laminate

Abstract

【Problem】To provide a laminate having good elasticity, excellent air permeability and flame retardancy, and less likely to expose fluff from an opening. 【Solution】A laminate (1) composed of a base cloth layer (11) and a resin composition layer (12) having a polyvinyl chloride-based resin as a main component, the resin composition layer (12) having an impregnated portion (12a) impregnated in the base cloth layer (11), having a plurality of openings (20) extending through the base cloth layer (11) and the resin composition layer (12) in a thickness direction, having a mass of the resin composition layer (12) of 30 to 100 parts by mass with respect to 100 parts by mass of a mass of the base cloth layer (11), having a tensile strength in a longitudinal direction and a lateral direction of the base cloth layer (11) of 100 N / cm or more, and having a constant load elongation of 20% or more, and having an air permeability of 50 cc / cm 2 or more, the laminate (1).

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a laminate sheet. More specifically, the present disclosure relates to a laminate sheet suitable for use in synthetic leather. TECHNICAL BACKGROUND

[0002] Synthetic leather is widely used as a substitute for natural leather or as a leather material having better physical properties than natural leather. In particular, synthetic leather used as a seat surface of a vehicle such as an automobile, in order to obtain a natural leather-like hand and texture, is generally placed on a fiber base cloth (for example, a nonwoven fabric, a woven fabric, a knitted fabric, or the like) and is known to have a resin layer composed mainly of a polyurethane-based resin or a polyvinyl chloride-based resin.

[0003] In the laminate sheet for the above-described synthetic leather, in order to impart moisture permeability and air permeability, it can be subjected to a perforation process (perforation processing) (see Patent Documents 1 to 4). For example, Patent Document 1 describes a fiber mass base material, a polyurethane-based resin layer on the surface of the fiber mass base material, and a fabric attached to the back of the fiber mass base material by a polyurethane-based resin adhesive layer, and discloses a composite skin material having a plurality of openings on the surface of the polyurethane-based resin layer.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENTS

[0006] [Patent Document 1] Japanese Patent No. 2017-165209

[0007] [Patent Document 2] Japanese Patent No. 2016-129994

[0008] [Patent Document 3] International Publication No. 2015 / 022722

[0009] [Patent Document 4] International Publication No. 2014 / 097999 SUMMARY OF THE INVENTION

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] When the laminate sheet is perforated, there is a problem that fluff produced by abrasion of the base material comes out of the hole (opening) and damages the appearance. In addition, when the laminate sheet is used for a seat surface of a vehicle such as an automobile, from the viewpoint of ensuring the air permeability of the laminate sheet, a foamed sheet is generally laminated on the base material and sewn without using an adhesive. However, in this case, due to the friction between the base material and the foamed sheet, fluff is more likely to come out of the opening. Furthermore, there is a problem that the back of the base material is rubbed, and the back of the base material is also likely to be abraded and fluffed.

[0012] As the composite skin material of Patent Document 1, by attaching a backing material such as a fabric to the back side of the base material via an adhesive layer, the fluffing of the back side of the base material can be suppressed. However, the composite skin material of Patent Document 1 cannot suppress the exposure of the fluff from the opening. In addition, the laminate of Patent Document 1 uses a polyurethane-based resin as the resin impregnated in the fabric, and thus has a problem of flame retardancy.

[0013] The laminate of Patent Document 4 uses a base cloth layer impregnated with a resin composition containing a polyurethane-based resin in a fabric, suppresses the abrasion of the surface of the base material, and makes it difficult for fluff to be exposed from the opening. However, the laminate of Patent Document 4 has a problem in that, because the stretching of the base material is insufficient, wrinkles are easily generated at the time of attachment, and the elasticity is poor, and thus can only be used for specific board shapes.

[0014] The present application was completed in view of the above problems, and aims to provide a laminate having good elasticity, excellent air permeability, and flame retardancy, and in which fluff is not easily exposed from the opening.

[0015]

Means for solving the problems

[0016] The present inventors have found, as a result of intensive studies for achieving the above object, a base cloth layer having specific properties and a polyvinyl chloride-based resin impregnated in the base cloth layer to have a specific impregnation amount. A sheet having a resin composition layer as a main component, has a plurality of openings that penetrate the base cloth layer and the resin composition layer in the thickness direction, and has a specific air permeability. A laminate having good elasticity, excellent air permeability, and flame retardancy, and in which fluff is not easily exposed from the opening can be provided. The present disclosure relates to objects completed based on these findings.

[0017] That is, the laminate of the present application is composed of a base cloth layer and a resin composition layer having a polyvinyl chloride-based resin as a main component,

[0018] The above resin composition layer has an impregnated portion impregnated in the above base cloth layer,

[0019] has a plurality of openings that penetrate the above base cloth layer and the above resin composition layer in the thickness direction,

[0020] The mass of the above resin composition layer is 30 to 100 parts by mass with respect to 100 parts by mass of the mass of the above base cloth layer

[0021] The tensile strength of the above base cloth layer in the longitudinal and lateral directions is 100 N / cm or more, and the constant load elongation is 20% or more

[0022] The air permeability of the above laminate is 50 cc / cm 2 50 cc / cm or more, and the laminate having the above conditions is provided.

[0023] The impregnated portion is exposed on one surface of the base fabric layer and is not exposed on the other surface.

[0024] In the impregnated portion, the resin composition layer is impregnated from one surface of the base fabric layer to the inside of the base fabric layer to a depth of 10 to 90% of the thickness of the base fabric layer.

[0025] The resin composition layer has a protrusion protruding from one surface of the base fabric layer to the outside of the base fabric layer.

[0026] The back surface of the base fabric layer further contains a backing material having a gas permeability of 100 cc / cm 2 or more.

[0027] The backing material is provided on the back surface of the base fabric layer via an adhesive layer.

[0028] The opening does not penetrate the backing material.

[0029] The base fabric layer or the resin composition layer and the laminate having the backing material on both end surfaces have a constant load elongation of 10% or more in the vertical and horizontal directions and a gas permeability of 50 cc / cm 2 or more.

[0030] A foamed resin layer having a polyvinyl chloride-based resin as a main component is further provided on one surface of the base fabric layer.

[0031] The foamed resin layer contains a thermoplastic polyurethane elastomer.

[0032] The laminate further has a skin layer containing a polyurethane-based resin on the side opposite to the side on which the foamed resin layer and the base fabric layer are present.

[0033] The laminate is used for synthetic leather.

[0034] [Effects of the Invention]

[0035] The laminate of the present application can provide a laminate having good elasticity, excellent gas permeability and flame retardancy, and less exposure of fluff from the opening, and particularly a laminate suitable for use in synthetic leather. [BRIEF DESCRIPTION OF DRAWINGS]

[0036] [SUMMARY] Figure 1 is a schematic view (front cross-sectional view) showing one embodiment of the laminate of the present application.

[0037] [PHOTOGRAPH] Figure 2 is a cross-sectional photograph of the laminate produced according to Example 1.

[0038] [FORMS FOR CARRYING OUT THE INVENTION]

[0039] [laminate]

[0040] The laminate of the present application comprises at least a base cloth layer and a resin composition layer. The laminate can comprise other layers in addition to the base cloth layer and the resin composition layer. The other layers include a foamed resin layer provided on one surface of the base cloth layer, a skin layer provided on the surface opposite to the side on which the foamed resin layer is provided on the base cloth layer, a surface treatment layer provided on the surface opposite to the side on which the foamed resin layer is provided, and a backing material provided on the back surface of the base cloth layer.

[0041] The laminate has a plurality of openings extending through the base cloth layer and the resin composition layer in the thickness direction. When the laminate comprises one or more of the foamed resin layer, the skin layer, and the surface treatment layer, it is preferable that these layers be penetrated by the plurality of openings in the thickness direction. In addition, the plurality of openings preferably do not penetrate the backing material and the adhesive for fixing the backing material to the base cloth layer.

[0042] The resin composition layer has a polyvinyl chloride-based resin as a main component, has an impregnated portion, and at least a portion of the layer is impregnated in the base cloth layer. In the present specification, the "main component" means a component contained in the largest amount by mass in the layer. By having such a structure, the fibers constituting the base cloth layer are bound by the resin composition layer, and are less likely to be cracked, and the exposure of fluff from the openings is suppressed. The impregnated portion is preferably exposed on one surface of the base cloth layer (particularly, the surface on the side of the opening surface). In this case, since the fibers on the surface of the base cloth layer are bound by the resin composition, the exposure of fluff from the openings is further suppressed. In addition, it is preferable that the impregnated portion not be exposed on the other surface of the base cloth layer (particularly, the surface opposite to the opening surface). In this case, there is a region in which the resin composition layer is not impregnated, and the extensibility of the base cloth layer is sufficiently maintained, and the elasticity of the laminate is improved. In addition, the laminate also has the advantages of good air permeability, light weight, good texture, and the like.

[0043] In the impregnated portion, it is preferable that the resin composition layer be impregnated from the one surface of the base cloth layer (particularly, the surface on the side of the opening surface) to a depth of 10% to 90% (preferably, 30% to 70%) of the inside of the base cloth layer. When the impregnation is to a depth of 10% or more of the inside of the base cloth layer, the fibers near the surface of the base cloth layer are bound by the resin composition layer, the fuzzing of the surface of the base cloth layer is further suppressed, and the exposure of fluff is further suppressed.

[0044] The aforementioned resin composition layer preferably has a protrusion (non-impregnated portion) extending outward from one surface (particularly the open side) of the base fabric layer. With this configuration, when other layers, such as the foamed resin layer, are laminated through the protrusion of the resin composition layer, the protrusion acts as an adhesive layer, further improving the adhesion between the base fabric layer and the other layers. Furthermore, this prevents misalignment between layers, reduces friction, and minimizes wear on the base fabric layer. Moreover, the resin composition layer at the protrusion does not penetrate the base fabric layer.

[0045] The mass of the resin composition layer relative to 100 parts by mass of the base fabric layer is 30 to 100 parts by mass, preferably 50 to 90 parts by mass, and most preferably 50 to 80 parts by mass. When the mass of the resin composition layer is 30 parts by mass or more, the base fabric layer is sufficiently impregnated, further improving the adhesion with the other layers. As a result, the base fabric layer experiences wear, and the leakage of fibers from openings can be prevented. When the mass of the resin composition layer is 100 parts by mass or less, the elongation of the base fabric layer can be adequately maintained, and the elasticity of the laminate is improved. Furthermore, it has the advantages of reducing the weight of the laminate and improving its texture.

[0046] Figure 1 One embodiment of the aforementioned laminate is shown in the document. For example... Figure 1 As shown, the laminate 1 includes a base fabric layer 11, a resin composition layer 12 partially impregnated from one surface 11a of the base fabric layer 11, a foamed resin layer 13, a skin layer 14, and a surface protective layer 15 located on the outermost surface of the laminate 1, and are shown in sequence. The base fabric layer 11 and the foamed resin layer 13 are bonded together by the resin composition layer 12. Furthermore, a backing material 17 is laminated onto another surface 11b of the base fabric layer 11 via a partially arranged adhesive layer 16. The laminate sheet 1 is provided with a plurality of openings 20 extending from the base fabric layer 11 to the surface protective layer 15.

[0047] The resin composition layer 12 is composed of an impregnated portion 12a impregnated in the base fabric layer 11 and a protrusion (unimpregnated portion) 12b protruding outward from the surface 11a of the base fabric layer 11. The impregnated portion 12a is impregnated from the surface (the side facing the opening face 20a) 11a of the base fabric layer 11 to the back side (the side opposite to the opening face 20a) of the base fabric layer 11 to 50% of the thickness of the base fabric layer 11. That is, the resin composition layer 12 is exposed on the front surface 11a of the base fabric layer 11 rather than on the back surface 11b of the base fabric layer 11. The protrusion 12b protrudes from the surface 11a of the base fabric layer 11. Since the protrusion 12b acts as an adhesive, the adhesion between the foamed resin layer 13 and the base fabric layer 11 is excellent.

[0048] (Base layer fabric)

[0049] The base fabric layer has a tensile strength of 100 N / cm or more and a constant load elongation ratio in the longitudinal and transverse directions of 20% or more. Due to these properties, the laminate in which the base fabric layer is impregnated with the resin composition layer is less likely to generate wrinkles at the time of bonding and has good elasticity. The tensile strength and the constant load elongation ratio are the values of the base fabric layer in the unimpregnated state of the resin composition layer.

[0050] The tensile strength in the longitudinal and transverse directions is each 100 N / cm or more, preferably 120 N / cm or more. When the tensile strength is 100 N / cm or more, even in the state in which perforation processing is performed, the laminate has an appropriate strength. The tensile strength is a value measured and calculated by the following tensile test.

[0051] < Tensile Test >

[0052] Three test pieces each having a width of 50 mm and a length of 150 mm are collected from the warp and weft directions on the base fabric layer. Under the conditions of room temperature 20 ± 2°C and humidity 65 ± 5% RH, the test pieces are gripped at both ends by a gripping tool without slack, and a tensile test machine grips the test pieces with a tensile grip. The test pieces are pulled by moving the gripping tool at a speed of 200 mm / min with a gripping width of 50 mm and a gripping interval of 100 mm, and the test pieces are broken. Then, the maximum load per unit width (N / cm) until the test pieces are broken is measured, and the average value of three test pieces is obtained.

[0053] The constant load elongation ratio in the vertical and horizontal directions is each 20% or more, preferably 30% or more. When the constant load elongation ratio is 20% or more, even in the state in which perforation processing is performed, the constant load elongation ratio is sufficiently extended, wrinkles are less likely to be generated at the time of stretching, and the laminate has good elasticity. The constant load elongation ratio is a value measured and calculated by the following constant load elongation ratio test.

[0054] < Constant Load Elongation Ratio Test >

[0055] Three test pieces each having a width of 50 mm and a length of 150 mm are collected from the warp and weft directions on the base fabric layer. Next, two marker lines are connected to the center portion of the test pieces so that the distance between the marker lines is 100 mm. This is connected to the test equipment with a gripping interval of 150 mm and a load of 78.4 N (8 kgf) is gently applied. In the case of the load, 10 minutes are maintained, and then the distance between the marker lines is determined. Then, the constant load elongation ratio is calculated by the following formula, and the average value of three test pieces is obtained.

[0056] Constant load elongation ratio (%) = A - 100

[0057] A: Distance between marker lines after 10 minutes of load (mm)

[0058] The base fabric layer includes, for example, a woven fabric, a knitted fabric, a nonwoven fabric, and the like, and a fibrous base material such as natural leather. The type of fiber constituting the fibrous fabric is not particularly limited, and includes synthetic fibers such as polyester-based resins, polyamide-based resins, polyacrylonitrile-based resins, polyolefin-based resins, polyvinyl alcohol, and the like; natural fibers such as cotton, hemp, and the like; regenerated fibers such as rayon, silk, acetate, and the like; and semi-synthetic fibers. The above-mentioned fiber can be used singly or two or more types of fibers can be used. Of these, from the viewpoint of more excellent strength and processability, a knitted fabric of synthetic fiber, particularly a knitted fabric of polyester fiber is preferred. The base fabric layer can be a single layer or a plurality of layers.

[0059] The unit gauge of the base fabric layer is not particularly limited, and is preferably 100 to 400 g / m 2 , more preferably 150 to 300 g / m 2 . When the unit gauge is 100 g / m 2 or more, sufficient strength as an interior material for an automobile can be obtained. When the unit gauge is 300 g / m 2 or less, the weight of the laminate can be reduced.

[0060] <Resin composition layer>

[0061] The resin composition layer contains a polyvinyl chloride-based resin as a main component. That is, the resin composition contains a polyvinyl chloride-based resin in the largest mass ratio. As a result, the fibers constituting the base fabric layer in the impregnated portion are bound by the resin composition layer, and are less likely to be cracked, and the protruding fluff from the opening is suppressed. In addition, the flame retardancy of the laminate can be improved, and the cost can be suppressed, thereby achieving excellent economy. The resin composition layer preferably contains a polyvinyl chloride-based resin as a bonding component. In this case, when the other layers are stacked on the base fabric layer, the adhesion between the base fabric layer and the other layers is improved. In addition, as a result, the layers are less likely to be misaligned, and are less likely to be rubbed, and the base fabric layer is less likely to be worn. The polyvinyl chloride-based resin can be used singly or two or more types can be used.

[0062] The polyvinyl chloride-based resin is a polymer containing a vinyl chloride or a vinylidene chloride as an essential monomer component. That is, the polyvinyl chloride-based resin is a polymer containing at least a structural unit derived from a vinyl chloride or a vinylidene chloride in the molecule (in one molecule).

[0063] The polyvinyl chloride-based resin includes a polymer of a vinyl chloride, a polymer of a vinylidene chloride, a copolymer of a vinyl chloride or a vinylidene chloride and another monomer, a chlorinated polyvinyl chloride, and a chlorinated polyolefin. The chlorinated polyolefin includes a chlorinated polyethylene and a chlorinated polypropylene.

[0064] The above-mentioned copolymers include chloroethylene-vinyl acetate copolymer, chloroethylene-ethylene copolymer, chloroethylene-propylene copolymer, chloroethylene-styrene copolymer, chloroethylene-isobutylene copolymer, chloroethylene-urethane copolymer, chloroethylene-butadiene copolymer, chloroethylene-isoprene copolymer, chloroethylene-chlorinated propylene copolymer, chloroethylene-maleate copolymer, chloroethylene-(meth)acrylate copolymer, and the like chloroethylene- vinyl ester copolymer, chloroethylene-acrylonitrile copolymer, chloroethylene-vinyl ether copolymer, chloroethylene-anhydrous styrene-maleate tercopolymer, chloroethylene-styrene-acrylonitrile tercopolymer, chloroethylene-vinylidene chloride-vinyl acetate tercopolymer, and ethylene-vinyl acetate-chloroethylene copolymer. The above-mentioned copolymers include block copolymer, random copolymer, graft copolymer, and the like.

[0065] Among the above-mentioned polyvinyl chloride-based resins, polyvinyl chloride (chloroethylene polymer) is preferred.

[0066] The above-mentioned polyvinyl chloride-based resins can be obtained by known or conventional polymerization. The polymerization method of the above-mentioned polyvinyl chloride-based resins is not particularly limited, and emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and the like can be used. Among them, the polyvinyl chloride-based resins obtained by emulsion polymerization or suspension polymerization are preferred.

[0067] The average polymerization degree of the above-mentioned polyvinyl chloride-based resins (based on JIS K6721) is not particularly limited, and is preferably 800 to 4000, more preferably 1100 to 3500, and most preferably 1300 to 2800. When the above-mentioned average polymerization degree is within the above-mentioned range, the exposure of the pile from the opening is further suppressed.

[0068] The content ratio of the polyvinyl chloride-based resins in the above-mentioned resin composition is not particularly limited, and is preferably 70% by mass or more, and most preferably 90% by mass or more, relative to 100% by mass of the total amount of the resin composition. When the above-mentioned content ratio is 70% by mass or more, the flame retardancy of the laminate is more excellent. The above-mentioned content ratio can also be 100% by mass.

[0069] The resin composition layer preferably further contains a plasticizer. Thereby, the processability of the laminate becomes more excellent.

[0070] The above-mentioned plasticizer can be used a general plasticizer used in a polyvinyl chloride-based resin. The above-mentioned plasticizer includes di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and C9-11 mixed alkyl phthalate butyl phthalate, isophthalate; aliphatic carboxylic acid ester, diisooctyl adipate, diisodecyl adipate, di-2-ethylhexyl sebacate; tri-n-butyl trimellitate (TBTM), trimellitate (2-tolylhexyl) (TOTM), and other trimellitates; diethylene glycol dibenzoate, dipropylene glycol dibenzoate, polypropylene glycol dibenzoate, polyethylene glycol dibenzoate, and other glycol dibenzoates; tricresyl phosphate, trimethylsilyl phosphate, and other phosphate esters; chlorinated paraffin, chlorinated fatty acid ester, and other halogen-containing compounds; epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized castor oil, and other epoxy group-containing fatty acids; and polyester. The plasticizer can be used singly or in combination of two or more.

[0071] The content of the above-mentioned plasticizer is preferably 50 to 120 parts by mass, and more preferably 60 to 100 parts by mass, relative to 100 parts by mass of the polyvinyl chloride-based resin. When the content is 50 parts by mass or more, the processability of the laminate becomes better. When the content is 90 parts by mass or less, the aging speed of the resin composition layer can be slowed down.

[0072] The above-mentioned resin composition layer can contain other components than the above-mentioned components. The above-mentioned other components include a resin other than the polyvinyl chloride-based resin, a processing aid, a reinforcing agent, a flame retardant, a colorant (dye, pigment, and the like), an antifoaming agent, a leveling agent, a crosslinking agent, and a silane coupling agent. The above-mentioned other components can be used singly or in combination of two or more.

[0073] <foamed resin layer>

[0074] The foamed resin layer preferably contains a polyvinyl chloride-based resin as a main component. That is, the foamed resin layer contains a polyvinyl chloride-based resin at the largest mass ratio. In this case, since the main components of the resin composition layer and the foamed resin layer are both polyvinyl chloride-based resins, the adhesion between the base layer portion and the foamed resin layer is further improved by the resin composition layer, the interlayer misregistration is suppressed, and the wear resistance and the bending resistance (particularly, low-temperature bending resistance) are improved. In addition, by suppressing the interlayer misregistration, the generation of fluff on the surface of the base layer portion can be further suppressed. The polyvinyl chloride-based resin can be used alone or two or more kinds can be used.

[0075] The polyvinyl chloride-based resin in the foamed resin layer is exemplified and described in the polyvinyl chloride-based resin contained in the resin composition layer. As the polyvinyl chloride-based resin, polyvinyl chloride is preferred.

[0076] The average particle diameter of the polyvinyl chloride-based resin is not particularly limited, and is preferably 0.1 to 5 μm, and more preferably 0.2 to 4 μm. When the average particle diameter is 0.1 μm or more, the productivity at the calendering process is good. When the average particle diameter is 5 μm or less, the dispersibility of the thermoplastic polyurethane elastomer particles in the vinyl chloride composition is good. The average particle diameter is a value measured by a laser diffraction / scattering method.

[0077] The foamed resin layer preferably further contains a thermoplastic polyurethane elastomer. Thereby, a laminate having a light weight and excellent wear resistance can be obtained. The thermoplastic polyurethane elastomer can be used alone or two or more kinds can be used.

[0078] The thermoplastic polyurethane elastomer (TPU) is composed of a hard segment and a soft segment. The thermoplastic polyurethane elastomer is generally obtained by reacting a polyisocyanate, a long-chain polyol, a chain extender, and other isocyanate-reactive compounds.

[0079] The polyisocyanate is a compound having two or more isocyanate groups in the molecule. The polyisocyanate includes an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate, and an aromatic aliphatic polyisocyanate. In addition, a dimer or a trimer, a reaction product, or a polymer of the aliphatic polyisocyanate, the cycloaliphatic polyisocyanate, the aromatic polyisocyanate, and / or the aromatic aliphatic polyisocyanate (for example, a dimer or a trimer of diphenylmethane diisocyanate, a reaction product of trimethylolpropane and toluene diisocyanate, a reaction product of trimethylolpropane and hexamethylene diisocyanate, a poly-methylene polyphenyl isocyanate, a polyether polyisocyanate, a polyester polyisocyanate, and the like) and the like are also included. The polyisocyanate can be used alone or two or more kinds can be used.

[0080] The long-chain polyol includes a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polyacrylic polyol, and the like. The number average molecular weight of the long-chain polyol is usually 500 or more, preferably 500 to 10,000, more preferably 600 to 6,000, and most preferably 800 to 4,000. The long-chain polyol can be used singly or in combination of two or more.

[0081] The chain extender can be used in combination with a chain extender usually used for producing the thermoplastic polyurethane elastomer, such as a low-molecular-weight polyol and a polyamine. The molecular weight of the chain extender is usually 500 or less, and preferably 300 or less. The chain extender can be used singly or in combination of two or more.

[0082] The Shore A hardness of the thermoplastic polyurethane elastomer is preferably 50 to 80, and more preferably 55 to 75. When the Shore A hardness is within the above range, the compatibility with the polyvinyl chloride-based resin is improved. Thus, when the Shore A hardness is 50 or more, the processability and the cuttability of the resin composition as a precursor of the foamed resin layer are excellent, and the granulation is facilitated. In addition, when the Shore A hardness is 80 or less, the flexibility and the bending resistance (particularly, low-temperature bending resistance) of the laminate are further improved. Furthermore, the compatibility with the polyvinyl chloride-based resin is improved, and the sheet processability when the unfoamed resin sheet as a precursor of the foamed resin layer is obtained by the calendering method is excellent.

[0083] The melting point of the thermoplastic polyurethane elastomer is preferably 140 to 200°C, and more preferably 150 to 180°C. When the melting point is 140°C or more, the foamed resin layer is formed well, and the heat resistance when used as an automotive interior material is maintained. When the melting point is 200°C or less, the compatibility with the polyvinyl chloride-based resin is good, and the calendering processability is excellent.

[0084] The content of the thermoplastic polyurethane elastomer is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, and most preferably 8 to 35 parts by mass, relative to 100 parts by mass of the polyvinyl chloride-based resin. When the content is 1 part by mass or more, the content of the thermoplastic polyurethane elastomer is further sufficient, and the wear resistance and the bending resistance (particularly, low-temperature bending resistance) are further improved. When the content is 50 parts by mass or less, the content of the polyvinyl chloride-based resin is sufficiently ensured, and the performance of the polyvinyl chloride-based resin is further exerted. In addition, the processability of the unfoamed resin sheet by the calendering method is further improved.

[0085] The foamed resin layer preferably contains a plasticizer. The use of the plasticizer further improves the flexibility of the foamed resin layer and the laminate, and the bending resistance (particularly, low-temperature bending resistance) is further improved.

[0086] The plasticizer in the foamed resin layer is exemplified and described as a plasticizer that can be included in the resin composition layer. One kind of the plasticizer can be used alone, or two or more kinds can be used.

[0087] The content of the plasticizer is preferably 50 to 90 parts by mass, and more preferably 60 to 90 parts by mass, relative to 100 parts by mass of the polyvinyl chloride-based resin. When the content is greater than 50 parts by mass, the texture of the laminate becomes better. When the content is less than 90 parts by mass, the plasticizer can be inhibited from bleeding to the surface of the foamed resin layer, and high adhesion to the adjacent layer can be maintained, thereby further improving the wear resistance. In addition, the performance of the polyvinyl chloride-based resin can be more effectively exhibited.

[0088] The foamed resin layer preferably contains a filler. By containing the filler, the rigidity and durability of the foamed resin layer can be improved.

[0089] The filler is not particularly limited, and includes inorganic fillers such as calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate, calcium sulfite, calcium borate, calcium silicate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium oxide, magnesium hydroxide, barium sulfate, aluminum hydroxide, titanium oxide, antimony oxide, silicon dioxide, zinc borate, zinc stannate, zinc hydroxystannate, mica, talc, kaolin, clay, asbestos, synthetic zeolite, synthetic hydrotalcite, and the like. One kind of the filler can be used alone, or two or more kinds can be used.

[0090] The content of the filler is preferably 1 to 100 parts by mass, and more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the polyvinyl chloride-based resin. When the content is greater than 1 part by mass, the foamed resin layer is more likely to form a closed cell structure. In addition, the rigidity and durability of the foamed resin layer are improved. When the content is less than 100 parts by mass, the content can be included without affecting the bending resistance and wear resistance.

[0091] The foamed resin layer can contain other components in addition to the above-described components. The other components can be components included in known or conventional foams. The other components are exemplified and described as components that can be included in the resin composition layer. One kind of the other components can be used alone, or two or more kinds can be used.

[0092] The surface density of the foamed resin layer is preferably 0.3 to 0.7 g / cm 3 , and more preferably 0.4 to 0.5 g / cm 3 . When the surface density is 0.3 g / cm 3 or less, the wear resistance of the laminate becomes better. When the surface density is 0.7 g / cm 3 or more, the weight becomes lighter, a sufficient thickness can be ensured, and the softness becomes better. In addition, even when the surface density is less than 0.7 g / cm 3The foamed resin layer described above can also maintain the strength resulting from the mixing of the polyvinyl chloride-based resin. In addition, by setting the surface density described above within the range described above, the texture of the laminate will become better. The method of calculating the surface density described above is to cut the foamed resin layer into a size of 30 cm square, set the thickness to an average value of n = 5, calculate the volume of the cut foamed resin layer, and calculate the mass and volume of the foamed resin layer.

[0093] The average cell diameter of the foamed resin layer described above is preferably 50 to 250 μm, more preferably 55 to 160 μm, and most preferably 60 to 100 μm. When the average cell diameter described above is 50 μm or more, the softness becomes better. When the average cell diameter described above is less than 250 μm, the abrasion resistance becomes better.

[0094] The maximum cell diameter of the foamed resin layer described above is preferably 0 to 400 μm, more preferably 90 to 250 μm, and most preferably 100 to 200 μm. When the maximum cell diameter described above is 80 μm or more, the softness becomes better. When the maximum cell diameter described above is less than 400 μm, the abrasion resistance becomes better.

[0095] The expansion ratio of the foamed resin layer described above is preferably 2.0 to 4.0 times, and most preferably 2.5 to 3.0 times. When the expansion ratio described above is 2.0 times or more, the texture of the laminate becomes better. When the expansion ratio described above is 4.0 times or less, the abrasion resistance of the laminate becomes better.

[0096] The method of obtaining the expansion ratio described above is as follows. An electron micrograph (50x) of the cross section of the foamed resin layer in the thickness direction is read into a computer using a scanner, the foamed portion is colored white, and then the colors of the foamed portion and the unfoamed portion are binarized to white and black. The white points are counted by integration. Then, the expansion ratio is obtained by using the following formula.

[0097] Expansion ratio = (foamed portion area + unfoamed portion area) / unfoamed portion area

[0098] The cell structure of the foamed resin layer described above can be any one of a closed cell structure, a semi-independent semi-open cell structure, and an open cell structure, but preferably has a closed cell structure. When it has a closed cell structure, the abrasion resistance and the bending resistance (particularly low-temperature bending resistance) become better.

[0099] The thickness of the foamed resin layer described above is not particularly limited, and is preferably 200 to 650 μm, more preferably 250 to 600 μm, and most preferably 300 to 500 μm. When the thickness described above is greater than 200 μm, the abrasion resistance becomes better. When the thickness described above is less than 650 μm, the weight is further reduced.

[0100] (Skin layer)

[0101] From the viewpoint of further improving the abrasion resistance, the above-mentioned skin layer is preferably a non-foamed resin layer. The above-mentioned skin layer is preferably selected to contain a polyurethane-based resin. The skin layer containing a polyurethane-based resin has better adhesion to the above-mentioned foamed resin layer in the case of containing a thermoplastic polyurethane elastomer. Thereby, the interlayer misregistration between the skin layer and the foamed resin layer is suppressed, and the abrasion resistance is improved. Further, the texture of the laminate becomes better. The above-mentioned skin layer (non-foamed resin layer) can be a single layer or a plurality of layers.

[0102] The above-mentioned polyurethane-based resin is generally obtained by reacting a polyisocyanate, a long-chain polyol, a chain extender, and other isocyanate-reactive compounds. The above-mentioned polyisocyanate, long-chain polyol, and chain extender include examples and illustrations of constituent components of a thermoplastic polyurethane elastomer that can be contained in the foamed resin layer, respectively. The above-mentioned polyisocyanate, long-chain polyol, and chain extender can be used only one kind, or two or more kinds can be used.

[0103] The above-mentioned long-chain polyol is particularly preferably a polycarbonate polyol. That is, the polyurethane-based resin that can be contained in the skin layer is preferably a polycarbonate-based polyurethane-based resin. By using a polycarbonate-based polyurethane-based resin, the abrasion resistance of the laminate is further improved.

[0104] The polyurethane-based resin in the above-mentioned skin layer is preferably an aqueous polyurethane-based resin. That is, the polyurethane-based resin is preferably an aqueous polycarbonate-based polyurethane-based resin. By having such a structure, the abrasion resistance becomes more excellent, and the resistance to oleic acid (oleic acid resistance) from the sebum component also becomes more excellent. Further, since an organic solvent is not used, it also contributes to the reduction of environmental load.

[0105] The content ratio of the polyurethane-based resin (particularly, polycarbonate-based polyurethane-based resin) in the above-mentioned skin layer is not particularly limited, and is preferably 30% by mass or more, and more preferably 50% by mass or more, based on 100% by mass of the total amount of the above-mentioned skin layer. When the above-mentioned content ratio is more than 30% by mass, the adhesion to the foamed resin layer becomes higher, and the abrasion resistance of the laminate becomes better.

[0106] The above-mentioned skin layer can contain other components in addition to the polyurethane-based resin. The above-mentioned other components include examples and illustrations of other components that can be contained in the above-mentioned resin composition layer. The above-mentioned other components can be used only one kind, or two or more kinds can be used.

[0107] The thickness of the above-mentioned skin layer is not particularly limited, and is preferably 10 to 100 μm, and more preferably 20 to 40 μm. When the above-mentioned thickness is 10 μm or more, the abrasion resistance of the laminate is further improved. When the above-mentioned thickness is less than 100 μm, the weight of the laminate is further reduced.

[0108] (Surface protective layer)

[0109] The surface protective layer is the outermost layer of the laminate and is a layer that protects the inside, such as the skin layer, the foamed resin layer, the resin composition layer, and the base fabric layer, from the effects of friction and the like, and further improves the wear resistance of the laminate.

[0110] The surface protective layer preferably contains a polyurethane-based resin. When a polyurethane-based resin is contained, the adhesion of the surface protective layer containing the polyurethane-based resin to the skin layer is better. As a result, a gap is less likely to occur between the surface protective layer and the skin layer, and the wear resistance becomes very good. In addition, the texture of the laminate also becomes better.

[0111] The polyurethane-based resin is generally obtained by reacting a polyisocyanate, a long-chain polyol, a chain extender, and, if necessary, another isocyanate-reactive compound. The polyisocyanate, the long-chain polyol, and the chain extender include those exemplified and described as constituent components of the thermoplastic polyurethane elastomer that can be contained in the foamed resin layer, respectively. As the polyisocyanate, the long-chain polyol, and the chain extender, only one kind can be used, or two or more kinds can be used.

[0112] The long-chain polyol is particularly preferably a polycarbonate polyol. That is, the polyurethane-based resin that can be contained in the skin layer is preferably a polycarbonate-based polyurethane-based resin. By using a polycarbonate-based polyurethane-based resin, the wear resistance of the laminate is further improved.

[0113] The polyurethane-based resin in the surface layer skin is preferably a water-based polyurethane-based resin. That is, the polyurethane-based resin is preferably a water-based polycarbonate-based polyurethane-based resin. By having such a structure, the adhesion of the skin layer containing the water-based polyurethane-based resin described above becomes better, the wear resistance becomes more excellent, and the acid resistance to oil also becomes more excellent. In addition, since no organic solvent is used, it also contributes to the reduction of environmental load.

[0114] The content ratio of the polyurethane-based resin (particularly a polycarbonate-based polyurethane-based resin) in the surface protective layer is not particularly limited, and is preferably 60% by mass or more, and more preferably 90% by mass or more, based on 100% by mass of the total amount of the surface protective layer described above. When the content ratio described above is 60% by mass or more, the wear resistance of the laminate becomes good. The content ratio described above can also be 100% by mass.

[0115] When the surface protective layer contains a polyurethane-based resin, the polyurethane-based resin (particularly, the water-based polycarbonate-based polyurethane-based resin) in the surface protective layer is preferably crosslinked by a carbodiimide-based crosslinking agent. The carbodiimide-based crosslinking agent includes dicyclohexylmethane carbodiimide, dicyclohexyl carbodiimide, tetramethylxylylene carbodiimide, and polyurethane-denatured carbodiimide. As the carbodiimide-based crosslinking agent, a water-based carbodiimide-based crosslinking agent is preferable. One kind or two or more kinds of carbodiimide-based crosslinking agents can be used.

[0116] The surface protective layer is preferably a water-based polycarbonate-based polyurethane-based resin crosslinked with a water-based carbodiimide-based crosslinking agent. Since the surface protective layer becomes a crosslinked film having high oleic acid resistance, the laminate has excellent wear resistance in addition to the wear resistance, and thus can maintain good wear resistance even when adhered to sweat, sebum, moisturizing lotion, or the like in contact with the human body.

[0117] The content of the structural moiety derived from the carbodiimide-based crosslinking agent in the surface protective layer (i.e., the content of the carbodiimide-based crosslinking agent to be incorporated when the surface protective layer is formed) is not particularly limited, and is preferably 0.5 to 10.0 parts by mass, and more preferably 2.0 to 5.0 parts by mass, based on 100 parts by mass of the polyurethane-based resin.

[0118] The surface protective layer preferably contains a silicon-based compound. The addition of the silicon-based compound improves the smoothness of the surface, and further improves the wear resistance of the laminate. One kind or two or more kinds of silicon-based compounds can be used.

[0119] The silicon-based compound is preferably a silicon compound having a silicone bonding amount of 2000 or less. The silicon-based compound includes silicone oil, modified silicone oil, and silicone resin.

[0120] The silicone oil (pure silicone oil) includes dimethyl silicone oil and methylphenyl silicone oil.

[0121] The modified silicone oil includes polyether-modified silicone oil (polyether-modified dimethyl silicone oil, etc.), alkyl-modified silicone oil (alkyl-modified dimethyl silicone oil, etc.), aralkyl-modified silicone oil (aralkyl-modified dimethyl silicone oil, etc.), higher fatty acid ester-modified silicone oil (higher fatty acid ester-modified dimethyl silicone oil, etc.), and fluoroalkyl-modified silicone oil (fluoroalkyl-modified dimethyl silicone oil, etc.).

[0122] The silicone resin includes linear silicone resin and modified silicone resin. The linear silicone resin includes methyl silicone resin and methylphenyl silicone resin. The modified silicone resin includes alkyd-modified silicone resin, epoxy-modified silicone resin, acrylic-modified silicone resin, and polyester-modified silicone resin.

[0123] When the surface protective layer contains the polyurethane-based resin, the content of the silicon compound in the surface protective layer is not particularly limited, and is preferably 3.0 to 20.0 parts by mass, and more preferably 6.0 to 13.0 parts by mass, based on 100 parts by mass of the polyurethane-based resin.

[0124] The surface protective layer can contain other components in addition to the above components. The other components include those listed as the other components that can be contained in the resin composition layer. As the other components, one kind can be used alone, or two or more kinds can be used.

[0125] The thickness of the surface protective layer is not particularly limited, and is preferably 5 to 40 μm, and more preferably 10 to 20 μm. When the thickness is 5 μm or more, the wear resistance of the laminate is further improved. When the thickness is 40 μm or less, the bending resistance of the laminate is further improved.

[0126] (backing material)

[0127] The backing material is used by being attached to the back surface (the surface on the opposite side of the opening surface side) of the base cloth layer, and can suppress fluffing of the back surface of the base cloth layer.

[0128] The air permeability of the backing material is preferably 100 cc / cm 2 or more, and more preferably 150 cc / cm 2 or more. When the air permeability is higher than 100 cc / cm 2 , the laminate having a plurality of openings can maintain high air permeability. The air permeability is a value measured based on the 8.26.1A method (Frazier method) of JIS L1096 (2010).

[0129] The backing material includes a fiber fabric such as a fabric, a woven fabric, and a nonwoven fabric, and a fiber base material such as natural leather. Among them, the woven fabric is preferable from the viewpoint of high degree of freedom of extension. The fiber constituting the fiber fabric includes those exemplified and described as the fiber constituting the fiber fabric in the base cloth layer. In addition, as the fiber, dyed yarn is preferable from the viewpoint of suppressing bleeding and coloring of the resin composition layer. The fiber can use only one kind of fiber, or two or more kinds can be used. The backing material can be a single layer or a plurality of layers.

[0130] The backing material is preferably adhered to the back surface of the base cloth layer by an adhesive layer. The backing material is preferably adhered to the back surface of the base cloth layer at a plurality of points by an adhesive layer. Thereby, the adhesion can be performed while ensuring the air permeability of the laminate.

[0131] The adhesive used to form the above-mentioned adhesive layer is not particularly limited, and a known or commonly used adhesive can be used. Among them, the above-mentioned adhesive has the advantage of not using a solvent, and can be processed by melting by heating, and the adhesion can be easily exhibited locally even if it is coated on the entire surface. A melt type adhesive is preferred because it has the advantage that a greater adhesive force can be obtained by a heat sealing process.

[0132] The above-mentioned adhesive is preferably a curable adhesive. That is, the above-mentioned adhesive is preferably a curable hot melt type adhesive. The above-mentioned curing includes curing by active energy ray irradiation, curing by heat (thermosetting), curing by moisture (moisture curing), and two-component reaction type curing (two-component reaction curing). When the curing is performed at room temperature, no additional curing treatment such as active energy ray irradiation, heating, or the like is required. The active energy ray includes visible light, ultraviolet rays, and electron beams.

[0133] The above, the embodiment of the above-mentioned Figure 1 described above, but the laminate is not limited to such an embodiment. In addition, the laminate does not have the protrusion 12b and the skin layer 14 as essential components. For example, a structure does not have the protrusion 12b, a structure does not have the skin layer 14, or it is also possible that there is no protrusion 12b and the skin layer 14. In addition, the laminate can have other layers in addition to the above-mentioned layers as long as the effects of the present application are not impaired. The other layers include a primer layer for improving the adhesion between the foamed resin layer and the skin layer.

[0134] (laminate)

[0135] The above-mentioned laminate has an air permeability of 50 cc / cm 2 or more, preferably 60 cc / cm 2 or more, and most preferably 90 cc / cm 2 or more. The air permeability of 50 cc / cm 2 or more is excellent in air permeability, and less stuffy when used in a laminated seat. The above-mentioned air permeability is a value measured based on JIS L1096 (2010) 8.26.1A method (Frazier method).

[0136] In the above-described laminate, the constant load elongation of the laminate in the up-and-down and left-and-right directions is preferably 10% or more, more preferably 15% or more. When the constant load elongation is 10% or more, the constant load elongation of the laminate is easily increased. The measurement and calculation are performed in the same manner as the constant load elongation test of the above-described laminate except that the above-described laminate is used as a test piece. The above-described laminate is a laminate in which the backing material is used as one end surface and the above-described base fabric layer or the above-described resin composition layer is used as the other end surface. When the above-described resin composition layer has the above-described protruding portion, the above-described resin composition layer is used as the other end surface, and the above-described laminate is a laminate in which the above-described resin composition layer and the above-described backing material are used as two end surfaces. On the other hand, when the above-described resin composition layer does not have the above-described protruding portion, the above-described base fabric layer is used as the other end surface, and the above-described laminate is a laminate in which the above-described base fabric layer and the above-described backing material are used as two end surfaces.

[0137] In the above-described laminate, the air permeability of the laminate in which the above-described base fabric layer or the above-described resin composition layer and the above-described backing material are used as two end surfaces is preferably 50 cc / cm 2 ·s or more, more preferably 60 cc / cm 2 ·s. When the air permeability is higher than 50 cc / cm 2 ·s, the laminate having a plurality of openings can maintain high air permeability. The air permeability is a value measured based on the method of JIS L1096 (2010) 8.26.1A (Frazier method).

[0138] The BLC value of the above-described laminate is preferably 4.0 to 6.0, more preferably 4.5 to 5.7. When the BLC value is 4.0 or more, the texture of the laminate is not too hard, and when the BLC value is 6.0 or less, the texture of the laminate is not too soft, and thus a moderate hand feeling can be obtained within the above-described range. The BLC value refers to a strain measurement value when pushed in with a load of 500 g, and can be measured using a tactile measuring instrument (trade name "GT303 Leather Softness Tester" (manufactured by GOTECH TESTING MACHINES INC.).

[0139] The above-described laminate can be used as synthetic leather, is preferably used as vehicle interior synthetic leather (particularly, for automobile interior synthetic leather), and is more preferably used as vehicle seat synthetic leather (particularly, for automobile seat synthetic leather).

[0140] The laminate 1 as one embodiment of the above-described laminate can be manufactured as follows. First, a laminate in which the resin composition layer 12 is impregnated in the base cloth layer 11 is manufactured. As the resin composition for forming the resin composition layer 12, the polyvinyl chloride-based resin is added, and additives such as the above-described other components are added as necessary, and the resin composition (I) is prepared by dissolving and mixing in a solvent as necessary. The content of each component in the resin composition (I) is adjusted so that the content in the resin composition layer 12 is within the above-described preferable range.

[0141] Next, the resin composition (I) for forming the resin composition layer 12 is applied to the base cloth layer 11, and the base cloth layer 11 is impregnated, and then heating is performed using a heating device such as an oven. When the resin composition (I) contains a solvent, the solvent is volatilized by the above-described heating. The protrusions 12b can be formed by performing heating to stop impregnation before the resin composition (I) is completely impregnated in the base cloth layer 11 after the resin composition (I) is applied, or by adjusting the viscosity of the resin composition (I). Furthermore, the above-described heating is performed after the base cloth layer 11 is left to stand after being impregnated to the desired depth. The heating is performed at a temperature of, for example, 100 to 150°C for 1 to 5 minutes.

[0142] The resin composition (I) can be applied by a known or commonly used method, examples of which include reverse coating, roll coating, die coating, wire bar coating, and blade coating. In addition, as other methods, a method in which the base cloth layer 11 is impregnated in the resin composition (I) can be given.

[0143] Next, the foamed resin layer 13 is formed on the impregnation side of the base cloth layer 11 in which the resin composition (I) is impregnated. The foamed resin layer 13 can be formed as follows. First, a resin component such as a polyvinyl chloride-based resin is heated and melted and mixed, and a plasticizer, a filler, the above-described other components, a blowing agent, a blowing promoter, a cell regulator, and the like can be added as necessary. The agent is added and kneaded, and then cooled to prepare a resin composition (II) (pellet or the like). The preferable content of each component in the resin composition (II), such as a polyvinyl chloride-based resin, a thermoplastic polyurethane elastomer, and the like, is the same as the content in the above-described foamed resin layer.

[0144] The above-described blowing agent includes a supercritical fluid; inorganic blowing agents such as ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and azide; organic blowing agents such as azo-based blowing agents, nitroso-based blowing agents, hydrazide-based blowing agents, carbazide-based blowing agents, and triazine-based blowing agents; heat-expandable compounds such as isobutane and pentane; and the above-described heat-expandable compounds include heat-expandable microparticles (heat-expandable microcapsules) encapsulated in microcapsules made of a thermoplastic resin such as polyvinylidene chloride, polyacrylonitrile, and poly(meth)acrylate. As the blowing agent, one kind can be used alone, or two or more kinds can be used.

[0145] The above-mentioned azo-based foaming agent includes azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, diethyl azodicarboxylate, diisopropyl azodicarboxylate and azobis(hexamethylene cyanohydrin). The above-mentioned nitroso-based foaming agent includes N,N'-dimethyl-N,N'-dinitrosoparaphenylenediamine, N,N'-dinitrosopentamethylenetetramine and the like. The above-mentioned hydrazo-based foaming agent includes benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, 3,3'-disulfonyl hydrazide benzophenone, toluene disulfonyl ketoxime, thio-bis(benzenesulfonyl hydrazide), p,p'-oxybis(benzenesulfonyl hydrazide). The above-mentioned carbohydrazide-based foaming agent includes p-toluenesulfonyl carbazide and 4,4'-oxybis(benzenesulfonyl carbazide). The above-mentioned triazine-based foaming agent includes trihydrazinotriazine and 1,3-bis(o-biphenyl triazine).

[0146] The foamed resin layer is preferably produced using a foaming agent, and is preferably produced using a thermally expandable microcapsule. When a foaming agent is used, the bubble diameter in the foamed resin layer becomes more uniform compared to a method of foaming by mechanical stirring or the like. Further, when a thermally expandable microcapsule is used, a foamed resin layer having a finer and more uniform cell diameter can be produced.

[0147] The content of the foaming agent in the resin composition (II) is not particularly limited, but is appropriately selected in consideration of the use of the foamed resin layer. For example, 0.1 to 10 parts by mass, and preferably 1 to 5 parts by mass, is excellent with respect to 100 parts by mass of the polyurethane-based resin.

[0148] Second, a foamed resin layer 13 is formed from the resin composition (II). For example, after the resin composition (II) containing a foaming agent is melted or dissolved, it is processed into a sheet shape to form an unfoamed resin sheet (non-foamed resin layer), and the obtained unfoamed resin sheet is used as a resin composition (unfoamed resin layer). The unfoamed resin sheet is attached to the impregnation side of the base cloth layer 11 impregnated with the resin composition (I), and heat treatment is performed while applying pressure using a heating device such as an oven as necessary, to cause the foaming agent to foam and the solvent to volatilize, thereby forming the foamed resin layer 13. The molding method of the unfoamed resin sheet can be performed by a known or commonly used method, but from the viewpoint of facilitating sheet formation of a high-viscosity resin composition and facilitating the manufacture of a wide laminated sheet, a calendar method is preferable. As another method, after the resin composition (II) is melted or dissolved, a coating film (non-foamed resin layer) is formed by coating on a release sheet or the like substrate, and the obtained coating film is molded into a resin. The foaming agent can be formed by adhering it to the impregnation side of the base cloth layer 11 impregnated with the object (I), and then using a heating device such as an oven to cause the foaming agent to foam. The foamed resin layer 13 is formed by heating when the foaming agent foams, and the resin composition layer 12 (impregnation portion 12a and protrusion portion 12b) is formed from the resin composition (I) impregnated in the base cloth layer 11. The impregnated resin composition layer 12 restrains the fibers of the base cloth layer 11. In addition, as another method, after the unfoamed resin layer is foamed to prepare the foamed resin layer 13, the obtained foamed resin layer 13 is attached to the impregnation side of the base cloth layer 11 impregnated with the resin composition (I).

[0149] Second, a skin layer 14 is formed on the surface of the foamed resin layer 13. A resin composition for the skin layer 14 is coated on the surface of the foamed resin layer 13 to form a coating film, and then the coating film is heat-treated together with isocyanate using a heating device such as an oven, and a polyurethane resin is formed by promoting reaction with a polyol, solvent volatilization, and curing of a crosslinking agent to form the skin layer 14. The resin composition can be performed by a known or commonly used method.

[0150] Second, a surface protective layer 15 is formed on the surface of the skin layer 14. A resin composition for forming the surface protective layer 15 is coated on the surface of the skin layer 14 to form a coating film, and then the coating film is heat-treated together with isocyanate using a heating device such as an oven, and a polyurethane resin is formed by promoting reaction with a polyol, solvent volatilization, and curing of a crosslinking agent to form the surface protective layer 15. The above-mentioned resin composition can be performed by a known or commonly used method. As described above, a laminate including the base cloth layer 11, the resin composition layer 12 impregnated in the base cloth layer 11, the foamed resin layer 13, the skin layer 14, and the surface protective layer 15 in this order can be manufactured.

[0151] Second, the above-mentioned laminate is perforated to form an opening 20. The perforation process is performed by a known or commonly used method to obtain the desired shape.

[0152] Next, the backing material 17 is attached to the back surface lib of the base fabric layer 11 of the above-described laminate which has been perforated by the adhesive layer 16. First, the adhesive of the adhesive layer 16 is applied to the back surface lib of the base fabric layer 11 by a gravure coating technique or the like so as to be dispersed on the back surface lib of the base fabric layer 11. Thereafter, the adhesive surface of the backing material 17 is superimposed on the back surface lib of the base fabric layer 11, and then the adhesive is heated and melted and heat-cured to form the adhesive layer 16 which is adhered to the backing material 17.

[0153] The surface of the surface protective layer 15 can be subjected to an embossing process to obtain a textured pattern. As described above, the laminate sheet 1 can be manufactured.

[0154] According to the above-described laminate sheet, a laminate sheet having good elasticity and from which fluff is less likely to be exposed from the openings, particularly a synthetic leather, can be provided. Therefore, it has an excellent appearance, and the fabric of the base fabric layer can be seen through the openings without being interfered by fluff. By changing the color and pattern of the fabric, a highly designed perforated laminate sheet, particularly a perforated synthetic leather, can be produced. In addition, the adhesion of the base fabric layer to other layers such as the foamed resin layer is excellent, particularly the adhesion when the foamed resin layer has a polyvinyl chloride-based resin as a main component is particularly excellent, and therefore the perforation process is performed. Even at the time of application, it has high adhesion and excellent wear resistance. Therefore, the laminate sheet can be used for the seat surface of an automobile seat, which is particularly susceptible to interlayer friction. In addition, by using a polyvinyl chloride-based resin, the flame retardancy and economy are excellent compared to the case where a polyurethane-based resin is used. In addition, according to the above-described laminate sheet, since a plurality of openings are provided, when used as a synthetic leather for an automobile seat, the air permeability of the seat surface contacted by an occupant can be ensured, and a stuffy feeling can be prevented. Therefore, the laminate sheet can be particularly preferably used for an automobile that is left outdoors for a long time. EXAMPLE

[0155] The application of the present disclosure will be described in more detail below with reference to Examples, but the application of the present disclosure is not limited to these Examples. The amounts of addition shown in the Tables are the amounts of blending of each component (i.e., the amounts of blending of effective components in each raw material, the so-called pure content), and are expressed in "mass parts" unless otherwise specified.

[0156] Example 1

[0157] A polyester base fabric (trade name "TU16002," save-textile manufacturing, grain surface: 255 g / m 2A paste resin composition was prepared by kneading 100 parts by mass of polyvinyl chloride (average degree of polymerization: 1300), 90 parts by mass of a dialkyl phthalate plasticizer, and 10 parts by mass of a water-based polycarbonate-based polyurethane resin (trade name "Hydran WLS-210", manufactured by DIC Corporation) at 160°C for 5 minutes. The obtained paste resin composition was made into a sheet by a calendering method to obtain a non-foamed resin sheet. The non-foamed resin sheet was then attached to the surface of the resin composition of the resin temporarily fixed base fabric in a heated state, and the dialkyl phthalate plasticizer was foamed by heating at 210°C for 2 minutes. The dialkyl phthalate plasticizer was foamed to form a resin foam body having a thickness of 500 μm, and the temporarily fixed resin composition was cured, and the fibers of the base fabric were restrained in the impregnated portion, and protrusions were formed.

[0158] On the other hand, 100 parts by mass of polyvinyl chloride (average degree of polymerization: 2000), 10 parts by mass of a thermoplastic polyurethane elastomer (Shore A hardness: 75, melting point: 170°C), 90 parts by mass of a dialkyl phthalate plasticizer, 2.5 parts by mass of a foaming agent (dimethylformamide), and 15 parts by mass of an additive (including a filler, a stabilizer, a light resistance enhancer, a pigment, a flame retardant) were kneaded at 160°C for 5 minutes, and then cooled. The obtained resin composition was made into a sheet by a calendering method to obtain a non-foamed resin sheet, and then attached to the surface of the resin composition of the resin temporarily fixed base fabric in a heated state. The dialkyl phthalate plasticizer was foamed by heating at 210°C for 2 minutes. The dialkyl phthalate plasticizer was foamed to form a resin foam body having a thickness of 500 μm, and the temporarily fixed resin composition was cured, and the fibers of the base fabric were restrained in the impregnated portion, and protrusions were formed.

[0159] Next, a composition in which 100 parts by mass of a water-based polycarbonate-based polyurethane resin (trade name "Hydran WLS-210", manufactured by DIC Corporation), 10 parts by mass of a pigment, 0.3 parts by mass of a wetting agent, 0.3 parts by mass of an antifoaming agent, and 3 parts by mass of a crosslinking agent were mixed was coated to form a coating film on the surface of the resin foam body using a reverse coater, and the coating film was dried and heated and crosslinked at 130°C for 5 minutes to form a surface layer having a thickness of 30 μm. Then, on the surface of the surface layer, a coating film was formed by mixing a water-based polycarbonate-based polyurethane resin (trade name "WF-78-143", manufactured by Stahl), a silicon-based compound (trade name "HM-54-002", manufactured by Stahl), and a carbodiimide-based crosslinking agent using a reverse coater, and the coating film was dried and heated and crosslinked at 130°C for 5 minutes to form a surface treatment layer having a thickness of 20 μm. Then, the formed surface treatment layer was embossed to provide a texture pattern.

[0160] Next, a punch needle having a diameter of 1.1 mm was moved up and down continuously at an interval of 5 mm with a punch plate having rhombic holes, and the above-described laminate was passed through.

[0161] Next, a urethane reactive hot melt adhesive (trade name "NH128," manufactured by DIC Corporation) was heated to 90°C on the non-impregnated surface (the surface on which the resin foam was not present), dispersed by gravure coating, and then a polyester backing material (trade name "CU19702," manufactured by save-textile Co., Ltd., knitted) was attached to the adhesive-coated surface of the base fabric. The base fabric was left to stand at room temperature for 24 hours, and then the backing material was attached to the non-impregnated surface of the base fabric. A laminate was produced as described above.

[0162] Examples 2 to 4, Comparative Examples 1 and 2

[0163] A laminate was produced in the same manner as in Example 1, except that the amount of resin impregnated was changed as shown in the table.

[0164] Comparative Example 3

[0165] A laminate was produced in the same manner as in Example 1, except that a polyester base fabric (trade name "WO19401," manufactured by save-textile, basis weight: 202 g / m 2 ) was used as the base fabric.

[0166] Comparative Example 4

[0167] A laminate was produced in the same manner as in Example 1, except that a punch having a diameter of 0.8 mm was used during the perforation process.

[0168] Comparative Example 5

[0169] A polyester base fabric (trade name "TU16002," manufactured by save-textile, knitted, basis weight: 255 g / m 2 , thickness: 800 μm) was coated with a polyurethane resin (trade name "MP-865PS," manufactured by DIC Corporation), impregnated with 56 parts by mass per 100 parts by mass of base fabric, allowed to wet-cure, and then dried at 120°C for 3 minutes to obtain a resin-impregnated base fabric. A laminate was produced in the same manner as in Example 1, except that this resin-impregnated base fabric was used.

[0170] <Assessment>

[0171] The laminates obtained in the examples and comparative examples were subjected to the following assessments. The results are shown in Table 1.

[0172] (1) Tensile strength

[0173] From the base fabric used in the examples and comparative examples, three test pieces each having a width of 50 mm and a length of 150 mm were collected in the longitudinal direction and the transverse direction, respectively. Under the conditions of room temperature 20 ± 2°C, humidity 65 ± 5% RH, the test pieces were gripped at both ends by a gripper so as to be free of slack, and using a tensile testing machine (trade name "Autograph," manufactured by Shimadzu Corporation), the test pieces were pulled to break with a grip width of 50 mm, a grip interval of 100 mm, and a grip tool moving speed of 200 mm / min. Then, on each of the longitudinal and transverse directions, the maximum load per unit width (N / cm) until the test piece broke was measured, and the average value of the three test pieces was calculated.

[0174] (2) Constant load elongation (base fabric, backing material, laminate (A))

[0175] From the base fabric, backing material, and laminate (A) used or produced in the examples and comparative examples, three test pieces each having a width of 50 mm and a length of 250 mm were collected in each of the longitudinal and transverse directions. Next, two marker lines were connected to the center portion of the test piece so that the distance between the marker lines was 100 mm. This was spaced 150 mm apart and mounted to a test device (trade name "Autograph," manufactured by Shimadzu Corporation), and a load of 78.4 N (8 kgf) was gently applied. After the load was applied, 10 minutes were allowed to elapse, and then the distance between the marker lines was measured. Thereafter, for each of the test pieces obtained in the longitudinal and transverse directions, the constant load elongation was calculated by the following formula, and the average value thereof was calculated. The laminate (A) was obtained by peeling the surface protection layer, the skin layer, and the resin foam from the laminated sheet produced in the examples and comparative examples.

[0176] Constant load elongation (%) = A - 100

[0177] A: applied load, distance between marker lines after 10 minutes (mm)

[0178] (3) Air permeability

[0179] The backing material and laminate (A) used or produced in the examples and comparative examples were measured using a test device (trade name "FX3300," manufactured by TEXTEST Corporation) under the conditions of JIS L1096 (2010) 8.26.1A method (Frazier method).

[0180] (4) Elasticity

[0181] When the laminated sheet obtained in the examples and comparative examples was used as a cover layer (skin material) for an automobile seat, visual evaluation was performed by 5 people, and the elasticity of the laminated sheet was judged in accordance with the following criteria.

[0182] [Judgment criteria]

[0183] O (Good): Evaluated as "elastic and no wrinkles" by 3 or more people

[0184] X (Poor): Evaluated as "elastic and no wrinkles" by 2 or less people

[0185] (5) Appearance

[0186] The vicinity of the opening of the laminate obtained in the examples and comparative examples was visually evaluated by 5 people. The appearance of the laminate was judged according to the following criteria.

[0187] [Judgment criteria]

[0188] O (Good): Evaluated as "clean opening, no fluff" by 3 or more people

[0189] X (Poor): Evaluated as "clean opening, no fluff" by 2 or less people

[0190] (6) Fluff (front)

[0191] The surface of the backing material of the laminate obtained in the examples and comparative examples was abraded 100 times using a Daver abrasion tester (trade name "Taber-type abrasion tester," manufactured by Yasuda Seiki Mfg. Co., Ltd.) with a CS#10 abrader under a load of 4.9 N. After that, the surface was sucked from the surface protective layer side with a vacuum cleaner, and the vicinity of the opening was visually observed, and the fluff on the surface was judged according to the following criteria.

[0192] [Judgment criteria]

[0193] O (Good): No fluff was confirmed at the opening on the surface protective layer side

[0194] X (Poor): Fluff was confirmed at the opening on the surface protective layer side

[0195] (7) Flame retardancy

[0196] For the laminates obtained in the examples and comparative examples, a test piece of 350 mm x 100 mm was cut from the vertical and horizontal directions, and according to the FMVSS No. 302 flammability test method, the test piece was placed horizontally and indirectly burned on a 38 mm flame for 15 seconds, the burning rate between the A-mark line and the B-mark line 254 mm was measured, and the flame retardancy of the laminate was judged according to the following criteria.

[0197] [Judgment criteria]

[0198] O (Good): Burning rate less than or equal to 80 mm / min

[0199] X (Poor): Burning rate greater than 81 mm / min

[0200] (8) Wear resistance

[0201] From the laminated sheet obtained in the examples and comparative examples, a test piece of 10 mm in width and 150 mm in length was collected in the vertical direction (longitudinal direction), and a polyurethane foam of 10 mm in width, 15 mm in length, and 3 mm in thickness was attached to the back surface (surface of the backing material) thereof. Using a "Learning Type Dyeing Rubbing Stiffness Tester" (manufactured by Oita Seisakusho Co., Ltd.) prescribed in JIS L0849, a rubbing test was performed on JIS L3102 No. 6 cotton cloth. A test was performed in which the rubbing was repeated 30,000 times under a load of 1 kg. Then, the test piece after the rubbing (surface of the surface protective layer) was visually observed, and the wear resistance was judged according to the following criteria.

[0202] [Criteria for Judgment]

[0203] O (Good): The surface protective layer is not scraped off by the rubbing, and the skin layer is not exposed.

[0204] Δ (Usable): The surface protective layer is scraped off by the rubbing, but the base cloth layer is not exposed.

[0205] X (Poor): The base cloth layer is exposed.

[0206] (9) BLC value (hand feeling)

[0207] From the laminated sheet obtained in the examples and comparative examples, a test piece of 150 mm square was taken out, and a strain measurement value (BLC value) at the time of pushing in under a load of 500 g was measured using a "GT303 Leather Softness Tester" (manufactured by GOT ECH TESTING MACHINRS INC.). The greater the strain measurement value, the softer the texture.

[0208] (10) Depth of impregnated portion

[0209] Using an electron microscope (trade name "VHX-5000," manufactured by KEYENCE CORPORATION), the cross section in the thickness direction of the laminated sheet obtained in the examples was observed. The cross-sectional photograph of Example 1 is shown in FIG. 1. Figure 1 The results showed that the depth of the impregnated portion in the laminated sheet was in the range of 30% to 70% of the thickness of the base cloth. Figure 2 The laminated sheet shown in FIG. 2 was not attached to the backing material.

[0210] (Table 1)

[0211]

[0212] The laminates of Examples 1 to 4 were excellent in elasticity and appearance, and the front surface was not easily fluffed and no fluffing-out phenomenon occurred. Further, they had excellent air permeability, flame retardancy and vibration resistance. On the other hand, when the amount of the resin composition was small (Comparative Example 1), the binding of the base fabric layer was insufficient, the appearance was poor, and the front surface was observed to be fluffed. When the amount of the resin composition was large (Comparative Example 2), the elongation of the base fabric layer was reduced, the elasticity was deteriorated, and the appearance was also deteriorated. When the constant load elongation of the base fabric layer was low (Comparative Example 3), the elasticity was poor and the appearance was also poor. When the air permeability of the laminate was low (Comparative Example 4), the air permeability was poor. When a polyurethane-based resin was used as the resin to be impregnated in the base fabric layer (Comparative Example 5), the flame retardancy and vibration resistance were poor.

[0213] SYMBOL EXPLANATION

[0214] 1 laminate

[0215] 11 base fabric layer

[0216] 11a front surface

[0217] 11b back surface

[0218] 12 resin composition layer

[0219] 12a impregnated portion

[0220] 12b protruding portion

[0221] 13 foamed resin layer

[0222] 14 skin layer

[0223] 15 surface protection layer

[0224] 16 adhesive layer

[0225] 17 backing material

[0226] 20 opening

[0227] 20a opening surface

Claims

1. A laminate composed of a base cloth layer and a resin composition layer having a polyvinyl chloride-based resin as a main component, wherein the resin composition layer has an impregnated portion impregnated in the base cloth layer, the laminate has a plurality of openings extending through the base cloth layer and the resin composition layer in a thickness direction, the mass of the resin composition layer is 50 to 100 parts by mass with respect to 100 parts by mass of the mass of the base cloth layer, the tensile strength of the base cloth layer in both the longitudinal and transverse directions is 100 N / cm or more, and the constant load elongation is 20% or more, The above laminated board has an air permeability of 50 cc / cm 2 • s or more.

2. The laminate according to claim 1, wherein the impregnated portion is exposed on one surface of the base cloth layer and is not exposed on the other surface.

3. The laminate according to claim 2, wherein in the impregnated portion, the resin composition layer is impregnated from one surface of the base cloth layer to a depth of 10 to 90% of the thickness of the base cloth layer inside the base cloth layer.

4. The laminate according to claim 2 or 3, wherein the resin composition layer has a protrusion protruding from one surface of the base cloth layer to the outside of the base cloth layer.

5. The laminate according to any one of claims 1 to 3, wherein The back surface of the above base cloth layer also contains a gas permeability of 100 cc / cm 2 • a backing material of s or more.

6. The laminate according to claim 5, wherein the backing material is provided on the back surface of the base cloth layer via an adhesive layer.

7. The laminate according to claim 5, wherein the openings do not penetrate the backing material.

8. The laminate according to claim 5, wherein The constant load elongation of the above base fabric layer or the above resin composition layer and the laminate having a backing material on both end faces is 10% or more in both the vertical and horizontal directions, and the air permeability is 50 cc / cm 2 • s or more.

9. The laminate according to any one of claims 1 to 3, wherein one surface of the base cloth layer further has a foamed resin layer having a polyvinyl chloride-based resin as a main component.

10. The laminate according to claim 9, wherein the foamed resin layer contains a thermoplastic polyurethane elastomer.

11. The laminate according to claim 9, wherein the foamed resin layer further has a skin layer containing a polyurethane resin on the side opposite to the side on which the base cloth layer is present.

12. Use of the laminate according to any one of claims 1 to 11 for synthetic leather.

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