viscosity of the adhesive layer resin composition liquid was 65000 mPa·s (BII viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 6, 10 rpm, 23° C.).
・塩化ビニル系樹脂(水酸基を持つモノマーを共重合してなる水酸基含有ポリ塩化ビニル樹脂、平均重合度1300、固形分100質量%):100質量部
・可塑剤(フタル酸ジアルキル(C9~C11)、固形分100質量%):100質量部
・Ca-Zn系熱安定剤(有機酸カルシウム塩/有機酸亜鉛塩、固形分100質量%):2質量部
・難燃剤(三酸化アンチモン、固形分100質量%):8質量部
・架橋剤(イソシアネート系架橋剤、固形分100質量%):6.5質量部
調製法:塩化ビニル系樹脂及び可塑剤を混合した後、Ca-Zn系熱安定剤、難燃剤を添加・混合し、更に架橋剤を添加・混合して、接着層用樹脂組成液を得た。接着層用樹脂組成液の粘度は65000mPa・s(BII形粘度計(BHII型)、東機産業株式会社製、ローターNo.6、10rpm、23℃)であった。 <Prescription 3: Resin composition liquid for adhesive layer>
・ Vinyl chloride resin (hydroxyl group-containing polyvinyl chloride resin obtained by copolymerizing a monomer having a hydroxyl group, average polymerization degree 1300, solid content 100% by mass): 100 parts by mass ・ Plasticizer (dialkyl phthalate (C9 to C11) , solid content 100% by mass): 100 parts Ca-Zn-based heat stabilizer (organic acid calcium salt / organic acid zinc salt, solid content 100% by mass): 2 parts by mass Flame retardant (antimony trioxide, solid content 100% by mass): 8 parts by mass Cross-linking agent (isocyanate-based cross-linking agent, solid content 100% by mass): 6.5 parts by mass Preparation method: After mixing vinyl chloride resin and plasticizer, Ca-Zn-based heat stabilization A resin composition liquid for an adhesive layer was obtained by adding and mixing an agent and a flame retardant, and then adding and mixing a cross-linking agent. The viscosity of the adhesive layer resin composition liquid was 65000 mPa·s (BII viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 6, 10 rpm, 23° C.).
<処方4:アンダーコート層用樹脂組成液>
・ポリウレタン樹脂(ポリエステル系ポリウレタン樹脂の水分散液、固形分20.5質量%):100質量部
・架橋剤(イソシアネート系架橋剤の水分散液、固形分50質量%):2質量部
調製法:ポリウレタン樹脂に架橋剤を添加し、混合して、アンダーコート層用樹脂組成液を得た。アンダーコート層用樹脂組成液の粘度は3000mPa・s(BII形粘度計(BHII型)、東機産業株式会社製、ローターNo.3、10rpm、23℃)であった。 <Prescription 4: Resin composition liquid for undercoat layer>
・Polyurethane resin (aqueous dispersion of polyester polyurethane resin, solid content 20.5% by mass): 100 parts ・Crosslinking agent (aqueous dispersion of isocyanate-based crosslinker, solid content 50% by mass): 2 parts by mass Preparation method : A cross-linking agent was added to a polyurethane resin and mixed to obtain a resin composition liquid for an undercoat layer. The viscosity of the undercoat layer resin composition liquid was 3000 mPa·s (BII type viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23° C.).
・ポリウレタン樹脂(ポリエステル系ポリウレタン樹脂の水分散液、固形分20.5質量%):100質量部
・架橋剤(イソシアネート系架橋剤の水分散液、固形分50質量%):2質量部
調製法:ポリウレタン樹脂に架橋剤を添加し、混合して、アンダーコート層用樹脂組成液を得た。アンダーコート層用樹脂組成液の粘度は3000mPa・s(BII形粘度計(BHII型)、東機産業株式会社製、ローターNo.3、10rpm、23℃)であった。 <Prescription 4: Resin composition liquid for undercoat layer>
・Polyurethane resin (aqueous dispersion of polyester polyurethane resin, solid content 20.5% by mass): 100 parts ・Crosslinking agent (aqueous dispersion of isocyanate-based crosslinker, solid content 50% by mass): 2 parts by mass Preparation method : A cross-linking agent was added to a polyurethane resin and mixed to obtain a resin composition liquid for an undercoat layer. The viscosity of the undercoat layer resin composition liquid was 3000 mPa·s (BII type viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23° C.).
<処方5:保護層用樹脂組成液>
・ポリウレタン樹脂(ポリカーボネート系ポリウレタン樹脂の水分散液、固形分30質量%):100質量部
・架橋剤(カルボジイミド系架橋剤の水分散液、固形分49.5質量%):2質量部
・滑剤(シリコーン樹脂の水分散液、固形分40質量部):6質量部
調製法:ポリウレタン樹脂に滑剤を混合した後、架橋剤を添加・混合して、保護層用樹脂組成液を得た。保護層用樹脂組成液の粘度は1000mPa・s(BII形粘度計(BHII型)、東機産業株式会社製、ローターNo.3、10rpm、23℃)であった。 <Prescription 5: Resin composition liquid for protective layer>
Polyurethane resin (aqueous dispersion of polycarbonate-based polyurethane resin, solid content 30% by mass): 100 parts by mass Crosslinking agent (aqueous dispersion of carbodiimide-based cross-linking agent, solid content 49.5% by mass): 2 parts by mass Lubricant (Aqueous dispersion of silicone resin, solid content: 40 parts by mass): 6 parts by mass Preparation method: After mixing a lubricant with a polyurethane resin, a cross-linking agent was added and mixed to obtain a protective layer resin composition liquid. The viscosity of the protective layer resin composition liquid was 1000 mPa·s (BII viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23° C.).
・ポリウレタン樹脂(ポリカーボネート系ポリウレタン樹脂の水分散液、固形分30質量%):100質量部
・架橋剤(カルボジイミド系架橋剤の水分散液、固形分49.5質量%):2質量部
・滑剤(シリコーン樹脂の水分散液、固形分40質量部):6質量部
調製法:ポリウレタン樹脂に滑剤を混合した後、架橋剤を添加・混合して、保護層用樹脂組成液を得た。保護層用樹脂組成液の粘度は1000mPa・s(BII形粘度計(BHII型)、東機産業株式会社製、ローターNo.3、10rpm、23℃)であった。 <Prescription 5: Resin composition liquid for protective layer>
Polyurethane resin (aqueous dispersion of polycarbonate-based polyurethane resin, solid content 30% by mass): 100 parts by mass Crosslinking agent (aqueous dispersion of carbodiimide-based cross-linking agent, solid content 49.5% by mass): 2 parts by mass Lubricant (Aqueous dispersion of silicone resin, solid content: 40 parts by mass): 6 parts by mass Preparation method: After mixing a lubricant with a polyurethane resin, a cross-linking agent was added and mixed to obtain a protective layer resin composition liquid. The viscosity of the protective layer resin composition liquid was 1000 mPa·s (BII viscometer (BHII type), manufactured by Toki Sangyo Co., Ltd., rotor No. 3, 10 rpm, 23° C.).
<合成皮革の作製>
上述の処方1に従い調製した非発泡層用樹脂組成液を、フラットな離型紙(商品名「VX-12」、リンテック株式会社製)に、コンマコーターにて塗布厚さが160μmになるようにシート状に塗布し、乾燥機にて180℃で2分30秒間熱処理して、非発泡層を形成した。 <Production of synthetic leather>
The non-foaming layer resin composition liquid prepared according to theabove recipe 1 is coated on a flat release paper (trade name “VX-12”, manufactured by Lintec Corporation) with a comma coater so that the thickness is 160 μm. and heat-treated in a dryer at 180° C. for 2 minutes and 30 seconds to form a non-foaming layer.
上述の処方1に従い調製した非発泡層用樹脂組成液を、フラットな離型紙(商品名「VX-12」、リンテック株式会社製)に、コンマコーターにて塗布厚さが160μmになるようにシート状に塗布し、乾燥機にて180℃で2分30秒間熱処理して、非発泡層を形成した。 <Production of synthetic leather>
The non-foaming layer resin composition liquid prepared according to the
次いで、上述の処方2に従い調製した発泡層用樹脂組成液を、離型紙上に形成された非発泡層上に、コンマコーターにて塗布厚さが140μmになるようにシート状に塗布し、乾燥機にて200℃で2分30秒間熱処理して、発泡層を形成した。
Next, the foamed layer resin composition liquid prepared according to Formulation 2 above is coated on the non-foamed layer formed on the release paper with a comma coater so that the coating thickness becomes 140 μm in a sheet form, and dried. A foam layer was formed by heat-treating at 200° C. for 2 minutes and 30 seconds using a machine.
次いで、上述の処方3に従い調製した接着層用樹脂組成液を、発泡層上に、ナイフコーターにて塗布厚さが90μmになるようにシート状に塗布した。その後、繊維質基材を重ねて、乾燥機にて180℃で2分30秒間処理して接着層の形成及び繊維質基材との貼り合わせを実施した。その後、離型紙を剥離し、非発泡層、発泡層、接着層、及び繊維質基材からなる積層体を得た。
Next, the adhesive layer resin composition liquid prepared according to Formulation 3 above was coated on the foam layer in a sheet form with a knife coater so that the coating thickness was 90 μm. After that, the fibrous base material was superimposed and treated in a dryer at 180° C. for 2 minutes and 30 seconds to form an adhesive layer and bond with the fibrous base material. After that, the release paper was peeled off to obtain a laminate composed of a non-foamed layer, a foamed layer, an adhesive layer, and a fibrous base material.
次いで、上述の処方4に従い調製したアンダーコート層用樹脂組成液を、離型紙を剥離した後の非発泡層の表面に、グラビアコーターにて塗布厚さが12μmになるようにシート状に塗布し、乾燥機にて130℃で2分間熱処理して、アンダーコート層を形成した。
Next, the undercoat layer resin composition liquid prepared according to Formulation 4 above was coated on the surface of the non-foamed layer after peeling off the release paper in a sheet form with a gravure coater so that the coating thickness was 12 μm. and heat-treated at 130° C. for 2 minutes in a dryer to form an undercoat layer.
次いで、上述の処方5に従い調製した保護層用樹脂組成液を、アンダーコート層の表面に、グラビアコーターにて塗布厚さが15μmになるようにシート状に塗布し、乾燥機にて130℃で1分間熱処理して、保護層を形成した。
Next, the protective layer resin composition solution prepared according to Formulation 5 above was applied to the surface of the undercoat layer in the form of a sheet using a gravure coater so that the coating thickness was 15 μm. A heat treatment was performed for 1 minute to form a protective layer.
次いで、得られた積層体を赤外線ヒーターにて170℃で15秒間予備加熱した後、真空エンボス機にて保護層のオモテ面にシボ模様を形成し、実施例1の合成皮革を得た。非発泡層の厚さは160μmであり、発泡層の発泡倍率は1.5倍、発泡層の厚さは210μmであった。
Next, after preheating the obtained laminate at 170°C for 15 seconds with an infrared heater, a grain pattern was formed on the front surface of the protective layer with a vacuum embossing machine to obtain the synthetic leather of Example 1. The non-foamed layer had a thickness of 160 μm, the foamed layer had an expansion ratio of 1.5, and the foamed layer had a thickness of 210 μm.
各樹脂層の厚さは、合成皮革の垂直断面をマイクロスコープ(キーエンス株式会社製、デジタルHFマイクロスコープVH-8000)で観察し、任意の10か所についての厚さを測定し、これらの平均値を算出することにより得られる値である。
The thickness of each resin layer is obtained by observing the vertical cross section of the synthetic leather with a microscope (manufactured by Keyence Corporation, Digital HF Microscope VH-8000), measuring the thickness at any 10 points, and averaging these It is a value obtained by calculating the value.
発泡層の発泡倍率は、発泡層用樹脂組成液を離型紙上にコンマコーターにて塗布厚が140μmとなるようにシート状に塗布した後、200℃で2分30秒間乾燥した。得られた発泡シートの膜厚を測定し、次式により算出した。
発泡倍率(倍)=発泡シートの膜厚/{塗布厚(140μm)×発泡層用樹脂組成液の固形分率} The expansion ratio of the foam layer was determined by coating the resin composition liquid for the foam layer on release paper with a comma coater in the form of a sheet to a coating thickness of 140 μm, followed by drying at 200° C. for 2 minutes and 30 seconds. The thickness of the obtained foamed sheet was measured and calculated by the following formula.
Expansion ratio (times)=film thickness of foam sheet/{coating thickness (140 μm)×solid content of resin composition liquid for foam layer}
発泡倍率(倍)=発泡シートの膜厚/{塗布厚(140μm)×発泡層用樹脂組成液の固形分率} The expansion ratio of the foam layer was determined by coating the resin composition liquid for the foam layer on release paper with a comma coater in the form of a sheet to a coating thickness of 140 μm, followed by drying at 200° C. for 2 minutes and 30 seconds. The thickness of the obtained foamed sheet was measured and calculated by the following formula.
Expansion ratio (times)=film thickness of foam sheet/{coating thickness (140 μm)×solid content of resin composition liquid for foam layer}
[実施例2~14、比較例1~6]
各樹脂層用樹脂組成物の処方を表1~4のように変更した以外は全て実施例1と同様にして合成皮革を得た。表1~4中の固形分について「%」は質量%である。なお、ポリエステル系可塑剤について、表1~4中のアジピン酸系ポリエステルの粘度と数平均分子量は表1~4中に記載のとおりである。詳細には、表1~4中のアジピン酸系ポリエステルは、いずれもアジピン酸と1,3-ブタンジオール及び1,4-ブタンジオールとを重縮合させて得られたものである。実施例7では数平均分子量が800で粘度(25℃)200mPa・sのアジピン酸系ポリエステルを用いた。実施例8では数平均分子量が2200で粘度(25℃)5000mPa・sのアジピン酸系ポリエステルを用いた。その他の実施例及び比較例で用いたアジピン酸系ポリエステルは実施例1と同じ上記のとおりである。 [Examples 2 to 14, Comparative Examples 1 to 6]
A synthetic leather was obtained in the same manner as in Example 1, except that the formulation of the resin composition for each resin layer was changed as shown in Tables 1 to 4. "%" for the solid content in Tables 1 to 4 is mass%. Regarding the polyester plasticizer, the viscosity and number average molecular weight of the adipic acid-based polyester in Tables 1-4 are as shown in Tables 1-4. Specifically, the adipic acid-based polyesters in Tables 1 to 4 are all obtained by polycondensing adipic acid with 1,3-butanediol and 1,4-butanediol. In Example 7, an adipic acid-based polyester having a number average molecular weight of 800 and a viscosity (25° C.) of 200 mPa·s was used. In Example 8, an adipic acid-based polyester having a number average molecular weight of 2,200 and a viscosity (25° C.) of 5,000 mPa·s was used. The adipic acid-based polyesters used in other examples and comparative examples are the same as in Example 1, as described above.
各樹脂層用樹脂組成物の処方を表1~4のように変更した以外は全て実施例1と同様にして合成皮革を得た。表1~4中の固形分について「%」は質量%である。なお、ポリエステル系可塑剤について、表1~4中のアジピン酸系ポリエステルの粘度と数平均分子量は表1~4中に記載のとおりである。詳細には、表1~4中のアジピン酸系ポリエステルは、いずれもアジピン酸と1,3-ブタンジオール及び1,4-ブタンジオールとを重縮合させて得られたものである。実施例7では数平均分子量が800で粘度(25℃)200mPa・sのアジピン酸系ポリエステルを用いた。実施例8では数平均分子量が2200で粘度(25℃)5000mPa・sのアジピン酸系ポリエステルを用いた。その他の実施例及び比較例で用いたアジピン酸系ポリエステルは実施例1と同じ上記のとおりである。 [Examples 2 to 14, Comparative Examples 1 to 6]
A synthetic leather was obtained in the same manner as in Example 1, except that the formulation of the resin composition for each resin layer was changed as shown in Tables 1 to 4. "%" for the solid content in Tables 1 to 4 is mass%. Regarding the polyester plasticizer, the viscosity and number average molecular weight of the adipic acid-based polyester in Tables 1-4 are as shown in Tables 1-4. Specifically, the adipic acid-based polyesters in Tables 1 to 4 are all obtained by polycondensing adipic acid with 1,3-butanediol and 1,4-butanediol. In Example 7, an adipic acid-based polyester having a number average molecular weight of 800 and a viscosity (25° C.) of 200 mPa·s was used. In Example 8, an adipic acid-based polyester having a number average molecular weight of 2,200 and a viscosity (25° C.) of 5,000 mPa·s was used. The adipic acid-based polyesters used in other examples and comparative examples are the same as in Example 1, as described above.
実施例1~14及び比較例1~6についての評価結果は表1~4に示す通りである。比較例1では、非発泡層及び発泡層に含まれるフタル酸エステル系可塑剤とポリエステル系可塑剤との質量比が93:7であり、フタル酸エステル系可塑剤の配合量が多いため、耐油性が劣っていた。比較例3~5では、非発泡層及び/又は発泡層にフタル酸エステル系可塑剤のみ含まれているため、耐油性が劣っていた。比較例2は、非発泡層及び発泡層に含まれるフタル酸エステル系可塑剤とポリエステル系可塑剤との質量比が67:33であり、ポリエステル系可塑剤の含有量が多いため、耐油性には優れていたものの、泡かみが生じ、加工性が劣っていた。比較例6では、可塑剤の含有量が少なく加工性が劣っていた。これに対し、実施例1~14では、耐油性、加工性が優れていた。
The evaluation results for Examples 1-14 and Comparative Examples 1-6 are shown in Tables 1-4. In Comparative Example 1, the mass ratio of the phthalate ester plasticizer and the polyester plasticizer contained in the non-foamed layer and the foamed layer was 93:7, and the amount of the phthalate ester plasticizer was large. was inferior. In Comparative Examples 3 to 5, the non-foamed layer and/or the foamed layer contained only the phthalate ester plasticizer, so the oil resistance was poor. In Comparative Example 2, the mass ratio of the phthalate plasticizer and the polyester plasticizer contained in the non-foamed layer and the foamed layer was 67:33, and the content of the polyester plasticizer was large, so oil resistance was improved. Although it was excellent, foam entrapment occurred and the workability was poor. In Comparative Example 6, the content of the plasticizer was small and the workability was poor. In contrast, Examples 1 to 14 were excellent in oil resistance and workability.
本発明は以下に示される実施形態を含む。
[1] 繊維質基材と、塩化ビニル系樹脂と可塑剤とを含む発泡層と、塩化ビニル系樹脂と可塑剤とを含む非発泡層とを、この順で含む合成皮革であって、前記発泡層及び前記非発泡層のそれぞれにおいて、前記可塑剤の含有量が前記塩化ビニル系樹脂100質量部に対して60~100質量部であり、また前記可塑剤がフタル酸エステル系可塑剤とポリエステル系可塑剤とを含み、更に前記フタル酸エステル系可塑剤と前記ポリエステル系可塑剤の質量比が73:27~87:13(好ましくは77:23~83:17)である、合成皮革。
[2] 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤の数平均分子量が500~2500(好ましくは1200~2000)である、[1]に記載の合成皮革。
[3] 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤の25℃での粘度が150~5000mPa・s(好ましくは2000~5000mPa・s)である、[1]又は[2]に記載の合成皮革。
[4] 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤が、アジピン酸系ポリエステル、セバシン酸系ポリエステル、及びフタル酸系ポリエステルからなる群から選択される少なくとも1種、好ましくはアジピン酸系ポリエステル可塑剤である、[1]~[3]のいずれか1項に記載の合成皮革。
[5] 前記発泡層及び前記非発泡層における前記フタル酸エステル系可塑剤が、フタル酸ジブチル、フタル酸ジオクチル、フタル酸ジノニル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジトリデシル、フタル酸ジウンデシル、フタル酸ベンジルブチル、フタル酸ノニルウンデシル、及びフタル酸ジアルキル(C9~C11)からなる群から選択される少なくとも1種、好ましくはフタル酸ジアルキル(C9~C11)である、[1]~[4]のいずれか1項に記載の合成皮革。
[6] 前記非発泡層の厚さが100~300μm(好ましくは130~250μm)である、[1]~[5]のいずれか1項に記載の合成皮革。
[7] 前記発泡層及び前記非発泡層がそれぞれ熱安定剤(好ましくは有機酸カルシウム塩及び/又は有機酸亜鉛塩)を更に含み、好ましくは前記熱安定剤の含有量が前記塩化ビニル系樹脂100質量部に対して0.1~10質量部(好ましくは0.5~5質量部)である、[1]~[6]のいずれか1項に記載の合成皮革。
[8] 前記発泡層及び前記非発泡層がそれぞれ耐アミン剤(好ましくは過塩素酸塩)を更に含み、好ましくは前記耐アミン剤の含有量が前記塩化ビニル系樹脂100質量部に対して0.05~5質量部(好ましくは0.1~2質量部)である、[1]~[7]のいずれか1項に記載の合成皮革。
[9] 前記発泡層が発泡層用樹脂組成液に発泡剤(好ましくは有機系発泡剤)を添加することにより形成された、[1]~[8]のいずれか1項に記載の合成皮革。
[10] 前記発泡層の発泡倍率が2倍以下(好ましくは1.1倍以上2倍以下、より好ましくは1.2倍以上1.7倍以下)である、[1]~[9]のいずれか1項に記載の合成皮革。
[11] 前記発泡層の厚さが150~370μm(好ましくは190~370μm、より好ましくは200~300μm)である、[1]~[10]のいずれか1項に記載の合成皮革。
[12] 前記繊維質基材と前記発泡層との間に、ポリウレタン樹脂及び/又は塩化ビニル系樹脂を含む接着層を更に有する、[1]~[11]のいずれか1項に記載の合成皮革。
[13] 前記非発泡層上に、ポリウレタン樹脂(好ましくはポリカーボネート系ポリウレタン樹脂)を含む保護層を更に有する、[1]~[12]のいずれか1項に記載の合成皮革。
[14] 前記保護層の厚さが2~30μm(好ましくは5~20μm)である、[13]に記載の合成皮革。
[15] 前記非発泡層と前記保護層との間に、ポリウレタン樹脂(好ましくはポリエステル系ポリウレタン樹脂)を含むアンダーコート層を更に有する、[13]又は[14]に記載の合成皮革。
[16] 前記非発泡層が、非発泡層用樹脂組成液を離型性基材上に塗布して形成される樹脂層であり、前記発泡層が、前記離型性基材上に形成された前記非発泡層上に発泡層用樹脂組成液を塗布して形成される樹脂層であり、前記非発泡層用樹脂組成液及び前記発泡層用樹脂組成液がそれぞれ、塩化ビニル系樹脂と、フタル酸エステル系可塑剤とポリエステル系可塑剤を73:27~87:13の質量比で含む可塑剤と、を含み、前記塩化ビニル系樹脂100質量部に対する前記可塑剤の含有量が60~100質量部である、[1]~[15]のいずれか1項に記載の合成皮革。
[17] オモテ面に凹凸模様(好ましくはシボ模様)が設けられた、[1]~[16]のいずれか1項に記載の合成皮革。 The present invention includes embodiments shown below.
[1] A synthetic leather comprising, in this order, a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer, In each of the foamed layer and the non-foamed layer, the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the plasticizer is a phthalate plasticizer and a polyester synthetic leather, wherein the mass ratio of the phthalate plasticizer and the polyester plasticizer is 73:27 to 87:13 (preferably 77:23 to 83:17).
[2] The synthetic leather according to [1], wherein the polyester plasticizer in the foamed layer and the non-foamed layer has a number average molecular weight of 500 to 2500 (preferably 1200 to 2000).
[3] According to [1] or [2], wherein the polyester plasticizer in the foamed layer and the non-foamed layer has a viscosity at 25° C. of 150 to 5000 mPa·s (preferably 2000 to 5000 mPa·s). synthetic leather.
[4] The polyester-based plasticizer in the foamed layer and the non-foamed layer is at least one selected from the group consisting of adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters, preferably adipic acid-based plasticizers. The synthetic leather according to any one of [1] to [3], which is a polyester plasticizer.
[5] The phthalate ester plasticizer in the foam layer and the non-foam layer is dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, phthalate. Any of [1] to [4], which is at least one selected from the group consisting of benzyl butyl acid, nonylundecyl phthalate, and dialkyl phthalate (C9-C11), preferably dialkyl phthalate (C9-C11) 1. Synthetic leather according toitem 1.
[6] The synthetic leather according to any one of [1] to [5], wherein the non-foamed layer has a thickness of 100 to 300 μm (preferably 130 to 250 μm).
[7] The foamed layer and the non-foamed layer each further contain a heat stabilizer (preferably a calcium salt of an organic acid and/or a zinc salt of an organic acid), and preferably the content of the heat stabilizer is the vinyl chloride resin. The synthetic leather according to any one of [1] to [6], which is 0.1 to 10 parts by mass (preferably 0.5 to 5 parts by mass) per 100 parts by mass.
[8] The foamed layer and the non-foamed layer each further contain an amine-resistant agent (preferably perchlorate), and preferably the content of the amine-resistant agent is 0 with respect to 100 parts by mass of the vinyl chloride resin. 05 to 5 parts by mass (preferably 0.1 to 2 parts by mass), the synthetic leather according to any one of [1] to [7].
[9] The synthetic leather according to any one of [1] to [8], wherein the foam layer is formed by adding a foaming agent (preferably an organic foaming agent) to the foam layer resin composition liquid. .
[10] The foaming layer of [1] to [9], wherein the expansion ratio of the foam layer is 2 times or less (preferably 1.1 times or more and 2 times or less, more preferably 1.2 times or more and 1.7 times or less). The synthetic leather according to any one of items 1 and 2.
[11] The synthetic leather according to any one of [1] to [10], wherein the foam layer has a thickness of 150 to 370 μm (preferably 190 to 370 μm, more preferably 200 to 300 μm).
[12] The synthesis according to any one of [1] to [11], further comprising an adhesive layer containing a polyurethane resin and/or a vinyl chloride resin between the fibrous base material and the foam layer. leather.
[13] The synthetic leather according to any one of [1] to [12], further comprising a protective layer containing a polyurethane resin (preferably a polycarbonate-based polyurethane resin) on the non-foamed layer.
[14] The synthetic leather according to [13], wherein the protective layer has a thickness of 2 to 30 μm (preferably 5 to 20 μm).
[15] The synthetic leather according to [13] or [14], further comprising an undercoat layer containing a polyurethane resin (preferably a polyester polyurethane resin) between the non-foamed layer and the protective layer.
[16] The non-foamed layer is a resin layer formed by applying a non-foamed layer resin composition liquid onto a releasable substrate, and the foamed layer is formed on the releasable substrate. a resin layer formed by applying a resin composition liquid for a foamed layer onto the non-foamed layer, wherein the resin composition liquid for the non-foamed layer and the resin composition liquid for the foamed layer are each composed of a vinyl chloride resin; A plasticizer containing a phthalate plasticizer and a polyester plasticizer in a mass ratio of 73:27 to 87:13, and the content of the plasticizer is 60 to 100 with respect to 100 parts by mass of the vinyl chloride resin. The synthetic leather according to any one of [1] to [15], which is parts by mass.
[17] The synthetic leather according to any one of [1] to [16], which has an uneven pattern (preferably a embossed pattern) on the front side.
[1] 繊維質基材と、塩化ビニル系樹脂と可塑剤とを含む発泡層と、塩化ビニル系樹脂と可塑剤とを含む非発泡層とを、この順で含む合成皮革であって、前記発泡層及び前記非発泡層のそれぞれにおいて、前記可塑剤の含有量が前記塩化ビニル系樹脂100質量部に対して60~100質量部であり、また前記可塑剤がフタル酸エステル系可塑剤とポリエステル系可塑剤とを含み、更に前記フタル酸エステル系可塑剤と前記ポリエステル系可塑剤の質量比が73:27~87:13(好ましくは77:23~83:17)である、合成皮革。
[2] 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤の数平均分子量が500~2500(好ましくは1200~2000)である、[1]に記載の合成皮革。
[3] 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤の25℃での粘度が150~5000mPa・s(好ましくは2000~5000mPa・s)である、[1]又は[2]に記載の合成皮革。
[4] 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤が、アジピン酸系ポリエステル、セバシン酸系ポリエステル、及びフタル酸系ポリエステルからなる群から選択される少なくとも1種、好ましくはアジピン酸系ポリエステル可塑剤である、[1]~[3]のいずれか1項に記載の合成皮革。
[5] 前記発泡層及び前記非発泡層における前記フタル酸エステル系可塑剤が、フタル酸ジブチル、フタル酸ジオクチル、フタル酸ジノニル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジトリデシル、フタル酸ジウンデシル、フタル酸ベンジルブチル、フタル酸ノニルウンデシル、及びフタル酸ジアルキル(C9~C11)からなる群から選択される少なくとも1種、好ましくはフタル酸ジアルキル(C9~C11)である、[1]~[4]のいずれか1項に記載の合成皮革。
[6] 前記非発泡層の厚さが100~300μm(好ましくは130~250μm)である、[1]~[5]のいずれか1項に記載の合成皮革。
[7] 前記発泡層及び前記非発泡層がそれぞれ熱安定剤(好ましくは有機酸カルシウム塩及び/又は有機酸亜鉛塩)を更に含み、好ましくは前記熱安定剤の含有量が前記塩化ビニル系樹脂100質量部に対して0.1~10質量部(好ましくは0.5~5質量部)である、[1]~[6]のいずれか1項に記載の合成皮革。
[8] 前記発泡層及び前記非発泡層がそれぞれ耐アミン剤(好ましくは過塩素酸塩)を更に含み、好ましくは前記耐アミン剤の含有量が前記塩化ビニル系樹脂100質量部に対して0.05~5質量部(好ましくは0.1~2質量部)である、[1]~[7]のいずれか1項に記載の合成皮革。
[9] 前記発泡層が発泡層用樹脂組成液に発泡剤(好ましくは有機系発泡剤)を添加することにより形成された、[1]~[8]のいずれか1項に記載の合成皮革。
[10] 前記発泡層の発泡倍率が2倍以下(好ましくは1.1倍以上2倍以下、より好ましくは1.2倍以上1.7倍以下)である、[1]~[9]のいずれか1項に記載の合成皮革。
[11] 前記発泡層の厚さが150~370μm(好ましくは190~370μm、より好ましくは200~300μm)である、[1]~[10]のいずれか1項に記載の合成皮革。
[12] 前記繊維質基材と前記発泡層との間に、ポリウレタン樹脂及び/又は塩化ビニル系樹脂を含む接着層を更に有する、[1]~[11]のいずれか1項に記載の合成皮革。
[13] 前記非発泡層上に、ポリウレタン樹脂(好ましくはポリカーボネート系ポリウレタン樹脂)を含む保護層を更に有する、[1]~[12]のいずれか1項に記載の合成皮革。
[14] 前記保護層の厚さが2~30μm(好ましくは5~20μm)である、[13]に記載の合成皮革。
[15] 前記非発泡層と前記保護層との間に、ポリウレタン樹脂(好ましくはポリエステル系ポリウレタン樹脂)を含むアンダーコート層を更に有する、[13]又は[14]に記載の合成皮革。
[16] 前記非発泡層が、非発泡層用樹脂組成液を離型性基材上に塗布して形成される樹脂層であり、前記発泡層が、前記離型性基材上に形成された前記非発泡層上に発泡層用樹脂組成液を塗布して形成される樹脂層であり、前記非発泡層用樹脂組成液及び前記発泡層用樹脂組成液がそれぞれ、塩化ビニル系樹脂と、フタル酸エステル系可塑剤とポリエステル系可塑剤を73:27~87:13の質量比で含む可塑剤と、を含み、前記塩化ビニル系樹脂100質量部に対する前記可塑剤の含有量が60~100質量部である、[1]~[15]のいずれか1項に記載の合成皮革。
[17] オモテ面に凹凸模様(好ましくはシボ模様)が設けられた、[1]~[16]のいずれか1項に記載の合成皮革。 The present invention includes embodiments shown below.
[1] A synthetic leather comprising, in this order, a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer, In each of the foamed layer and the non-foamed layer, the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the plasticizer is a phthalate plasticizer and a polyester synthetic leather, wherein the mass ratio of the phthalate plasticizer and the polyester plasticizer is 73:27 to 87:13 (preferably 77:23 to 83:17).
[2] The synthetic leather according to [1], wherein the polyester plasticizer in the foamed layer and the non-foamed layer has a number average molecular weight of 500 to 2500 (preferably 1200 to 2000).
[3] According to [1] or [2], wherein the polyester plasticizer in the foamed layer and the non-foamed layer has a viscosity at 25° C. of 150 to 5000 mPa·s (preferably 2000 to 5000 mPa·s). synthetic leather.
[4] The polyester-based plasticizer in the foamed layer and the non-foamed layer is at least one selected from the group consisting of adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters, preferably adipic acid-based plasticizers. The synthetic leather according to any one of [1] to [3], which is a polyester plasticizer.
[5] The phthalate ester plasticizer in the foam layer and the non-foam layer is dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, phthalate. Any of [1] to [4], which is at least one selected from the group consisting of benzyl butyl acid, nonylundecyl phthalate, and dialkyl phthalate (C9-C11), preferably dialkyl phthalate (C9-C11) 1. Synthetic leather according to
[6] The synthetic leather according to any one of [1] to [5], wherein the non-foamed layer has a thickness of 100 to 300 μm (preferably 130 to 250 μm).
[7] The foamed layer and the non-foamed layer each further contain a heat stabilizer (preferably a calcium salt of an organic acid and/or a zinc salt of an organic acid), and preferably the content of the heat stabilizer is the vinyl chloride resin. The synthetic leather according to any one of [1] to [6], which is 0.1 to 10 parts by mass (preferably 0.5 to 5 parts by mass) per 100 parts by mass.
[8] The foamed layer and the non-foamed layer each further contain an amine-resistant agent (preferably perchlorate), and preferably the content of the amine-resistant agent is 0 with respect to 100 parts by mass of the vinyl chloride resin. 05 to 5 parts by mass (preferably 0.1 to 2 parts by mass), the synthetic leather according to any one of [1] to [7].
[9] The synthetic leather according to any one of [1] to [8], wherein the foam layer is formed by adding a foaming agent (preferably an organic foaming agent) to the foam layer resin composition liquid. .
[10] The foaming layer of [1] to [9], wherein the expansion ratio of the foam layer is 2 times or less (preferably 1.1 times or more and 2 times or less, more preferably 1.2 times or more and 1.7 times or less). The synthetic leather according to any one of
[11] The synthetic leather according to any one of [1] to [10], wherein the foam layer has a thickness of 150 to 370 μm (preferably 190 to 370 μm, more preferably 200 to 300 μm).
[12] The synthesis according to any one of [1] to [11], further comprising an adhesive layer containing a polyurethane resin and/or a vinyl chloride resin between the fibrous base material and the foam layer. leather.
[13] The synthetic leather according to any one of [1] to [12], further comprising a protective layer containing a polyurethane resin (preferably a polycarbonate-based polyurethane resin) on the non-foamed layer.
[14] The synthetic leather according to [13], wherein the protective layer has a thickness of 2 to 30 μm (preferably 5 to 20 μm).
[15] The synthetic leather according to [13] or [14], further comprising an undercoat layer containing a polyurethane resin (preferably a polyester polyurethane resin) between the non-foamed layer and the protective layer.
[16] The non-foamed layer is a resin layer formed by applying a non-foamed layer resin composition liquid onto a releasable substrate, and the foamed layer is formed on the releasable substrate. a resin layer formed by applying a resin composition liquid for a foamed layer onto the non-foamed layer, wherein the resin composition liquid for the non-foamed layer and the resin composition liquid for the foamed layer are each composed of a vinyl chloride resin; A plasticizer containing a phthalate plasticizer and a polyester plasticizer in a mass ratio of 73:27 to 87:13, and the content of the plasticizer is 60 to 100 with respect to 100 parts by mass of the vinyl chloride resin. The synthetic leather according to any one of [1] to [15], which is parts by mass.
[17] The synthetic leather according to any one of [1] to [16], which has an uneven pattern (preferably a embossed pattern) on the front side.
なお、明細書に記載の種々の数値範囲は、それぞれそれらの上限値と下限値を任意に組み合わせることができ、それら全ての組み合わせが好ましい数値範囲として本明細書に記載されているものとする。また、「X~Y」との数値範囲の記載は、特に言及しない限り、X以上Y以下を意味する。
It should be noted that the various numerical ranges described in the specification can be arbitrarily combined with their upper and lower limits, and all combinations thereof are described in this specification as preferred numerical ranges. In addition, the description of a numerical range of "X to Y" means X or more and Y or less unless otherwise specified.
1,10,100…合成皮革、2…繊維質基材、3…発泡層、4…非発泡層、5…接着層、6…保護層、7…アンダーコート層
DESCRIPTION OF SYMBOLS 1, 10, 100... Synthetic leather, 2... Fiber base material, 3... Foaming layer, 4... Non-foaming layer, 5... Adhesive layer, 6... Protective layer, 7... Undercoat layer
DESCRIPTION OF
Claims (9)
- 繊維質基材と、塩化ビニル系樹脂と可塑剤とを含む発泡層と、塩化ビニル系樹脂と可塑剤とを含む非発泡層とを、この順で含む合成皮革であって、
前記発泡層及び前記非発泡層のそれぞれにおいて、前記可塑剤の含有量が前記塩化ビニル系樹脂100質量部に対して60~100質量部であり、また前記可塑剤がフタル酸エステル系可塑剤とポリエステル系可塑剤とを含み、更に前記フタル酸エステル系可塑剤と前記ポリエステル系可塑剤の質量比が73:27~87:13である、合成皮革。 A synthetic leather containing, in this order, a fibrous base material, a foamed layer containing a vinyl chloride resin and a plasticizer, and a non-foamed layer containing a vinyl chloride resin and a plasticizer,
In each of the foamed layer and the non-foamed layer, the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the plasticizer is a phthalate plasticizer. A synthetic leather comprising a polyester plasticizer and a mass ratio of the phthalate plasticizer and the polyester plasticizer of 73:27 to 87:13. - 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤の数平均分子量が500~2500である、請求項1に記載の合成皮革。 The synthetic leather according to claim 1, wherein the polyester plasticizer in the foamed layer and the non-foamed layer has a number average molecular weight of 500 to 2,500.
- 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤の25℃での粘度が150~5000mPa・sである、請求項1又は2に記載の合成皮革。 The synthetic leather according to claim 1 or 2, wherein the polyester plasticizer in the foamed layer and the non-foamed layer has a viscosity at 25°C of 150 to 5000 mPa·s.
- 前記発泡層及び前記非発泡層における前記ポリエステル系可塑剤がアジピン酸系ポリエステル可塑剤である、請求項1~3のいずれか1項に記載の合成皮革。 The synthetic leather according to any one of claims 1 to 3, wherein the polyester-based plasticizer in the foamed layer and the non-foamed layer is an adipic acid-based polyester plasticizer.
- 前記発泡層及び前記非発泡層における前記フタル酸エステル系可塑剤がフタル酸ジアルキル(C9~C11)である、請求項1~4のいずれか1項に記載の合成皮革。 The synthetic leather according to any one of claims 1 to 4, wherein the phthalate plasticizer in the foam layer and the non-foam layer is dialkyl phthalate (C9-C11).
- 前記繊維質基材と前記発泡層との間に、ポリウレタン樹脂及び/又は塩化ビニル系樹脂を含む接着層を更に有する、請求項1~5のいずれか1項に記載の合成皮革。 The synthetic leather according to any one of claims 1 to 5, further comprising an adhesive layer containing a polyurethane resin and/or a vinyl chloride resin between the fibrous base material and the foam layer.
- 前記非発泡層上に、ポリウレタン樹脂を含む保護層を更に有する、請求項1~6のいずれか1項に記載の合成皮革。 The synthetic leather according to any one of claims 1 to 6, further comprising a protective layer containing a polyurethane resin on the non-foamed layer.
- 前記非発泡層と前記保護層との間に、ポリウレタン樹脂を含むアンダーコート層を更に有する、請求項7に記載の合成皮革。 The synthetic leather according to claim 7, further comprising an undercoat layer containing a polyurethane resin between the non-foamed layer and the protective layer.
- 前記非発泡層が、非発泡層用樹脂組成液を離型性基材上に塗布して形成される樹脂層であり、
前記発泡層が、前記離型性基材上に形成された前記非発泡層上に発泡層用樹脂組成液を塗布して形成される樹脂層であり、
前記非発泡層用樹脂組成液及び前記発泡層用樹脂組成液がそれぞれ、塩化ビニル系樹脂と、フタル酸エステル系可塑剤とポリエステル系可塑剤を73:27~87:13の質量比で含む可塑剤と、を含み、前記塩化ビニル系樹脂100質量部に対する前記可塑剤の含有量が60~100質量部である、請求項1~8のいずれか1項に記載の合成皮革。
The non-foaming layer is a resin layer formed by applying a resin composition liquid for a non-foaming layer onto a releasable substrate,
The foamed layer is a resin layer formed by applying a resin composition liquid for a foamed layer onto the non-foamed layer formed on the release substrate,
The resin composition liquid for the non-foaming layer and the resin composition liquid for the foaming layer each contain a vinyl chloride resin, a phthalate plasticizer, and a polyester plasticizer in a mass ratio of 73:27 to 87:13. The synthetic leather according to any one of claims 1 to 8, wherein the content of the plasticizer is 60 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
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