WO2019044750A1 - Stratifié de résine d'uréthane et son procédé de production - Google Patents

Stratifié de résine d'uréthane et son procédé de production Download PDF

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Publication number
WO2019044750A1
WO2019044750A1 PCT/JP2018/031523 JP2018031523W WO2019044750A1 WO 2019044750 A1 WO2019044750 A1 WO 2019044750A1 JP 2018031523 W JP2018031523 W JP 2018031523W WO 2019044750 A1 WO2019044750 A1 WO 2019044750A1
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WIPO (PCT)
Prior art keywords
layer
urethane resin
resin
barrier layer
resin laminate
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PCT/JP2018/031523
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English (en)
Japanese (ja)
Inventor
忠 折本
金法　順正
行二 澤田
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小松マテーレ株式会社
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Publication of WO2019044750A1 publication Critical patent/WO2019044750A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • 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
    • D06N3/12—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • 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
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material

Definitions

  • the present invention relates to a urethane resin laminate and a method for producing the same.
  • Priority is claimed on Japanese Patent Application No. 2017-167038, filed Aug. 31, 2017, the content of which is incorporated herein by reference.
  • a urethane resin laminate in which a polyurethane resin is laminated on a fiber fabric is soft and stretchable as a waterproof cloth, so rainwear, jackets, windbreakers, ski wear, shoes, hats, gloves, sleeping bags, sheets Or used for tents. Furthermore, a urethane resin laminate in which a polyurethane resin is laminated on a fiber fabric is also used as synthetic leather or artificial leather because it is soft and has a good touch.
  • automotive interior materials such as automotive seats, furniture such as sofas, bags, cases for smartphones, clothes, gloves, hats, shoes, balls, gloves, etc. may be mentioned as examples.
  • Such a urethane resin film should be in contact with N, N'-diethyl-m-toluamide (also referred to as DEET) contained in insect repellents and lower alcohols contained in cosmetics. It is known that dissolution, destruction and waterproofness decrease. To solve such problems, it is known that, by using an organic polyisocyanate having a polyisocyanate having a functional group number of 3 or more as a raw material, it is possible to obtain a urethane resin film that can withstand solvents contained in insect repellents and cosmetics. There is. (Patent Document 1)
  • sunscreen creams In addition to the concern about the increase in ultraviolet light due to the destruction of the ozone layer, the number of people using sunscreen creams has increased in recent years in order to suppress skin damage caused by ultraviolet light due to rising health and beauty awareness. Furthermore, sunscreen creams are used not only in summer but also in spring and autumn, and also in winter, and the amount and frequency of use thereof are also increasing. Furthermore, a cream having a high UV shielding effect, such as Ultraviolet Protection Factor 50+ (sometimes abbreviated as UPF 50+), has come to be commercially available.
  • UPF 50+ Ultraviolet Protection Factor 50+
  • the inventors of the present invention even in synthetic leather or the like that is a urethane resin laminate using a polyurethane resin not having moisture permeability, when the sunscreen cream adheres, the location swells and the appearance quality It has been found that deterioration occurs such as a decrease in the film thickness or peeling of the urethane resin film.
  • the present invention has been made in view of such circumstances, and even when a sunscreen cream is attached, the swelling is suppressed and the texture is soft, and when used as a waterproof fabric, it is waterproof.
  • the object of the invention is to provide a urethane resin laminate having excellent appearance quality when used as a synthetic leather or an artificial leather.
  • Another object of the present invention is to provide a method for producing the urethane resin laminate.
  • the embodiment of the present invention has the following configuration.
  • a urethane resin laminate in which a laminate having a layer containing a polyurethane resin and a barrier layer containing a vinyl alcohol copolymer is bonded to a base fabric.
  • the urethane resin laminate according to [1] wherein the layer containing the polyurethane resin is two or more layers, at least one layer is a skin layer, and at least one layer is an adhesive layer.
  • the sunscreen cream adheres even when the sunscreen cream adheres, the swelling is suppressed and the texture is soft, and when used as a waterproof fabric, the waterproof property is maintained, and used as synthetic leather and artificial leather.
  • a urethane resin laminate having excellent appearance quality is provided. Furthermore, the manufacturing method of the said urethane resin laminated body is provided.
  • urethane resin laminate according to an embodiment of the present invention, and a method of manufacturing the urethane resin laminate will be described.
  • the following aspects are merely examples for describing the present embodiment, and it is not intended to limit the present embodiment only to this aspect.
  • the present embodiment can be implemented in various modes without departing from the scope of the present invention.
  • the urethane resin laminate of the present embodiment has a structure in which a laminate having a layer containing a polyurethane resin and a barrier layer containing a vinyl alcohol copolymer is bonded to a base cloth.
  • the urethane resin laminate of the present embodiment has a layer containing a polyurethane resin.
  • a polyurethane resin contained in the layer containing a polyurethane resin What is arbitrary, such as ether type, ester type, carbonate type, can be used.
  • the method for obtaining the polyurethane resin is not particularly limited, and a compound synthesized by a conventionally known production method may be used, or a commercially available product may be used.
  • a method for producing a conventionally known polyurethane resin for example, a method for producing by a urethanization reaction of a main component polyol and a curing agent polyisocyanate is mentioned.
  • a method for producing conventionally known ether-based, ester-based and carbonate-based polyurethane resins a method of producing by urethane reaction of an ether-based polyol and a polyisocyanate, an ester-based polyol and a polyisocyanate, or a carbonate-based polyol and a polyisocyanate are mentioned as an example.
  • the main component polyol and the curing agent polyisocyanate it may contain a catalyst.
  • the catalyst include conventionally known basic catalysts or tin-based catalysts (eg, dibutyltin dilaurate).
  • the layer containing a polyurethane resin may be composed of only one layer, or may be composed of two or more layers.
  • a layer containing the polyurethane resin of this embodiment a skin layer, an adhesive layer, a surface treatment layer, or an intermediate layer etc. are mentioned as an example.
  • the layer containing a polyurethane resin is composed of two or more layers, it is preferable that at least one layer is a skin layer and at least one layer is an adhesive layer.
  • the skin layer and the adhesive layer containing the polyurethane resin of the present embodiment will be described in detail.
  • the skin layer of the present embodiment contains a polyurethane resin.
  • a polyurethane resin arbitrary things, such as ether type, ester type, or carbonate type, can be used. In the case of being used for car seats and the like, from the viewpoint of durability, ether-based or carbonate-based polyurethane resins are preferable, and carbonate-based polyurethane resins are particularly preferable.
  • a polyurethane resin modified with fluorine or silicone it is preferable to use a polyurethane resin modified with fluorine or silicone, and in particular, using a silicone modified polycarbonate polyurethane resin Is preferred.
  • an ester-based or carbonate-based polyurethane resin is preferable from the viewpoint of suppressing the swelling when getting wet with water, and an ether-based material is preferable from the viewpoint of moisture permeability.
  • the polyurethane resin one-pack type or semi-one-pack type is preferably used.
  • One of these polyurethane resins may be used alone, or two or more thereof may be used in combination. Moreover, you may mix
  • the method for obtaining the polyurethane resin is not particularly limited, and a compound synthesized by a conventionally known production method may be used, or a commercially available product may be used.
  • the conventionally known production method and the commercially available product are the same as those described for the layer containing a polyurethane resin.
  • pigments for coloring, spherical particles for changing design and touch, UV absorbers, antioxidants, antibacterial agents, infrared reflectors, deodorants, dirt removers (hereinafter also referred to as SR agents) May contain an antistatic agent, a blowing agent, or a flame retardant.
  • the thickness of the surface layer of the present embodiment may be set arbitrarily according to the application, design, etc. of the urethane resin laminate, but in the case where the urethane resin laminate is synthetic leather, artificial leather, etc. described later, 1 ⁇ m
  • the thickness is preferably at least 5 ⁇ m, more preferably at least 5 ⁇ m, and still more preferably at least 10 ⁇ m.
  • the thickness of the skin layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and still more preferably 30 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the skin layer is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m. Sufficient abrasion strength is obtained as it is more than the said lower limit, and it is possible to obtain synthetic leather, artificial leather and the like having sufficient emboss feeling. Moreover, when the sunscreen cream which has a component which is mentioned later as it is below the said upper limit adheres, the effect which suppresses generation
  • the thickness of the skin layer may be arbitrarily set according to the application, design, etc.
  • the thickness of the waterproof fabric is preferably 1 ⁇ m or more, and 5 ⁇ m or more More preferably, the thickness is 10 ⁇ m or more.
  • the thickness of the skin layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and still more preferably 30 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the skin layer is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m. Sufficient waterproofness can be acquired as it is more than the above-mentioned lower limit.
  • the thickness of the skin layer means the dimension in the lamination direction of the skin layer in the urethane resin laminate. Although the details will be described in Examples, the thickness of the skin layer can be determined, for example, by observing a cross section in the lamination direction of the urethane resin laminate with an electron microscope.
  • the skin layer may be either a porous membrane or a nonporous membrane.
  • the adhesive layer in the present embodiment is, for example, a layer for laminating a base fabric and a barrier layer, a base fabric and an intermediate layer, or a base fabric and a skin layer.
  • the adhesive layer includes a structure capable of adhering or fixing these layers to one another.
  • a polyurethane resin arbitrary things, such as ether type, ester type, or carbonate type, can be used. When using for car seat etc., the polyurethane resin of ether system or carbonate system is preferable from a durable viewpoint, and especially carbonate system polyurethane resin is preferable.
  • the polyurethane resin a polyurethane resin of a hot melt type, a moisture curing type or a two-component reaction type is preferably used.
  • the resin solution forming the adhesive layer has a peel strength (adhesive strength) between the base cloth and the barrier layer, the base cloth and the intermediate layer, or the base cloth and the skin layer.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups will be described later.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • the catalyst is the same as that described in the layer containing a polyurethane resin. One of these polyurethane resins may be used alone, or two or more thereof may be used in combination.
  • the adhesive layer may be a nonporous membrane or a porous membrane.
  • the method for obtaining the polyurethane resin is not particularly limited, and a compound synthesized by a conventionally known production method may be used, or a commercially available product may be used.
  • the conventionally known production method and the commercially available product are the same as those described for the layer containing a polyurethane resin.
  • the thickness of the adhesive layer in the present embodiment also varies depending on the performance required according to the application etc., and also varies depending on whether the adhesive layer is a nonporous membrane or a porous membrane, but is 1 ⁇ m to 5000 ⁇ m. preferable.
  • the thickness of the adhesive layer in the case of a nonporous membrane is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 20 ⁇ m or more.
  • the thickness of the adhesive layer is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and still more preferably 100 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the adhesive layer in the case of the nonporous membrane is preferably 1 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and still more preferably 20 to 100 ⁇ m.
  • the thickness of the adhesive layer in the case of the porous membrane is preferably 10 ⁇ m or more, and more preferably 50 ⁇ m or more.
  • the thickness of the adhesive layer is preferably 1000 ⁇ m or less, more preferably 700 ⁇ m or less, and still more preferably 500 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the adhesive layer is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and still more preferably 50 to 500 ⁇ m.
  • the peel strength (adhesion strength) with the layer to be adhered to the lower limit value or more is sufficient, and the texture of the resulting urethane resin laminate is suppressed to be hard when the upper limit value or less.
  • the thickness of the adhesive layer means the dimension in the laminating direction of the adhesive layer in the urethane resin laminate.
  • the thickness of the adhesive layer can be determined, for example, by observing the cross section in the lamination direction of the urethane resin laminate with an electron microscope.
  • a porous film is used as the adhesive layer, when the urethane resin laminate is a synthetic leather, an artificial leather or the like, a synthetic leather, an artificial leather or the like having a voluminous feel can be obtained.
  • the adhesive layer may be a pigment for coloring, spherical particles for changing design or feel, UV absorber, antioxidant, antibacterial agent, infrared reflector, and the like without departing from the object of the present embodiment.
  • a deodorant, an SR agent, an antistatic agent, a foaming agent, or a flame retardant may be contained.
  • the barrier layer is a layer provided to prevent the penetration of the sunscreen cream into the adhesive layer, the intermediate layer or the like. It is preferable to use a vinyl alcohol copolymer as the barrier layer.
  • the vinyl alcohol-based copolymer include polyvinyl alcohol resin and ethylene-vinyl alcohol resin.
  • the polyvinyl alcohol resin or ethylene-vinyl alcohol resin may include one having an acetic acid group.
  • One of these polyvinyl alcohol copolymers may be used alone, or two or more thereof may be used in combination.
  • the sunscreen cream in this embodiment broadly points to a coating agent (sunscreen agent) containing a component having a protective effect against ultraviolet light.
  • Sunscreen creams contain ingredients that have the function of absorbing or scattering ultraviolet light, and water.
  • other organic compounds and organic solvents for example, alcohols such as lower alcohols
  • the component contained in the sunscreen cream include octyl triazone, avobenzone, ethylhexyl methoxycinnamate, benzotriazole or triazine.
  • Such a coating agent may be in the form of an emulsion or gel in addition to cream, and the sunscreen cream of the present embodiment also includes these.
  • the components of the sunscreen cream including the organic compound and the organic solvent are prevented from penetrating into the other layers, and the other layers may be modified, swelled and deformed by these components. It can prevent.
  • the method for obtaining the polyvinyl alcohol-based resin is not particularly limited, and a compound synthesized by a conventionally known production method may be used, or a commercially available product may be used.
  • a manufacturing method of conventionally well-known ponivinyl alcohol-type resin the method manufactured by saponifying polyvinyl acetate-type resin is mentioned as an example.
  • the polyvinyl acetate resin may be a copolymer of vinyl acetate and other monomers copolymerizable with vinyl acetate, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate.
  • Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
  • polymerizing vinyl acetate is mentioned as an example.
  • a method for producing ethylene-vinyl alcohol resin known in the prior art a method of producing by saponifying ethylene-vinyl acetate copolymer obtained by copolymerizing ethylene and vinyl acetate is mentioned as an example.
  • KURARAY POVAL PVA205 (trademark) of Kuraray Co., Ltd. is mentioned as an example.
  • ethylene-vinyl alcohol resin 16DX by Kuraray Co., Ltd. can be mentioned as an example.
  • polyvinyl alcohol-based resins are preferable from the viewpoints of appearance quality and design of the resulting urethane resin laminate and environmental considerations.
  • the ethylene-vinyl alcohol copolymer can not be dissolved in water, and therefore, it is necessary to use it dissolved in various organic solvents such as propyl alcohol.
  • a polyvinyl alcohol resin can be prepared as an aqueous solution not containing an organic solvent, and thus is preferable from the point of environmental consideration in the production of a urethane resin laminate.
  • pigments for coloring, spherical particles for changing design or touch, UV absorber, antioxidant, antibacterial agent, infrared reflector, deodorant, SR agent, antistatic agent, foaming agent Or may contain a flame retardant or the like.
  • the thickness of the barrier layer in the present embodiment is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and still more preferably 5 ⁇ m or more.
  • the thickness of the barrier layer is preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, and still more preferably 40 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the barrier layer is preferably 0.1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and still more preferably 5 to 40 ⁇ m.
  • the thickness of the barrier layer means the dimension in the stacking direction of the barrier layer in the urethane resin laminate. Although the details will be described in Examples, the thickness of the barrier layer can be determined, for example, by observing a cross section in the lamination direction of the urethane resin laminate with an electron microscope.
  • the barrier layer is preferably a nonporous membrane from the viewpoint of suppressing swelling of the barrier layer by the sunscreen cream or swelling of the other layer due to permeation from the barrier layer to the other layer.
  • the base fabric of this embodiment includes chemical fibers such as polyester, nylon, acrylic, polyurethane, acetate, rayon, polylactic acid, or aramid, natural fibers such as cotton, hemp, silk, or wool, or mixed fibers thereof It may be blended, woven or knitted, and is not particularly limited. Also, they may be in any form such as woven fabric, knitted fabric or non-woven fabric. Further, from the viewpoint of enhancing the adhesion between the adhesive layer and the base fabric, it is preferable to generate fuzz on the surface of the base fabric such as raising, sanding and buffing.
  • one side or both sides of the base fabric may be brushed, sanded, buffed or the like.
  • the base cloth is subjected to dyeing, printing, antistatic, water repellent, antibacterial deodorizing, antibacterial treatment, flame retardancy, ultraviolet shielding, deodorizing, water absorption, moisture absorption, etc. It is also good.
  • a porous layer made of polyurethane resin or the like may be provided on a woven fabric, a knitted fabric, a non-woven fabric or the like.
  • a non-woven fabric base using microfibers or a non-woven fabric using microfibers impregnated with a resin is used as a base cloth, for example, Exéne (registered trademark) of Toray Industries, Inc. Or the artificial leather before giving the silver surface of Clarino (registered trademark) of Kuraray Co., Ltd. or the like.
  • the thickness of the base fabric of the present embodiment may be set arbitrarily according to the application, design, etc. of the urethane resin laminate, but in the case where the urethane resin laminate is artificial leather or synthetic leather, it is 100 ⁇ m or more
  • the thickness is preferably 300 ⁇ m or more, and more preferably 500 ⁇ m or more.
  • the thickness of the base fabric is preferably 6000 ⁇ m or less, more preferably 4000 ⁇ m or less, and still more preferably 2000 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the base fabric is, as a preferable range, 100 to 6000 ⁇ m, more preferably 300 to 4000 ⁇ m, and still more preferably 500 to 2000 ⁇ m.
  • the strength and appearance grade of the artificial leather obtained or synthetic leather can be improved as it is more than the said lower limit.
  • the feel and handleability of artificial leather obtained or synthetic leather can be improved as it is below the said upper limit.
  • the said urethane resin laminated body is a waterproof fabric
  • the thickness of the base fabric is preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, and still more preferably 500 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the base fabric when the urethane resin laminate is a waterproof fabric is preferably 30 to 1000 ⁇ m, more preferably 50 to 800 ⁇ m, and still more preferably 100 to 500 ⁇ m.
  • the thickness of the base fabric means the dimension in the laminating direction of the base fabric in the urethane resin laminate. Although the details will be described in Examples, the thickness of the base fabric can be determined, for example, by observing a cross section in the lamination direction of the urethane resin laminate with an electron microscope.
  • the urethane resin laminate of the present embodiment does not deviate from the object of the present embodiment other than the skin layer containing the polyurethane resin described above, the barrier layer containing the vinyl alcohol copolymer, the adhesive layer containing the polyurethane resin, and the base cloth. In the range, it may further have other layers such as a surface treatment layer and an intermediate layer.
  • the resin used for the surface treatment layer can be arbitrarily selected without departing from the object of the present embodiment, and polyurethane resin, silicone resin, fluorine resin, vinyl chloride resin, acrylic resin, nylon resin, polyolefin resin, etc. Can be mentioned. One of these resins may be used alone, or two or more of these resins may be used in combination. From the viewpoint of the feel of the resulting urethane resin laminate, a polyurethane resin is preferably contained, and an ether, ester, or carbonate type arbitrary one can be used. One of these polyurethane resins may be used alone, or two or more thereof may be used in combination.
  • the polyurethane resin of an ether type and / or a carbonate type is preferable, and a carbonate type polyurethane resin is especially preferable.
  • the urethane resin laminate is artificial leather or synthetic leather and it is desired to impart dirt removing property to the surface of the urethane resin laminate, it is preferable to use a polyurethane resin modified with fluorine or silicone, In particular, it is preferable to use a silicone-modified polycarbonate urethane resin.
  • the method for obtaining the polyurethane resin is not particularly limited, and a compound synthesized by a conventionally known production method may be used, or a commercially available product may be used.
  • the conventionally known production method and the commercially available product are the same as those described for the layer containing a polyurethane resin.
  • the thickness of the surface treatment layer in the present embodiment is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and still more preferably 1 ⁇ m or more.
  • the thickness of the surface treatment layer is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and still more preferably 10 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the thickness of the surface treatment layer is preferably 0.01 to 30 ⁇ m, more preferably 0.1 to 20 ⁇ m, and still more preferably 1 to 10 ⁇ m.
  • the thickness of the surface treatment layer means the dimension in the lamination direction of the surface treatment layer in the urethane resin laminate. Although the details will be described in Examples, the thickness of the surface treatment layer can be determined, for example, by observing a cross section in the laminating direction of the urethane resin laminate with an electron microscope.
  • one or more intermediate layers may optionally be provided between the skin layer and the adhesive layer, the skin layer and the barrier layer, or the barrier layer and the adhesive layer, for example.
  • the intermediate layer may be a nonporous membrane or a porous membrane, and may be selected according to the target urethane resin laminate.
  • the thickness of the intermediate layer is not particularly limited either, and varies depending on whether it is a non-porous film or a porous film, but it is preferably 1 ⁇ m to 5000 ⁇ m.
  • the thickness of the intermediate layer means the dimension in the lamination direction of the intermediate layer in the urethane resin laminate. Details will be described in Examples, but the thickness of the intermediate layer can be determined, for example, by observing a cross section in the lamination direction of the urethane resin laminate with an electron microscope.
  • the resin forming the intermediate layer is preferably a polyurethane resin.
  • the polyurethane resin of ether system or carbonate system is preferable from a durable viewpoint, and especially carbonate system polyurethane resin is preferable.
  • One of these polyurethane resins may be used alone, or two or more thereof may be used in combination.
  • the method for obtaining the polyurethane resin is not particularly limited, and a compound synthesized by a conventionally known production method may be used, or a commercially available product may be used.
  • the conventionally known production method and the commercially available product are the same as those described for the layer containing a polyurethane resin.
  • the total thickness of the urethane resin laminate is preferably 120 ⁇ m or more, more preferably 350 ⁇ m or more, and still more preferably 550 ⁇ m or more.
  • the total thickness of the urethane resin laminate is preferably 10000 ⁇ m or less, more preferably 8000 ⁇ m or less, and still more preferably 4000 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the total thickness of the urethane resin laminate is preferably 120 to 10000 ⁇ m, more preferably 350 to 8000 ⁇ m, and still more preferably 120 to 4000 ⁇ m.
  • the total thickness of the urethane resin laminate is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and still more preferably 120 ⁇ m or more.
  • the total thickness of the urethane resin laminate is preferably 1000 ⁇ m or less, more preferably 850 ⁇ m or less, and still more preferably 550 ⁇ m or less.
  • the upper limit and lower limit which were mentioned above can be combined arbitrarily.
  • the total thickness of the urethane resin laminate is preferably 50 to 1000 ⁇ m, more preferably 70 to 850 ⁇ m, and still more preferably 120 to 550 ⁇ m.
  • total thickness of urethane resin laminate means the dimension in the lamination direction of the urethane resin laminate. That is, “the total thickness of the urethane resin laminate” refers to the thickness of the skin layer, the thickness of the barrier layer, the thickness of the adhesive layer, the thickness of the base fabric, the thickness of the surface treatment layer, the thickness of the intermediate layer, other urethane resin laminates Mean the total thickness of all the layers contained in.
  • the total thickness of the urethane resin laminate can be determined, for example, by observing the cross section in the lamination direction of the urethane resin laminate with an electron microscope.
  • the total thickness of the urethane resin laminate is the thickness of the skin layer, the thickness of the barrier layer, the thickness of the adhesive layer, the thickness of the base fabric, the thickness of the surface treatment layer, the thickness of the intermediate layer, and other urethanes. It can also be obtained by measuring the thicknesses of all the layers contained in the resin laminate and summing the values.
  • the urethane resin laminate of the present embodiment can be obtained by optionally laminating the above-described layers.
  • the urethane resin laminate of the present embodiment includes a skin layer as a layer containing a polyurethane resin, the barrier layer and the skin layer are preferably joined, and the skin layer is on the opposite side to the base fabric It is preferred to be located.
  • a particularly preferred laminated structure will be described with reference to FIGS.
  • the urethane resin laminate 20 of the present embodiment is a synthetic leather or an artificial leather.
  • it is a synthetic leather or artificial leather having a skin layer called silver.
  • a skin layer 10 containing a polyurethane resin, a barrier layer 11 containing a vinyl alcohol copolymer, an adhesive layer 12 containing a polyurethane resin, and a base cloth 13 are laminated in this order. It is the urethane resin laminated body 20 being carried out. That is, it is characterized in that the skin layer 10 is located on the opposite side of the barrier layer 11 to the side where the base fabric 13 is present.
  • the urethane resin laminate 20 of the present embodiment can be mainly used for interior materials for automobiles such as automotive seats, furniture such as sofas, bags, smartphone cases, clothes, gloves, hats, shoes, balls, gloves, etc. Is not limited to these.
  • the skin layer 10 and the barrier layer 11 are bonded.
  • the urethane resin laminate of the present embodiment is, for example, synthetic leather and used in a car seat
  • the surface of the urethane resin laminate opposite to the base cloth is the surface in contact with the person sitting on the sheet.
  • the side opposite to the base cloth of the urethane resin laminate is referred to as the “outside”, and the layer located on the outermost side is referred to as the “outmost layer”. That is, in the first embodiment, the outermost layer is the skin layer 10.
  • the urethane resin laminated body of this embodiment for a sheet
  • the outermost layer of the urethane resin laminate of the present embodiment is a surface treatment layer.
  • the surface treatment layer preferably covers the entire surface of the skin layer 10 without a gap, but may cover a part of the skin layer 10, such as a dot shape or a lattice shape.
  • the barrier layer 11 may be a porous layer, or one or more intermediate layers may be provided in the urethane resin laminate, or a porous layer may be provided on the surface of the base fabric. You may provide.
  • the urethane resin laminate 20 of the present embodiment prevents the penetration of the sunscreen cream into the adhesive layer 12 containing the polyurethane resin and the intermediate layer, and as a result, the urethane resin laminate 20 swells. Since the skin layer 10 containing the polyurethane resin is located outside the barrier layer 11, the effect of maintaining good touch feeling can be obtained.
  • the urethane resin laminate 21 of the present embodiment is a synthetic leather or an artificial leather.
  • it is a synthetic leather or artificial leather having a skin layer called silver.
  • the urethane resin laminate of the present embodiment can be mainly used for automotive interior materials, furniture, bags, smartphone cases, clothes, gloves, hats, shoes, balls, gloves, etc., but is not limited thereto. .
  • the synthetic leather of this embodiment is a urethane resin in which a barrier layer 11 containing a vinyl alcohol copolymer, a skin layer 10 containing a polyurethane resin, an adhesive layer 12 containing a polyurethane resin, and a base cloth 13 are laminated in this order. It is a laminate 21.
  • the urethane resin laminate 20 according to the first embodiment is different from the urethane resin laminate 20 in that the barrier layer 11 is laminated outside the skin layer 10. In this embodiment, since the barrier layer 11 is outside the skin layer 10, the effect of suppressing the swelling (swelling property) to the sunscreen cream is more easily exhibited.
  • the barrier layer 11 When the barrier layer 11 is provided as the outermost layer as in the second embodiment and provided on the outer surface of the skin layer 10 containing the polyurethane resin, the surface layer 10 is glossy as compared with the outermost layer. , There is a possibility that the touch may differ greatly. Therefore, in the barrier layer 11 of this embodiment, a vinyl chloride resin, an acrylic resin, and a silicone resin are used for the purpose of bringing the feel and gloss of the urethane resin laminate obtained into close to those on the outer surface of the skin layer made of polyurethane resin. You may add the granular material etc. which consist of silicone rubber, or an inorganic fine particle etc. The particle size of these particles is preferably about 0.1 to 30 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • the barrier layer 11 when the barrier layer 11 is the outermost layer, it has the gloss as described above, and the touch feeling may be largely different. In order to eliminate this point, it is preferable to provide a surface treatment layer further outside the barrier layer 11.
  • the surface treatment layer preferably covers the entire surface of the barrier layer 12 without any gap, but may cover a part of the barrier layer such as dots or grids.
  • the barrier layer may be a porous layer, or it may have one or more intermediate layers between a skin layer and an adhesive layer, or may be porous on the surface of a base fabric. It may have a layer.
  • the urethane resin laminate 21 of the present embodiment prevents the penetration of the sunscreen cream into the skin layer 10 containing the polyurethane resin, the adhesive layer 12, and the intermediate layer, and as a result, the urethane resin lamination is performed. Swelling of the body 21 can be suppressed.
  • the urethane resin laminate of the present embodiment is a waterproof fabric.
  • a waterproof membrane in the urethane resin laminate it becomes a waterproof fabric.
  • the waterproof fabric of the third embodiment and the fourth embodiment has a waterproof urethane resin in which a laminate having a layer containing a polyurethane resin and a barrier layer containing a vinyl alcohol copolymer is bonded to a base cloth. It is a laminate.
  • the waterproof film may be included in the layer containing the polyurethane resin, May be included as a layer of The urethane resin laminate according to the first embodiment and the second embodiment imitates natural leather, but the urethane resin laminate according to the third embodiment and the fourth embodiment is a cloth having waterproofness.
  • the urethane resin laminate which is a waterproof fabric according to the third embodiment, includes a barrier layer 11 containing a vinyl alcohol copolymer, a surface layer 14 containing a polyurethane resin, an adhesive layer 12 containing a polyurethane resin, and a base cloth 15. , And the like in this order. That is, it is characterized in that the skin layer 14 is located in the side where the base fabric 15 is present with respect to the barrier layer 11.
  • the urethane resin laminate which is a waterproof fabric of the fourth embodiment, includes a skin layer 14 containing a polyurethane resin, a barrier layer 11 containing a vinyl alcohol copolymer, an adhesive layer 12 containing a polyurethane resin, and a base cloth 15. , And the like in this order. That is, it is characterized in that the skin layer 14 is located on the opposite side of the barrier layer 11 to the side where the base fabric 15 is present.
  • the adhesive layer 12 A porous polytetrafluoroethylene membrane (hereinafter also referred to as a porous PTFE membrane) or the like may be provided as a waterproof membrane between the membrane and the base cloth 15, and the skin layer 14 and the adhesive layer 12 may be provided.
  • a porous PTFE membrane or the like is provided between the adhesive layer 12 and the base cloth 15.
  • the surface layer 14 containing a polyurethane resin and the barrier layer 11 containing a vinyl alcohol copolymer, the adhesion between the barrier layer 11 and the adhesive layer 12 containing a polyurethane resin, and the like A porous PTFE membrane or the like may be provided as a waterproof membrane between the layer 12 and the base fabric 15, and the adhesive layer 12 and the base fabric 15 or the barrier layer 11 and the adhesive layer 12 may be used. It is preferable to have a porous PTFE membrane or the like in between.
  • the base cloth 15 side may be the outer side (surface opposite to the skin side), or the third embodiment.
  • the barrier layer 11 side may be the outside (the surface opposite to the skin side) in the fourth embodiment.
  • the skin layer 14 is likely to be in direct contact with the skin, but has a good feel when touching the skin, and also has the barrier layer 11 next to the skin layer 14, so swelling occurs. Waterproofness can also be maintained while suppressing the
  • the water resistance of the resulting waterproof fabric is preferably 500 mm or more.
  • water resistance can be measured according to JIS L1092 water resistance test (hydrostatic pressure method) method A (low water pressure method).
  • a front side surface of the test piece which hits to water
  • the surface treatment layer is laminated further outside the barrier layer 11 located in the outermost layer.
  • the surface treatment layer is laminated on the outer side of the skin layer 14 located in the outermost layer.
  • the surface treatment layer is provided to provide various functional properties such as improvement in the abrasion strength of the resulting waterproof cloth, imparting of texture and feeling, coloring, and deodorizing performance, and design properties.
  • the surface treatment layer preferably covers the entire surface of the barrier layer 11 in the third embodiment and the entire surface of the skin layer 14 in the fourth embodiment without gaps, but covers part of the skin layer such as dots or grids. It may be one.
  • one or more intermediate layers may be provided between the skin layer and the adhesive layer, for example, for the purpose of improving the waterproofness, though it is optional.
  • the intermediate layer may be a nonporous membrane or a porous membrane, and may be selected according to the desired waterproof fabric.
  • the resin constituting the intermediate layer described above may be used, or in the present embodiment, a porous membrane of polytetrafluoroethylene or the like can be used.
  • the method for producing a synthetic leather according to the present embodiment comprises the steps of applying a resin solution containing a polyurethane resin on a releasable substrate to form a skin layer, and forming a vinyl alcohol copolymer on the skin layer. And applying a resin solution containing the solution to form a barrier layer, and bonding the barrier layer and the base fabric via an adhesive.
  • the releasable substrate used in the present embodiment is not particularly limited, but may be a substrate having releasability with respect to a polyurethane resin or polyvinyl alcohol resin, or a substrate subjected to a releasability treatment.
  • a release film made of a release paper, a release cloth, a water repellent treated cloth, a polyethylene resin, a polypropylene resin or the like, a fluorine resin release film, etc. may be mentioned as an example.
  • the releasable substrate may have a concavo-convex pattern, and by using such a releasable substrate, the surface of an artificial leather or synthetic leather is given a dull feeling or glossiness, or an emboss is produced. Designability can be imparted by molding or the like.
  • a resin solution containing a polyurethane resin is applied on a releasing substrate.
  • the polyurethane resin solution is obtained by dissolving, dispersing or emulsifying a polyurethane resin in a solvent.
  • the solvent may be any solvent such as water, dimethylformamide (hereinafter, also referred to as DMF), methyl ethyl ketone, toluene, ethyl alcohol, etc. or a combination thereof, but from the viewpoint of environmental impact, no organic solvent is used.
  • DMF dimethylformamide
  • methyl ethyl ketone methyl ethyl ketone
  • toluene ethyl alcohol
  • ethyl alcohol ethyl alcohol
  • the resin solution containing the polyurethane resin may be one obtained by melting the polyurethane resin by heating without containing a solvent.
  • the resin solution preferably contains a crosslinking agent or a catalyst from the viewpoint of suppressing the swelling of the polyurethane resin film by the sunscreen cream and improving the abrasion strength of the skin layer and the peel strength (adhesive strength) with the barrier layer.
  • a crosslinking agent or a catalyst from the viewpoint of suppressing the swelling of the polyurethane resin film by the sunscreen cream and improving the abrasion strength of the skin layer and the peel strength (adhesive strength) with the barrier layer.
  • the catalyst the same one as described in the layer containing a polyurethane resin can be used.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • a polyisocyanate type crosslinking agent having three or more functional groups for example, a urethane modified product obtained by reacting organic diisocyanate (3 mol) and trimethylolpropane (TMP) (1 mol) (for example, HDI or IPDI or TDI and TMP And the like), the biuret modified product in which organic diisocyanate (3 mol) and water (1 mol) are reacted (for example, the modified product in which HDI or IPDI is reacted with water), organic diisocyanate Isocyanurate modification (for example, trimer of HDI or IPDI or TDI, etc.), dimer of the modification (for example, urethane modification or biuret modification or isocyanurate modification (2 moles) and water or A modified product obtained by reacting EG (1 mol) and the like, a trimer of the modified product (eg, the urethane modified Or biuret modified products or isocyanurate modified product and (3 moles) of water
  • HDI is hexamethylene diisocyanate
  • IPDI is isophorone diisocyanate
  • TDI is toluene diisocyanate.
  • aliphatic polyisocyanates of isocyanurate modified products alicyclic polyisocyanurates of isocyanurate modified products, or a mixture of two or more of them are mentioned, and particularly preferably HDI isocyanurate modified products, IPDI And isocyanurate modified products or mixtures thereof.
  • the upper limit of the number of functional groups is not particularly limited, but is about 5.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • a pigment for coloring, spherical particles for changing designability and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent, an antistatic agent , A flame retardant, or a catalyst may be contained.
  • the resin solution may be applied to the releasing substrate by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to evaporate the solvent, and if necessary, heat treated at 130 ° C. to 180 ° C. for 15 seconds to 60 minutes. Form The step of forming the next barrier layer may be continuously performed or may be performed for each step. The aging conditions are about room temperature to 90 ° C. and about 0.5 hour to 100 hours.
  • a resin solution containing a vinyl alcohol copolymer is applied onto the skin layer to form a barrier layer.
  • the resin solution containing the vinyl alcohol copolymer is used after being dissolved, dispersed, emulsified or the like in a solvent.
  • the solvent may be any one such as water, DMF, methyl ethyl ketone, toluene, ethyl alcohol, methyl alcohol, etc. or a combination thereof, but water is used without using an organic solvent from the viewpoint of environmental impact. Is preferred.
  • the resin solution containing the vinyl alcohol copolymer may be one obtained by melting the vinyl alcohol copolymer by heating. You may add the granular material etc. which consist of a vinyl chloride resin, an acrylic resin, a silicone resin, silicone rubber, or an inorganic fine particle etc. to the resin solution containing the said vinyl alcohol-type copolymer.
  • the resin solution preferably contains a crosslinking agent and a catalyst from the viewpoint of improving the peel strength (adhesive strength) with the skin layer.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups is the same as that described in the method for producing the skin layer.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • the resin solution may be a pigment for coloring, spherical particles for changing design and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent and an antistatic agent. Or a flame retardant may be contained.
  • the resin solution may be applied onto the surface layer by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to volatilize the solvent, and if necessary, heat treated at 130 ° C. to 180 ° C. for 15 seconds to 60 minutes to carry out the barrier layer Form.
  • the process of bonding the next barrier layer and the base fabric via an adhesive may be continuously performed or may be performed after aging.
  • the aging conditions are about room temperature to 90 ° C. and about 0.5 hour to 100 hours.
  • the base fabric may be bonded after the adhesive is applied on the barrier layer to form an adhesive layer, or on the base fabric.
  • the barrier layer may be attached after an adhesive is applied to form an adhesive layer.
  • the resin solution containing the polyurethane resin for forming the adhesive layer is obtained by dissolving, dispersing or emulsifying the polyurethane resin in a solvent.
  • the solvent may be any one of water, DMF, methyl ethyl ketone, toluene, ethyl alcohol, etc., or a combination thereof, but it is preferable to use water without using an organic solvent from the viewpoint of environmental impact.
  • the resin solution containing the polyurethane resin may be one obtained by melting the polyurethane resin by heating without containing a solvent.
  • the resin solution preferably contains a crosslinking agent or a catalyst from the viewpoint of improving the peel strength (adhesive strength) between the barrier layer and the base cloth, or the intermediate layer and the base cloth.
  • a crosslinking agent or a catalyst from the viewpoint of improving the peel strength (adhesive strength) between the barrier layer and the base cloth, or the intermediate layer and the base cloth.
  • the catalyst the same one as described in the layer containing a polyurethane resin can be used.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups is the same as that described in the method for producing the skin layer.
  • the resin solution may be a pigment for coloring, spherical particles for changing design and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent and an antistatic agent.
  • a foaming agent, a flame retardant, or a catalyst may be contained.
  • the resin solution may be applied onto the barrier layer by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes as necessary to volatilize the solvent to form an adhesive layer.
  • a resin solution obtained by melting a polyurethane resin by heating is used, the resin solution is applied on the barrier layer according to the conditions of the crosslinking agent and the foaming agent, and then the polyurethane resin is cured, or The crosslinking agent contained in the resin solution may be reacted by heating, or the foaming agent may be foamed to make the adhesive layer porous.
  • the blowing agent may be of a type that foams when the polyurethane resin is heated and melted.
  • the formation of the adhesive layer is not limited to the formation of the solidified adhesive layer before laminating the next base fabric, and the flow of the adhesive layer in the wet state or semi-wet state is not limited when laminating the base fabric. It also includes those having sex.
  • the step of laminating and bonding the next base fabric may be continuously performed continuously, and from the viewpoint of peel strength (adhesive strength), after forming the adhesive layer, the base is continuously formed on the adhesive layer. It is preferable to carry out a process of laminating and bonding cloths.
  • a base cloth is laminated and bonded onto the adhesive layer.
  • the base fabric is laminated on the adhesive layer and laminated, and although depending on the type of the adhesive layer, the adhesive layer and the base fabric may be laminated and then nipped with a nip roll or the like.
  • a hot roll a metal or resin nip roll or the like
  • heat treatment may be performed at 130 ° C. to 180 ° C. for about 15 seconds to 15 minutes.
  • aging may be performed if necessary. The aging conditions are about room temperature to 90 ° C. and about 0.5 hour to 100 hours.
  • the release substrate is peeled off at any stage to obtain a synthetic leather.
  • the resin solution for forming a surface treatment layer may be given on a skin layer.
  • the resin solution may be applied onto the surface layer by a known method such as a knife coater, a bar coater, a comma coater, a die coater, a gravure coater, a reverse coater, a spray, or a padding method.
  • the resin solution is applied onto the skin layer, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to volatilize the solvent, if necessary, at 130 ° C. to 180 ° C. for 15 seconds to 60 minutes
  • Heat treatment may be performed to form a surface treatment layer.
  • a barrier layer is formed on the skin layer, and then a resin solution for forming the intermediate layer is formed on the barrier layer with a knife coater,
  • the solution is applied by a known method such as a bar coater, comma coater, die coater, or extrusion coater, dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to volatilize the solvent, and if necessary, 130 ° C. to 180 ° C. Heat treatment may be performed for 15 seconds to 60 minutes to form an intermediate layer.
  • an adhesive layer may be formed on the intermediate layer by the method described above.
  • Urethane resin laminates such as the above synthetic leathers and artificial leathers suppress swelling even when a sunscreen cream adheres, and they are soft and soft, synthetic leather excellent in appearance grade and texture such as surface emboss feeling, artificial, artificial Leather is obtained.
  • the waterproof cloth which is easy to exhibit the effect which suppresses swelling with respect to a sunscreen cream can be obtained.
  • a resin solution containing a vinyl alcohol copolymer is applied on a releasable substrate to form a barrier layer, and a polyurethane resin is formed on the barrier layer.
  • a step of forming a skin layer by applying a resin solution containing the above, and a step of bonding the skin layer and the base cloth via an adhesive.
  • a resin solution containing a vinyl alcohol copolymer is applied onto a releasable substrate.
  • the resin solution containing a vinyl alcohol copolymer one which is dissolved, dispersed or emulsified in a solvent is used.
  • the solvent may be any one such as water, DMF, methyl ethyl ketone, toluene, ethyl alcohol, methyl alcohol, etc. or a combination thereof, but water is used without using an organic solvent from the viewpoint of environmental impact. Is preferred.
  • the resin solution containing the vinyl alcohol copolymer may be one obtained by melting the vinyl alcohol copolymer by heating.
  • the resin solution preferably contains a crosslinking agent and a catalyst from the viewpoint of improving the peel strength (adhesive strength) with the skin layer.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups is the same as that described in the method for producing the skin layer in the method for producing a urethane resin laminate of the first embodiment.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • the resin solution may be a pigment for coloring, spherical particles for changing design and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent and an antistatic agent. Or a flame retardant may be contained.
  • the resin solution may be applied to the releasing substrate by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to volatilize the solvent, and if necessary, heat treated at 130 ° C. to 180 ° C. for 15 seconds to 60 minutes to carry out the barrier layer Form.
  • the step of forming the next skin layer may be continuously performed or may be performed after aging.
  • the aging conditions are about room temperature to 90 ° C. and about 0.5 hour to 100 hours.
  • a resin solution containing a polyurethane resin is applied to form a skin layer.
  • the polyurethane resin solution is obtained by dissolving, dispersing or emulsifying a polyurethane resin in a solvent.
  • the solvent may be any solvent such as water, dimethylformamide (hereinafter, also referred to as DMF), methyl ethyl ketone, toluene, ethyl alcohol, etc. or a combination thereof, but from the viewpoint of environmental impact, no organic solvent is used.
  • water is used.
  • the resin solution containing the polyurethane resin may be one obtained by melting the polyurethane resin by heating without containing a solvent.
  • the resin solution preferably contains a crosslinking agent or a catalyst from the viewpoint of suppressing the swelling of the polyurethane resin film by the sunscreen cream and improving the abrasion strength of the surface layer and the peel strength (adhesive strength) with the barrier layer.
  • a crosslinking agent or a catalyst from the viewpoint of suppressing the swelling of the polyurethane resin film by the sunscreen cream and improving the abrasion strength of the surface layer and the peel strength (adhesive strength) with the barrier layer.
  • the catalyst the same one as described in the layer containing a polyurethane resin can be used.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type and aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups is the same as that described in the method for producing the skin layer in the method for producing a urethane resin laminate of the first embodiment.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • the resin solution may be a pigment for coloring, spherical particles for changing design and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent and an antistatic agent.
  • a flame retardant, or a catalyst may be contained.
  • the resin solution may be applied to the barrier layer by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to evaporate the solvent, and if necessary, heat treated at 130 ° C. to 180 ° C. for 15 seconds to 60 minutes. Form The process of bonding the next skin layer and the base fabric via an adhesive may be continuously performed continuously, or aging may be performed for each process. The aging conditions are about room temperature to 90 ° C. and about 0.5 hour to 100 hours.
  • the base fabric may be bonded after the adhesive is applied on the skin layer to form an adhesive layer, or on the base fabric.
  • the skin layer may be attached after the adhesive is applied to form the adhesive layer.
  • the resin solution containing the polyurethane resin for forming the adhesive layer is obtained by dissolving, dispersing or emulsifying the polyurethane resin in a solvent.
  • the solvent may be any one of water, DMF, methyl ethyl ketone, toluene, ethyl alcohol, etc., and a combination thereof, but it is preferable to use water without using an organic solvent from the viewpoint of environmental impact.
  • the resin solution containing the polyurethane resin may be one obtained by melting the polyurethane resin by heating without containing a solvent.
  • the resin solution preferably contains a crosslinking agent, a catalyst or the like from the viewpoint of improving the peel strength (adhesive strength) between the skin layer and the base fabric, or the intermediate layer and the base fabric.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups is the same as that described in the method for producing a urethane resin laminate of the first embodiment.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • the resin solution may be a pigment for coloring, spherical particles for changing design and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent and an antistatic agent.
  • a foaming agent, a flame retardant, or a catalyst may be contained.
  • the resin solution may be applied onto the surface layer by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes as necessary to volatilize the solvent to form an adhesive layer.
  • a resin solution obtained by melting a polyurethane resin by heating is used, the resin solution is applied on the barrier layer according to the conditions of the crosslinking agent and the foaming agent, and then the polyurethane resin is cured, or The crosslinking agent contained in the resin solution may be reacted by heating, or the foaming agent may be foamed to make the adhesive layer porous.
  • the blowing agent may be of a type that foams when the polyurethane resin is heated and melted.
  • the formation of the adhesive layer is not limited to the formation of the solidified adhesive layer before laminating the next base fabric, and the flow of the adhesive layer in the wet state or semi-wet state is not limited when laminating the base fabric. It also includes those having sex.
  • the step of laminating and bonding the next base fabric may be continuously performed continuously, and from the viewpoint of peel strength (adhesive strength), after forming the adhesive layer, the base is continuously formed on the adhesive layer. It is preferable to carry out a process of laminating and bonding cloths.
  • a base cloth is laminated and bonded onto the adhesive layer.
  • the base fabric is laminated on the adhesive layer and laminated, and although depending on the type of the adhesive layer, the adhesive layer and the base fabric may be laminated and then nipped with a nip roll or the like.
  • a hot roll a metal or resin nip roll or the like
  • heat treatment may be performed at 130 ° C. to 180 ° C. for about 15 seconds to 15 minutes.
  • aging may be performed if necessary. The aging conditions are about room temperature to 90 ° C. and about 0.5 hour to 100 hours.
  • the subsequent peeling of the releasable substrate, and the method for providing the surface treatment layer and the intermediate layer can be carried out in the same manner as the method for producing a urethane resin laminate of the first embodiment.
  • the step of applying a resin solution containing a polyurethane resin on a releasable substrate to form a skin layer can be performed in the same manner as the method described in the method for producing a urethane resin laminate of the first embodiment.
  • the step of bonding the skin layer and the base fabric via an adhesive can be performed in the same manner as the method described in the first method of producing a urethane resin laminate of the second embodiment.
  • the releasable substrate is peeled off to obtain a synthetic leather.
  • a resin solution containing a vinyl alcohol copolymer is applied to the surface of the skin layer from which the releasable substrate has been peeled, to form a barrier layer.
  • the resin solution containing a vinyl alcohol copolymer one which is dissolved, dispersed or emulsified in a solvent is used.
  • the solvent may be any one such as water, DMF, methyl ethyl ketone, toluene, ethyl alcohol, methyl alcohol, etc. or a combination thereof, but water is used without using an organic solvent from the viewpoint of environmental impact. Is preferred.
  • the resin solution containing the vinyl alcohol copolymer may be one obtained by melting the vinyl alcohol copolymer by heating. You may add the granular material etc. which consist of a vinyl chloride resin, an acrylic resin, a silicone resin, silicone rubber, or an inorganic fine particle etc. to the resin solution containing the said vinyl alcohol-type copolymer.
  • the resin solution preferably contains a crosslinking agent and a catalyst from the viewpoint of improving the peel strength (adhesive strength) with the skin layer.
  • the crosslinking agent is not particularly limited, such as isocyanate type, melamine type, oxazoline type, carbodiimide type, epoxy type, or aziridine type.
  • the crosslinking agent which has 3 or more of functional groups is preferable, and the isocyanate type crosslinking agent which has 3 or more of functional groups is more preferable.
  • the isocyanate-based crosslinking agent having three or more functional groups is the same as that described in the method for producing a urethane resin laminate of the first embodiment.
  • the isocyanate-based crosslinking agent may be either block type or non-block type.
  • the resin solution may be a pigment for coloring, spherical particles for changing design and touch, an ultraviolet absorber, an antioxidant, an antibacterial agent, an infrared reflecting material, a deodorant, an SR agent and an antistatic agent. Or a flame retardant may be contained.
  • the resin solution may be applied onto the surface layer by a known method such as a knife coater, a bar coater, a comma coater, a die coater, or an extrusion coater. After the resin solution is applied, it is dried at 60 ° C. to 150 ° C. for about 15 seconds to 60 minutes to volatilize the solvent, and if necessary, heat treated at 130 ° C. to 180 ° C. for 15 seconds to 60 minutes to carry out the barrier layer Form.
  • ⁇ Thickness> The cross section in the laminating direction of the urethane resin laminate was observed with an electron microscope, the thickness of each of the five optional layers was measured, and the average value was taken as the thickness.
  • the adhesive layer or the surface treatment layer is applied in the form of dots or grids, and is applied in a state where the thickness is largely different depending on the place, any thick thickness to which an adhesive resin or the like is applied Five places were selected and thickness was measured.
  • a sunscreen cream (Anesa Perfect UV Aqua, manufactured by Shiseido Co., Ltd.) in the range of a diameter of 2.0 cm on the surface opposite to the surface having a base fabric of a urethane resin laminate (the outermost layer is a skin layer or a barrier layer or surface treatment layer).
  • 2.5 g of a booster SPF50 +, PA ++++ (trade name) was applied, and then, the portion of the urethane resin laminate coated with the sunscreen cream was sandwiched with a glass plate and allowed to stand in an environment of 80 ° C. for 1 hour. Next, the glass plate is removed and it is allowed to cool for 10 minutes under a room temperature environment.
  • the sunscreen cream was wiped off, and the appearance of the portion where the sunscreen cream of the urethane resin laminate was applied was observed.
  • Example 1 synthetic leather
  • a polyester warp-knitted fabric (84 dtex / 72 filaments, 50 / 2.5 cm course, 34 / 2.54 cm well) dyed in black using a treatment solution containing a disperse dye and a phosphorus-based flame retardant and processed at the same time as flame retardant was used as the base fabric.
  • the following surface resin solution was applied onto a release paper (having a textured pattern) using a comma coater, and dried at 120 ° C. for 2 minutes to obtain a surface layer comprising a polyurethane resin film.
  • Resin solution for skin layer
  • Polycarbonate-based polyurethane resin solution non-yellowing type, solid content 35%, remaining: water
  • Carbodiimide-based crosslinking agent functional group number 3 or more
  • Black pigment 10 parts
  • Thickener 1 part
  • Wetting improver 0.3 parts
  • Defoamer 0.1 part
  • the following resin solution to be a barrier layer is coated on the skin layer using a comma coater, dried at 120 ° C. for 2 minutes, aged at 60 ° C. for 48 hours, and coated with a polyurethane resin
  • a barrier layer consisting of a polyvinyl alcohol resin film was laminated thereon.
  • Resin solution for barrier layer
  • Polyvinyl alcohol resin solution solid content 25%, remaining: water
  • Isocyanate crosslinker 3 or more functional groups
  • the following resin solution for an adhesive layer is applied on the above barrier layer using a comma coater, dried at 120 ° C. for 1 minute, and an adhesive containing a polyurethane resin on the barrier layer made of a polyvinyl alcohol resin film Layers were stacked.
  • Resin solution for adhesive layer
  • Polycarbonate-based polyurethane resin solution hard yellowing type, solid content 45%, balance: water
  • Isocyanate-based crosslinking agent functional group number 3 or more
  • Phosphorus flame retardant solid content 41%): 25 parts
  • Bigor FV 6010 trademark
  • a fiber cloth was superposed on the surface of this adhesive layer and bonded by thermocompression bonding using a metal nip roll heated to 120 ° C. Next, aging was performed at 60 ° C. for 72 hours. After aging, the release paper was peeled off to obtain synthetic leather (urethane resin laminate) corresponding to the layer configuration of the first embodiment (FIG. 1).
  • the obtained synthetic leather is a urethane resin laminated in the order of a skin layer (thickness 20 ⁇ m) containing a polyurethane resin, a barrier layer (thickness 20 ⁇ m) consisting of a polyvinyl alcohol resin, an adhesive layer (thickness 30 ⁇ m) containing a polyurethane resin, It is a laminate.
  • the obtained synthetic leather had a soft texture and a good touch. In addition, surface emboss was also formed, and no swelling with sunscreen cream was observed.
  • the organic solvent was not used but synthetic leather was able to be obtained using a water-based solvent which is environmentally friendly.
  • Example 1 A synthetic leather was obtained in the same manner as in Example 1 except that the barrier layer was not provided.
  • the obtained synthetic leather had a soft texture and a good touch.
  • the sunscreen cream the portion to which the sunscreen cream was attached was greatly swollen and deformed.
  • Example 2 synthetic leather
  • a resin solution containing the following polyurethane resin was coated on the skin layer using a gravure coater, dried at 110 ° C., and 10 ⁇ m thick A surface treated layer was formed, and a surface treated layer was further laminated on the skin layer 10 of the first embodiment (FIG. 1) to obtain an antifouling synthetic leather.
  • Resin solution containing acrylic silicone compound 100 parts (emulsion of acrylic silicone compound) (Organic-inorganic hybrid resin containing 32% solids, compound of acrylic silicone and inorganic silica)
  • the obtained synthetic leather had a soft texture and a good touch. In addition, surface emboss was also formed, and no swelling with sunscreen cream was observed. Moreover, in the manufacturing process of this synthetic leather, the organic solvent was not used but synthetic leather was able to be obtained using a water-based solvent which is environmentally friendly. In addition, it has anti-staining properties against ketchup, coffee, whiteboard markers, and povidone-iodine used for disinfecting the mouth in hospitals etc., and these substances should be wiped off with a towel etc. The synthetic leather which is hard to be stained is obtained.
  • Example 3 synthetic leather
  • a polyester weft knit (84 dtex / 72 filaments, 28 gauge) was dyed black with a disperse dye, and a raised one was used as a base fabric.
  • the following resin solution for a barrier layer was coated on a release paper (having a textured pattern) using a comma coater and dried at 120 ° C. for 2 minutes to obtain a barrier layer composed of a ponivinyl alcohol resin film .
  • Resin solution for barrier layer
  • Polyvinyl alcohol resin solution solid content 25%, remaining: water
  • Isocyanate crosslinker 3 or more functional groups
  • the following resin solution that will be the skin layer is coated on the barrier layer using a comma coater, dried at 120 ° C. for 2 minutes, aged at 60 ° C. for 48 hours, and polyvinyl alcohol resin as a crosslinking agent It was made to react and the skin layer containing a polyurethane resin was laminated on the barrier layer which consists of polyvinyl alcohol resin films.
  • Resin solution for skin layer
  • Polycarbonate-based polyurethane resin solution non-yellowing type, solid content 30%
  • Isocyanate-based crosslinking agent functional group number 3 or more
  • Black pigment 10 parts
  • DMF 25 parts
  • the following resin solution for adhesive layer is applied on the above skin layer using a comma coater, dried at 120 ° C. for 1 minute, and an adhesive layer containing a polyurethane resin on the skin layer consisting of a polyurethane resin film Stacked.
  • Resin solution for adhesive layer
  • Polycarbonate-based polyurethane resin solution non-yellowing type, solid content 70%
  • Isocyanate-based crosslinking agent functional group number 3 or more
  • Catalyst 1 part
  • Flame retardant Brom / antimony composite type, solid content 70%
  • Black pigment 5 parts
  • DMF 60 parts
  • the raised surface of the fiber fabric was superposed on the surface of the adhesive layer and bonded by thermocompression bonding using a metal nip roll heated to 120 ° C. Next, aging was performed at 60 ° C. for 72 hours. After aging, the release paper was peeled off to obtain synthetic leather (urethane resin laminate) corresponding to the layer configuration of the second embodiment (FIG. 2).
  • the obtained synthetic leather is a urethane resin laminated in the following order: barrier layer (thickness 20 ⁇ m) made of polyvinyl alcohol resin, skin layer (thickness 20 ⁇ m) containing polyurethane resin, adhesive layer (thickness 30 ⁇ m) containing polyurethane resin, and base fabric It is a laminate.
  • barrier layer thinness 20 ⁇ m
  • skin layer thinness 20 ⁇ m
  • adhesive layer thinness 30 ⁇ m
  • base fabric It is a laminate.
  • the obtained synthetic leather had a soft texture and a good touch. In addition, surface emboss was also formed, and no swelling with sunscreen cream was observed.
  • Example 4 synthetic leather
  • a polyester weft knit (84 dtex / 72 filaments, 28 gauge) was dyed black with a disperse dye, and a raised one was used as a base fabric.
  • the following surface resin solution was applied onto a release paper (having a textured pattern) using a comma coater, and dried at 120 ° C. for 2 minutes to obtain a surface layer comprising a polyurethane resin film.
  • Resin solution for skin layer
  • Polycarbonate-based polyurethane resin solution non-yellowing type, solid content 35%, remaining: water
  • Carbodiimide-based crosslinking agent functional group number 3 or more
  • Black pigment 10 parts
  • Thickener 1 part
  • Wetting improver 0.3 parts
  • Defoamer 0.1 part
  • the following resin solution to be a barrier layer is coated on the skin layer using a comma coater, dried at 120 ° C. for 2 minutes, aged at 60 ° C. for 48 hours, and coated with a polyurethane resin
  • a barrier layer consisting of a polyvinyl alcohol resin film was laminated thereon.
  • Resin solution for barrier layer
  • Polyvinyl alcohol resin solution solid content 25%, remaining: water
  • Isocyanate crosslinker 3 or more functional groups
  • a hot melt polyurethane resin for adhesive layer is heated and melted, a solvent-free resin solution is applied on the barrier layer using an extrusion coater, and heated at 130 ° C. for 3 minutes to form an adhesive layer.
  • the polyurethane resin was foamed, and a porous adhesive layer containing a polyurethane resin was laminated on the barrier layer made of a polyvinyl alcohol resin film.
  • Hot melt ether-based urethane prepolymer having isocyanate group 100 parts Blowing agent (composition containing N, N'-dinitrosopentamethylenetetramine, urea, polyol): 25 parts Black pigment: 5 parts
  • the raised surface of the fiber fabric was superposed on the surface of the adhesive layer and bonded by thermocompression bonding using a metal nip roll heated to 120 ° C. Next, aging was performed at 60 ° C. for 72 hours. After aging, the release paper was peeled off to obtain synthetic leather (urethane resin laminate) corresponding to the layer configuration of the first embodiment (FIG. 1).
  • the obtained synthetic leather was laminated in order of a skin layer (thickness 20 ⁇ m) containing a polyurethane resin, a barrier layer (thickness 20 ⁇ m) consisting of a polyvinyl alcohol resin, a porous adhesive layer (thickness 200 ⁇ m) containing a polyurethane resin, and a base cloth It is a urethane resin laminate.
  • the resulting synthetic leather had a voluminous feel and a good touch. In addition, no swelling was observed in the sunscreen cream.
  • Example 5 waterproof cloth
  • a polyester plain weave fabric (warp 84 decitex / 72 filaments, weft 84 decitex / 72 filaments, basis weight 120 g / m 2 ) is dyed blue with a disperse dye, and a fluorine-based water repellent Asahi Guard AG-E081 (manufactured by Asahi Glass Co., Ltd.)
  • the water-repellent fabric was used as a base fabric using a 3% aqueous solution of
  • the following resin solution to be a barrier layer is coated on a release paper using a comma coater, dried at 120 ° C. for 2 minutes, aged at 60 ° C. for 48 hours, and the polyvinyl alcohol resin is reacted with a crosslinking agent to resist A polyvinyl alcohol resin film with improved DMF properties was obtained.
  • Resin solution for barrier layer
  • Polyvinyl alcohol resin solution solid content 25%, remaining: water
  • Isocyanate crosslinker 3 or more functional groups
  • the following resin solution to be a skin layer is coated on the barrier layer using a comma coater, and on the resin solution, a porous PTFE membrane (porosity 92%, thickness 38 ⁇ m) as an intermediate layer is subsequently formed. It laminated and dried at 120 degreeC.
  • Ether-based polyurethane resin solid content 30%: 100 parts methyl ethyl ketone: 60 parts white pigment: 8 parts
  • Resin solution for adhesive layer: Ether-based polyurethane resin (solid content 45%): 100 parts Toluene: 50 parts Isocyanate-based crosslinking agent (having 3 or more functional groups): 9 parts Amine catalyst: 1 part
  • the obtained waterproof cloth comprises a barrier layer (thickness 5 ⁇ m) made of polyvinyl alcohol resin, a surface layer (thickness 13 ⁇ m) containing a polyurethane resin, an intermediate layer (thickness 38 ⁇ m) made of a porous PTFE membrane, and an adhesive layer containing a polyurethane resin
  • a waterproof cloth (urethane resin laminated body) laminated in the order of thickness 15 ⁇ m) and base cloth.
  • the waterproof cloth was lightweight and soft, and the appearance of the membrane was glossy.
  • the water resistance was 2000 mm or more regardless of which of the base fabric and the barrier layer was used as the water contact surface. Also, no swelling was observed with the sunscreen cream.
  • Example 2 A waterproof cloth was obtained in the same manner as in Example 5 except that the barrier layer was not provided.
  • the resulting waterproof cloth had a soft texture, and the appearance was slightly glossy compared to Example 1, but was glossy.
  • the water resistance was 2000 mm or more regardless of which of the base cloth and the barrier layer was used as the water contact surface.
  • the sunscreen cream caused swelling of the skin layer containing the polyurethane resin and deformation occurred.
  • the urethane resin laminate of the present embodiment can be used as a synthetic leather, an artificial leather, or a waterproof fabric, and can be prevented from swelling or deformation even if a sunscreen cream adheres, the present embodiment Sunscreen creams when used for automotive interior materials such as car seats, furniture such as sofas, bags, smartphone cases, clothes, gloves, hats, shoes, balls or gloves, helmets, etc. Even if it adheres, various products excellent in swelling resistance can be obtained.
  • Reference Signs List 10 skin layer 11 barrier layer 12 adhesive layer 13 base fabric 14 skin layer 15 base fabric 20 urethane resin laminate 21 according to the first embodiment urethane resin laminate 22 according to the second embodiment urethane resin laminate according to the third embodiment Body 23 Urethane resin laminate according to the fourth embodiment

Landscapes

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

Abstract

L'objectif de la présente invention est de fournir un stratifié de résine d'uréthane qui, même si une crème d'écran solaire a adhéré à celui-ci, est empêché de gonfler et qui a une texture molle. Le stratifié de résine d'uréthane conserve des propriétés d'imperméabilisation lorsqu'il est utilisé en tant que tissu imperméable à l'eau, et présente une excellente qualité d'apparence lorsqu'il est utilisé en tant que cuir synthétique ou artificiel. Le stratifié de résine d'uréthane (20) comprend un tissu de base (13) et, stratifiées sur celui-ci, une structure multicouche comprenant deux couches contenant une résine de polyuréthane ou plus et une couche barrière (11) comprenant un copolymère à base d'alcool vinylique. Au moins l'une des couches contenant une résine de polyuréthane est une couche de peau (10) et au moins l'une de celles-ci est une couche adhésive (12).
PCT/JP2018/031523 2017-08-31 2018-08-27 Stratifié de résine d'uréthane et son procédé de production WO2019044750A1 (fr)

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JP2017167038A JP6974985B2 (ja) 2017-08-31 2017-08-31 ウレタン樹脂積層体、及びその製造方法

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012020519A (ja) * 2010-07-15 2012-02-02 Nihon Iac Kk 自動車用内装品の製造方法
JP2014129622A (ja) * 2012-12-28 2014-07-10 Kyowa Leather Cloth Co Ltd 合成皮革
JP2014181413A (ja) * 2013-03-18 2014-09-29 Kuraray Plastics Co Ltd 銀付調人工皮革及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012020519A (ja) * 2010-07-15 2012-02-02 Nihon Iac Kk 自動車用内装品の製造方法
JP2014129622A (ja) * 2012-12-28 2014-07-10 Kyowa Leather Cloth Co Ltd 合成皮革
JP2014181413A (ja) * 2013-03-18 2014-09-29 Kuraray Plastics Co Ltd 銀付調人工皮革及びその製造方法

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