JP7029736B1 - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet having good tension, excellent breathability and flame retardancy, and less likely to expose fluff from an opening. SOLUTION: The laminated sheet 1 includes a base cloth layer 11 and a resin composition layer 12 containing a polyvinyl chloride resin as a main component, and the resin composition layer 12 is an impregnated portion 12a impregnated into the base cloth layer 11. Has a plurality of openings 20 penetrating the base cloth layer 11 and the resin composition layer 12 in the thickness direction, and the mass of the resin composition layer 12 is 100 parts by mass with respect to the mass of the base cloth layer 11. The base fabric layer 11 has a tensile strength of 100 N / cm or more and a constant load elongation of 20% or more in both the vertical and horizontal directions, and the air permeability of the laminated sheet 1 is 50 cc / cm2 · s or more. There is a laminated sheet 1. [Selection diagram] Fig. 1

Description

The present disclosure relates to laminated sheets. More specifically, the present disclosure relates to laminated sheets suitable for application to synthetic leather.

Synthetic leather is widely used as a substitute for natural leather or as a leather material having better physical characteristics than natural leather. In particular, as synthetic leather used as a seat surface material for vehicles such as automobiles, in order to obtain a natural leather-like feel and texture, it is generally placed on a fibrous base cloth (for example, non-woven fabric, woven fabric, knitted fabric, etc.). Is known to have a resin layer mainly composed of a polyurethane-based resin or a polyvinyl chloride-based resin.

The laminated sheet used for the synthetic leather may be perforated (perforated) for the purpose of imparting moisture permeability and breathability (see Patent Documents 1 to 4). For example, Patent Document 1 describes a fibrous base material, a polyurethane resin layer provided on the front surface side of the fibrous base material, and an adhesive layer made of a polyurethane resin on the back surface side of the fibrous base material. Disclosed is a composite skin material comprising a pasted woven fabric and having a plurality of openings on the surface of the polyurethane resin layer. Patent Document 4 describes a base fabric layer having a porous structure in which a resin composition containing a polyurethane resin and an organic flame retardant is impregnated into a woven fabric having a tear strength of 150 N or more in length and 100 N or more in width, and the above-mentioned group. There is a disclosure of a laminated sheet having a skin layer laminated on a cloth layer and having a plurality of vents penetrating in the thickness direction.

Japanese Unexamined Patent Publication No. 2017-165209 Japanese Unexamined Patent Publication No. 2016-129994 International Publication No. 2015/022772 International Publication No. 2014/09799

When the laminated sheet is perforated, there is a problem that the fluff generated by fraying the base material comes out from the holes (openings) and spoils the appearance. Further, when the laminated sheet is used for the seat surface of a vehicle such as an automobile, for example, the foamed sheet is laminated and sewn on the base material without using an adhesive from the viewpoint of ensuring the air permeability of the laminated sheet. This is usually done, but in this case, the fluff is more likely to come out from the opening due to the friction between the base material and the foamed sheet. Further, there is also a problem that the back surface of the base material is rubbed, so that the base material is frayed even on the back surface of the base material and fluffing is likely to occur.

By attaching a backing material such as a woven fabric to the back surface side of the base material via an adhesive layer as in the composite skin material of Patent Document 1, fluffing on the back surface of the base material can be suppressed. However, the composite skin material of Patent Document 1 cannot suppress the exposure of fluff from the opening. Further, since the laminated sheet of Patent Document 1 uses a polyurethane resin as the resin to be impregnated in the woven fabric, there is a concern about flame retardancy.

The laminated sheet of Patent Document 4 uses a base fabric layer obtained by impregnating a woven fabric with a resin composition containing a polyurethane resin, so that fraying of the surface of the base material is suppressed and fluff is exposed from the opening. Is unlikely to occur. However, the laminated sheet of Patent Document 4 cannot be used only for a specific sheet shape because the base material is insufficiently stretched, wrinkles are likely to occur when it is attached to the sheet, and the tension is inferior.

The present disclosure has been made in view of the above problems, and an object thereof is to provide a laminated sheet having good tension, excellent breathability and flame retardancy, and less fluff exposure from openings. be.

As a result of diligent studies to achieve the above object, the inventors of the present disclosure have found a base cloth layer having specific physical properties and a polyvinyl chloride resin impregnated in the base cloth layer so as to have a specific impregnation amount. A laminated sheet including a resin composition layer as a main component, which has a plurality of openings penetrating the base fabric layer and the resin composition layer in the thickness direction, and has a specific air permeability. Therefore, it has been found that it is possible to provide a laminated sheet having good tension, excellent breathability and flame retardancy, and less likely to expose fluff from the opening. The present disclosure relates to what has been completed on the basis of these findings.

That is, the present disclosure is a laminated sheet including a base cloth layer and a resin composition layer containing a polyvinyl chloride resin as a main component.
The resin composition layer has an impregnated portion impregnated in the base fabric layer and has an impregnated portion.
It has a plurality of openings penetrating the base fabric layer and the resin composition layer in the thickness direction, and has a plurality of openings.
The mass of the resin composition layer is 30 to 100 parts by mass with respect to 100 parts by mass of the base fabric layer.
The base fabric layer has a tensile strength of 100 N / cm or more and a constant load elongation of 20% or more in both the vertical and horizontal directions.
Provided is a laminated sheet having an air permeability of 50 cc / cm ² · s or more.

It is preferable that the impregnated portion is exposed on one surface of the base fabric layer and not on the other surface.

In the impregnated portion, the resin composition layer is impregnated inside the base cloth layer from one surface of the base cloth layer to a depth of 10 to 90% with respect to the thickness of the base cloth layer. Is preferable.

The resin composition layer preferably has a protrusion protruding from one surface of the base cloth layer to the outside of the base cloth layer.

It is preferable that the laminated sheet is further provided with a backing material having an air permeability of 100 cc / cm ² · s or more on the back surface of the base cloth layer.

The backing material is preferably provided on the back surface of the layer via an adhesive layer.

It is preferable that the opening does not penetrate the backing material.

It is preferable that the constant load elongation of the base fabric layer or the laminate having the resin composition layer and the backing material on both end surfaces is 10% or more in both the vertical and horizontal directions, and the air permeability is 50 cc / cm ² · s or more. ..

It is preferable that the laminated sheet further includes a foamed resin layer containing a polyvinyl chloride resin as a main component on one surface of the base fabric layer.

The foamed resin layer preferably contains a thermoplastic polyurethane elastomer.

It is preferable that the laminated sheet further includes a skin layer containing a polyurethane resin on the side of the foamed resin layer opposite to the side where the base fabric layer is located.

The laminated sheet is preferably used for synthetic leather.

According to the laminated sheet of the present disclosure, it is possible to provide a laminated sheet having good tension, excellent breathability and flame retardancy, and less likely to expose fluff from an opening, particularly a laminated sheet suitable for synthetic leather applications. It is possible.

It is the schematic (front sectional view) which shows one Embodiment of the laminated sheet of this disclosure. It is sectional drawing of the laminated sheet produced in Example 1. FIG.

[Laminated sheet]
The laminated sheet of the present disclosure includes at least a base fabric layer and a resin composition layer. The laminated sheet may include a layer other than the base fabric layer and the resin composition layer. Examples of the other layers include a foamed resin layer provided on one surface of the base cloth layer, an epidermis layer provided on the surface opposite to the side on which the base cloth layer of the foamed resin layer is located, and the epidermis. Examples thereof include a surface treatment layer provided on a surface opposite to the side on which the foamed resin layer of the layer is located, a backing material provided on the back surface of the base fabric layer, and the like.

The laminated sheet has a plurality of openings penetrating the base fabric layer and the resin composition layer in the thickness direction. When the laminated sheet includes one or more of the foamed resin layer, the skin layer, and the surface treatment layer, it is preferable that the plurality of openings penetrate these layers in the thickness direction. It is preferable that the plurality of openings do not penetrate the backing material and the adhesive for fixing the backing material to the base fabric layer.

The resin composition layer contains a polyvinyl chloride-based resin as a main component, and has an impregnated portion in which at least a part of the layer is impregnated into the base fabric layer. In addition, in this specification, "principal component" means that it is contained in the largest mass ratio in a layer. By having such a structure, the fibers constituting the base fabric layer are restrained by the resin composition layer, are not easily frayed, and the exposure of fluff from the opening is suppressed. It is preferable that the impregnated portion is exposed on one surface of the base fabric layer (particularly, the surface on the opening surface side in the opening). In this case, since the fibers on the surface of the base fabric layer are restrained by the resin composition, the exposure of fluff from the openings is further suppressed. Further, it is preferable that the impregnated portion is not exposed on the other surface of the base fabric layer (particularly, the surface opposite to the opening surface side). In this case, there is a region that is not impregnated with the resin composition layer, the elongation of the base fabric layer is sufficiently maintained, and the tension of the laminated sheet is improved. Further, the laminated sheet has advantages such as excellent breathability, weight reduction, and good texture.

In the impregnated portion, the resin composition layer is 10 to 90% (preferably) from one surface of the base cloth layer (particularly, the surface on the opening surface side) with respect to the thickness of the base cloth layer. It is preferable to impregnate the inside of the base fabric layer to a depth of 30 to 70%). When the inside of the base cloth layer is invaded to a depth of 10% or more, the fibers near the surface of the base cloth layer are restrained by the resin composition layer, the fluffing on the surface of the base cloth layer is further suppressed, and the fluffing from the opening is further suppressed. The exposure of the fluff is further suppressed. When the inside of the base cloth layer is invaded to a depth of 90% or less, a region not impregnated with the resin composition layer is sufficiently present in the base cloth layer, and the base cloth layer is sufficiently stretched. The tension of the laminated sheet becomes better. Further, the laminated sheet has advantages such as excellent breathability, weight reduction, and good texture.

The resin composition layer preferably has a protruding portion (non-impregnated portion) protruding from one surface of the base fabric layer (particularly, the surface on the opening surface side) to the outside of the base fabric layer. With such a configuration, when other layers such as the foamed resin layer are laminated via the protrusion of the resin composition layer, the protrusion acts as an adhesive layer, and the base fabric layer and the base cloth layer are laminated. Adhesion with other layers is further improved. Further, as a result, the layers are less likely to be displaced, so that friction is less likely to occur, and the base fabric layer is less likely to fray. The resin composition layer in the protruding portion does not invade the base fabric layer.

The mass of the resin composition layer is 30 to 100 parts by mass, preferably 50 to 90 parts by mass, and more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the base fabric layer. When the mass of the resin composition layer is 30 parts by mass or more, the base cloth layer is sufficiently impregnated and the adhesion to the other layers is further improved, and as a result, the base cloth layer is frayed. It can be suppressed and the exposure of fluff from the opening can be suppressed. When the mass of the resin composition layer is 100 parts by mass or less, the elongation of the base fabric layer is sufficiently maintained, and the tension of the laminated sheet is improved. In addition, there are merits that the weight of the laminated sheet can be reduced and the texture is improved.

An embodiment of the laminated sheet is shown in FIG. As shown in FIG. 1, the laminated sheet 1 includes a base cloth layer 11, a resin composition layer 12 partially impregnated from one surface 11a side of the base cloth layer 11, a foamed resin layer 13, and a skin layer 14. And the surface protective layer 15 located on the outermost surface of the laminated sheet 1 are provided in this order. The base cloth layer 11 and the foamed resin layer 13 are joined by the resin composition layer 12. Further, the backing material 17 is laminated on the other surface 11b of the base cloth layer 11 via the partially arranged adhesive layer 16. The laminated sheet 1 is provided with a plurality of openings 20 penetrating from the base cloth layer 11 to the surface protection layer 15.

The resin composition layer 12 is composed of an impregnated portion 12a impregnated into the base cloth layer 11 and a protruding portion (non-impregnated portion) 12b protruding outward from the surface 11a of the base cloth layer 11. The impregnated portion 12a has a thickness of the base cloth layer 11 from the front surface of the base cloth layer 11 (the surface on the opening surface 20a side) 11a toward the back surface of the base cloth layer 11 (the surface opposite to the opening surface 20a side) 11b. It is impregnated to about 50% of the amount. That is, the resin composition layer 12 is exposed on the front surface 11a of the base cloth layer 11 and not on the back surface 11b of the base cloth layer 11. The protruding portion 12b protrudes from the surface 11a of the base cloth layer 11. Since the protruding portion 12b acts as an adhesive, the adhesion between the foamed resin layer 13 and the base cloth layer 11 is excellent.

(Base cloth layer)
The base fabric layer has a tensile strength of 100 N / cm or more and a constant load elongation of 20% or more in both the vertical and horizontal directions. By having such physical properties, the laminated sheet in a state where the base cloth layer is impregnated with the resin composition layer is less likely to cause wrinkles when it is stuck on the sheet, and the tension is good. The tensile strength and the constant load elongation are physical property values of the base fabric layer in a state where the resin composition layer is not impregnated.

The tensile strength is 100 N / cm or more in both the vertical and horizontal directions, preferably 120 N / cm or more. When the tensile strength is 100 N / cm or more, it has an appropriate strength even in a state where perforation processing is performed. The above tensile strength is a value measured and calculated by the following tensile test.

<Tensile test>
From the base cloth layer, three test pieces having a width of 50 mm and a length of 150 mm are collected from each of the warp direction and the weft direction. Under the conditions of room temperature 20 ± 2 ° C. and humidity 65 ± 5% RH, pinch both ends of the test piece with a gripping tool so that there is no slack, and use a tensile tester to grip the width of 50 mm, the gripping interval of 100 mm, and the gripping tool. The test piece is pulled at a moving speed of 200 mm / min to break the test piece. Then, the maximum load (N / cm) per unit width until the test piece breaks is measured, and the average value of the three test pieces is obtained.

The constant load elongation is 20% or more in both the vertical and horizontal directions, preferably 30% or more. When the constant load elongation is 20% or more, the elongation is sufficient even in the state where the perforation process is applied, wrinkles are less likely to occur when the perforation process is applied, and the tension is good. The constant load elongation is a value measured and calculated by the following constant load elongation test.

<Constant load elongation test>
From the base cloth layer, three test pieces having a width of 50 mm and a length of 250 mm are collected from each of the warp direction and the weft direction. Next, two marking lines are attached to the center of the test piece so that the distance between the marking lines is 100 mm. With this as a gripping interval of 150 mm, attach it to the test equipment and gently apply a load of 78.4 N (8 kgf). Leave it for 10 minutes with the load applied, and then determine the distance between the marked lines. Then, the constant load elongation rate is calculated by the following formula, and the average value of the three test pieces is obtained.
Constant load elongation rate (%) = A-100
A: Distance between marked lines (mm) 10 minutes after applying a load

Examples of the base fabric layer include fibrous fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics, and fibrous base materials such as natural leather. The types of fibers constituting the fibrous fabric are not particularly limited, but synthetic fibers such as polyester resin, polyamide resin, polyacrylonitrile resin, polyolefin resin, and polyvinyl alcohol; natural fibers such as cotton and linen; rayon, Regenerated fibers such as rayon and acetate; semi-synthetic fibers and the like can be mentioned. Only one type of the fiber may be used, or two or more types may be used. Among them, a knit made of synthetic fibers, particularly a knit made of polyester fibers, is preferable from the viewpoint of being more excellent in strength and processability. The base fabric layer may be a single layer or a plurality of layers.

The basis weight of the base fabric layer is not particularly limited, but is preferably 100 to 400 g / m ² , and more preferably 150 to 300 g / m ² . When the basis weight is 100 g / m ² or more, sufficient strength can be obtained as an automobile interior material. When the basis weight is 300 g / m ² or less, the weight of the laminated sheet can be reduced.

(Resin composition layer)
The resin composition layer contains a polyvinyl chloride resin as a main component. That is, the resin composition contains a polyvinyl chloride resin in the largest mass ratio. As a result, the fibers constituting the base fabric layer are restrained by the resin composition layer in the impregnated portion, are not easily frayed, and the exposure of fluff from the opening is suppressed. In addition, the flame retardancy of the laminated sheet can be improved, the cost can be suppressed, and the economy is excellent. The resin composition layer preferably contains a polyvinyl chloride resin as an adhesive component. In this case, the adhesion between the base cloth layer and the other layers when laminating the other layers on the base cloth layer is improved. Further, as a result, the layers are less likely to be displaced, so that friction is less likely to occur, and the base fabric layer is less likely to fray. As the polyvinyl chloride resin, only one kind may be used, or two or more kinds may be used.

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

Examples of the polyvinyl chloride-based resin include polyvinyl chloride, which is a homopolymer of vinyl chloride, polyvinylidene chloride, which is a homopolymer of vinylidene chloride, vinyl chloride, or a copolymer of vinylidene chloride and another monomer. Examples thereof include chlorinated polyvinyl chloride and chlorinated polyolefin. Examples of the chlorinated polyolefin include chlorinated polyethylene and chlorinated polypropylene.

Examples of the copolymer include vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer suspension, and the like. Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-maleic acid ester Vinyl chloride-vinyl ester copolymers such as polymers and vinyl chloride- (meth) acrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinyl ether copolymers, vinyl chloride-styrene-anhydrous. Examples thereof include a maleic acid ternary copolymer, a vinyl chloride-styrene-acrylonitrile ternary copolymer, a vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, and an ethylene-vinyl acetate-vinyl chloride copolymer. Examples of the copolymer include block copolymers, random copolymers, graft copolymers and the like.

As the polyvinyl chloride-based resin, polyvinyl chloride (vinyl chloride homopolymer) is particularly preferable.

The polyvinyl chloride resin can be obtained by known or conventional polymerization. The polymerization method of the polyvinyl chloride-based resin is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Of these, a polyvinyl chloride resin obtained by emulsion polymerization or suspension polymerization is preferable.

The average degree of polymerization of the polyvinyl chloride resin (based on JIS K6721) is not particularly limited, but is preferably 800 to 4000, more preferably 1100 to 3500, and further preferably 1300 to 2800. When the average degree of polymerization is within the above range, the exposure of fluff from the opening is further suppressed.

The content ratio of the polyvinyl chloride resin in the resin composition is not particularly limited, but is preferably 70% by mass or more, more preferably 90% by mass, based on 100% by mass of the total amount of the resin composition layer. % Or more. When the content ratio is 70% by mass or more, the flame retardancy of the laminated sheet is more excellent. The content ratio may be 100% by mass.

The resin composition layer preferably further contains a plasticizer. As a result, the workability of the laminated sheet is excellent.

As the plasticizer, general ones used for polyvinyl chloride resins can be used. Examples of the plasticizer include di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, and C _9-11 mixed alkyl phthalic acid phthalate. Aromatic carboxylic acid esters such as butylbenzyl and diisooctyl isophthalate; aliphatic carboxylic acid esters such as diisooctyl adipate, diisodecyl adipate, di-2-ethylhexyl sebacate; tri-n-butyl trimellitic acid (TBTM), tri Trimellitic acid esters such as tris (2-ethylhexyl) merit acid (TOTM); dibenzoic acid esters such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, polyoxypropylene glycol dibenzoate, polyoxyethylene glycol dibenzoate: phosphoric acid. Phosphate esters such as tricresyl and trixysilyl phosphate; halogen-containing compounds such as chlorinated paraffin and chlorinated fatty acid esters; epoxidized groups such as epoxidized soybean oil, epoxidized flaxseed oil, epoxidized safflower oil and epoxidized castor oil. Containing fatty acids; examples include polyester. As the plasticizer, only one kind may be used, or two or more kinds may be used.

The content of the plasticizer is preferably 50 to 120 parts by mass, more preferably 60 to 100 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. When the content is 50 parts by mass or more, the processability of the laminated sheet becomes better. When the content is 90 parts by mass or less, the aging rate of the resin composition layer can be slowed down.

The resin composition layer may contain other components other than the above-mentioned components. Examples of the above other components include resins other than polyvinyl chloride resins, processing aids, reinforcing agents, flame retardants, colorants (dye, pigment, etc.), defoaming agents, leveling agents, cross-linking agents, and silane couplings. Agent, Tixo-imparting agent, Adhesive-imparting agent, Wax, Heat-stabilizing agent and other stabilizers, Light-resistant agent, UV absorber, Weather-resistant imparting agent, Fluorescent whitening agent, Conductivity-imparting agent, Antistatic agent, Moisture permeability improvement Agents, water repellents, oil repellents, foaming agents, crystalline water-containing compounds, water absorbents, hygroscopic agents, deodorants, foam stabilizers, antifogging agents, fungicides, preservatives, algae repellents, pigment dispersants, Examples thereof include inert gas, slip agent, lubricant, anti-blocking agent, antioxidant, neutralizing agent, natural oil, synthetic oil, thickener and the like. As the above other components, only one kind may be used, or two or more kinds may be used.

(Effervescent resin layer)
The foamed resin layer preferably contains a polyvinyl chloride resin as a main component. That is, the foamed resin layer contains the polyvinyl chloride resin in 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 via the resin composition layer is further improved. It is excellent, suppresses misalignment between layers, and has better wear resistance and bending resistance (particularly, low temperature bending resistance). Further, by suppressing the displacement between the layers, it is possible to further suppress the generation of fluff on the surface of the base layer portion. As the polyvinyl chloride resin, only one kind may be used, or two or more kinds may be used.

Examples of the polyvinyl chloride-based resin in the foamed resin layer include those exemplified and described as the polyvinyl chloride-based resin contained in the above-mentioned resin composition layer. As the polyvinyl chloride-based resin, polyvinyl chloride is preferable.

The average particle size of the polyvinyl chloride resin is not particularly limited, but is preferably 0.1 to 5 μm, and more preferably 0.2 to 4 μm. When the average particle size is 0.1 μm or more, the productivity at the time of calendar processing is good. When the average particle size is 5 μm or less, the dispersibility of the thermoplastic polyurethane elastomer particles in the vinyl chloride composition is good. The average particle size is a value measured by a laser diffraction / scattering method.

The foamed resin layer preferably further contains a thermoplastic polyurethane elastomer. This makes it possible to obtain a laminated sheet that is lightweight and has excellent wear resistance. As the thermoplastic polyurethane elastomer, only one kind may be used, or two or more kinds may be used.

The thermoplastic polyurethane elastomer (TPU) is composed of a hard phase (hard segment) and a soft phase (soft segment). The thermoplastic polyurethane elastomer is usually obtained by reacting a polyisocyanate, a long-chain polyol, a chain extender, and, if necessary, another isocyanate-reactive compound.

The polyisocyanate is a compound having two or more isocyanate groups in the molecule. Examples of the polyisocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. The polyisocyanate may also be a dimer or trimer, a reaction product or a polymer of the aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and / or an aromatic aliphatic polyisocyanate. For example, diphenylmethane diisocyanate dimer or trimer, reaction product of trimethylol propane and tolylene diisocyanate, reaction product of trimethylol propane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, etc. (Polyester polyisocyanate, etc.) and the like. As the polyisocyanate, only one kind may be used, or two or more kinds may be used.

Examples of the long-chain polyol include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, and a polyacrylic polyol. The number average molecular weight of the long-chain polyol is usually 500 or more, preferably 500 to 10000, more preferably 600 to 6000, and even more preferably 800 to 4000. As the long-chain polyol, only one kind may be used, or two or more kinds may be used.

As the chain extender, a chain extender usually used for producing a thermoplastic polyurethane elastomer can be used, and examples thereof include low molecular weight polyols and polyamines. The molecular weight of the chain extender is usually less than 500, preferably 300 or less. As the chain extender, only one kind may be used, or two or more kinds may be used.

The shore A hardness of the thermoplastic polyurethane elastomer is preferably 50 to 80, more preferably 55 to 75. When the Shore A hardness is within the above range, the compatibility with the polyvinyl chloride resin becomes better. As a result, when the Shore A hardness is 50 or more, the resin composition which is the precursor of the foamed resin layer is excellent in processability and cutability, and pelletization becomes easy. Further, when the Shore A hardness is 80 or less, the flexibility and bending resistance (particularly, low temperature bending resistance) of the laminated sheet become better. Further, the compatibility with the polyvinyl chloride resin is improved, and the sheet processability when the unfoamed resin sheet which is the precursor of the foamed resin layer is obtained by the calendar method is excellent.

The melting point of the thermoplastic polyurethane elastomer is preferably 140 to 200 ° C, more preferably 150 to 180 ° C. When the melting point is 140 ° C. or higher, the foamed resin layer is formed well, and the heat resistance when used as an automobile interior material can be maintained. When the melting point is 200 ° C. or lower, the compatibility with the polyvinyl chloride resin is good and the calender workability is good.

The content of the thermoplastic polyurethane elastomer is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, and further preferably 8 to 35 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. It is a department. When the content is 1 part by mass or more, the content of the thermoplastic polyurethane elastomer becomes more sufficient, and the wear resistance and the bending resistance (particularly, the low temperature bending resistance) become better. When the content is 50 parts by mass or less, the content of the polyvinyl chloride resin can be sufficiently secured, and the performance of the polyvinyl chloride resin can be further exhibited. In addition, the workability of the unfoamed resin sheet by the calendar method becomes better.

The foamed resin layer preferably further contains a plasticizer. When the plasticizer is contained, the flexibility of the foamed resin layer and the laminated sheet is further improved, and the bending resistance (particularly, the low temperature bending resistance) is improved.

Examples of the plasticizer in the foamed resin layer include those exemplified and described as the plasticizer that can be contained in the above-mentioned resin composition layer. As the plasticizer, only one kind may be used, or two or more kinds may be used.

The content of the plasticizer is preferably 50 to 90 parts by mass, more preferably 60 to 90 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. When the content is 50 parts by mass or more, the texture of the laminated sheet becomes better. When the content is 90 parts by mass or less, bleeding out of the plasticizer to the surface of the foamed resin layer can be suppressed, and high adhesion to the adjacent layer can be maintained, so that wear resistance is further improved. In addition, the performance of the polyvinyl chloride resin can be further exhibited.

The foamed resin layer preferably further contains a filler. By including the filler, the rigidity of the foamed resin layer can be increased and the durability can be improved.

The filler is not particularly limited, and is, for example, calcium carbonate, calcium phosphate, calcium phosphate, 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, silica, zinc borate, zinc tintate, zinc hydroxytinate, myoban, talc, kaolin, clay, asbestos, synthetic zeolite, synthetic hydrotalcite and other inorganic fillers. Can be mentioned. As the filler, only one kind may be used, or two or more kinds may be used.

The content of the filler is preferably 1 to 100 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. When the content is 1 part by mass or more, 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 100 parts by mass or less, the content can be contained without affecting the bending resistance and the wear resistance.

The foamed resin layer may contain other components other than the above-mentioned components. Examples of the other components include components contained in known or conventional foams. Examples of the other components include those exemplified and described as those that can be contained in the above-mentioned resin composition layer. As the above other components, only one kind may be used, or two or more kinds may be used.

The foamed resin layer preferably has an apparent density of 0.3 to 0.7 g / cm ³ , more preferably 0.4 to 0.5 g / cm ³ . When the apparent density is 0.3 g / cm ³ or more, the wear resistance of the laminated sheet becomes better. When the apparent density is 0.7 g / cm ³ or less, the weight becomes lighter, so that a sufficient thickness can be secured and the flexibility is more excellent. Further, the foamed resin layer can maintain the strength due to the compounding of the polyvinyl chloride resin even if the apparent density is as low as 0.7 g / cm ³ or less. Further, by setting the apparent density within the above range, the texture of the laminated sheet becomes better. The apparent density is calculated by cutting out the foamed resin layer to a size of 30 cm square, setting the thickness to the average value of n = 5, calculating the volume of the cut out foamed resin layer, and calculating the mass and volume of the foamed resin layer. To.

The foamed resin layer preferably has an average cell diameter of 50 to 250 μm, more preferably 55 to 160 μm, and even more preferably 60 to 100 μm. When the average cell diameter is 50 μm or more, the flexibility becomes better. When the average cell diameter is 250 μm or less, the wear resistance becomes better.

The foamed resin layer preferably has a maximum cell diameter of 80 to 400 μm, more preferably 90 to 250 μm, and even more preferably 100 to 200 μm. When the maximum cell diameter is 80 μm or more, the flexibility becomes better. When the maximum cell diameter is 400 μm or less, the wear resistance becomes better.

The degree of foaming of the foamed resin layer is preferably 2.0 to 4.0 times, more preferably 2.5 to 3.0 times. When the degree of foaming is 2.0 times or more, the texture of the laminated sheet becomes better. When the degree of foaming is 4.0 times or less, the wear resistance of the laminated sheet becomes better.

The degree of foaming is obtained as follows. An electron micrograph (50x) of the thickness direction cross section of the foamed resin layer is read into a personal computer with a scanner, the foamed part is painted white, and then the colors of the foamed part and the non-foamed part are binarized into white and black to white. The dot part is totaled by integration. Then, the degree of foaming is obtained by using the following formula.
Foaming degree = (area of foaming part + area of non-foaming part) / area of non-foaming part

The bubble structure of the foamed resin layer may be any of a closed cell structure, a semi-independent semi-open cell structure, and an open cell structure, but it is preferable to have a closed cell structure. When it has a closed cell structure, wear resistance and bending resistance (particularly, low temperature bending resistance) become better.

The thickness of the foamed resin layer is not particularly limited, but is preferably 200 to 650 μm, more preferably 250 to 600 μm, and even more preferably 300 to 500 μm. When the thickness is 200 μm or more, the wear resistance becomes better. When the thickness is 650 μm or less, the weight is further reduced.

(Epidermis layer)
The skin layer is preferably a non-foaming resin layer from the viewpoint of further improving the wear resistance. The skin layer preferably contains a polyurethane resin. The skin layer containing the polyurethane-based resin has better adhesion to the foamed resin layer when the thermoplastic polyurethane elastomer is contained. As a result, the gap between the layers of the skin layer and the foamed resin layer is less likely to occur, and the wear resistance becomes extremely good. In addition, the texture of the laminated sheet becomes better. The skin layer (non-foaming resin layer) may be a single layer or a plurality of layers.

The polyurethane resin is usually obtained by reacting a polyisocyanate, a long-chain polyol, a chain extender, and, if necessary, another isocyanate-reactive compound. Examples of 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 described above, respectively. The polyisocyanate, the long-chain polyol, and the chain extender may be used alone or in combination of two or more.

As the long-chain polyol, a polycarbonate polyol is particularly preferable. That is, the polyurethane-based resin that can be contained in the skin layer is preferably a polycarbonate-based polyurethane resin. By using the polycarbonate-based polyurethane resin, the wear resistance of the laminated sheet is further improved.

The polyurethane-based resin in the skin layer is preferably an aqueous polyurethane-based resin. That is, the polyurethane-based resin is preferably an aqueous polycarbonate-based polyurethane resin. By having such a structure, it is excellent in abrasion resistance and also excellent in resistance to oleic acid derived from sebum components (oleic acid resistance). In addition, since no organic solvent is used, it also contributes to the reduction of environmental load.

The content ratio of the polyurethane-based resin (particularly, the polycarbonate-based polyurethane resin) in the epidermis is not particularly limited, but is preferably 30% by mass or more, more preferably 30% by mass, based on the total amount of 100% by mass of the epidermis layer. It is 50% by mass or more. When the content ratio is 30% by mass or more, the adhesion to the foamed resin layer becomes higher, and the wear resistance of the laminated sheet becomes better.

The skin layer may contain other components other than the polyurethane resin. Examples of the other components include those exemplified and described as other components that may be contained in the above-mentioned resin composition layer. As the above other components, only one kind may be used, or two or more kinds may be used.

The thickness of the epidermis layer is not particularly limited, but is preferably 10 to 100 μm, more preferably 20 to 40 μm. When the thickness is 10 μm or more, the wear resistance of the laminated sheet is further improved. When the thickness is 100 μm or less, the weight of the laminated sheet is further reduced.

(Surface protective layer)
The surface protective layer is the outermost layer in the laminated sheet, and is a layer that protects internal layers such as the skin layer, the foamed resin layer, the resin composition layer, and the base fabric layer from friction and the like. Therefore, the wear resistance of the laminated sheet is further improved.

The surface protective layer preferably contains a polyurethane resin. The surface protective layer containing the polyurethane-based resin has better adhesion to the skin layer when the polyurethane-based resin is contained. As a result, the gap between the layers of the surface protective layer and the skin layer is less likely to occur, and the wear resistance becomes extremely good. In addition, the texture of the laminated sheet becomes better.

The polyurethane resin is usually obtained by reacting a polyisocyanate, a long-chain polyol, a chain extender, and, if necessary, another isocyanate-reactive compound. Examples of 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 described above, respectively. The polyisocyanate, the long-chain polyol, and the chain extender may be used alone or in combination of two or more.

As the long-chain polyol, a polycarbonate polyol is particularly preferable. That is, the polyurethane-based resin that can be contained in the surface protective layer is preferably a polycarbonate-based polyurethane resin. By using the polycarbonate polyurethane resin, the wear resistance of the laminated sheet is further improved.

The polyurethane-based resin in the surface protective layer is preferably an aqueous polyurethane-based resin. That is, the polyurethane-based resin is preferably an aqueous polycarbonate-based polyurethane resin. By having such a structure, the adhesion to the skin layer when the aqueous polyurethane resin is contained becomes better, the wear resistance is further improved, and the olein acid resistance is also more excellent. In addition, since no organic solvent is used, it also contributes to the reduction of environmental load.

The content ratio of the polyurethane-based resin (particularly, the polycarbonate-based polyurethane resin) in the surface protective layer is not particularly limited, but is preferably 60% by mass or more with respect to the total amount of 100% by mass of the surface protective layer. More preferably, it is 90% by mass or more. When the content ratio is 60% by mass or more, the wear resistance of the laminated sheet becomes extremely good. The content ratio may be 100% by mass.

When the surface protective layer contains a polyurethane resin, it is preferable that the polyurethane resin (particularly, an aqueous polycarbonate-based polyurethane resin) in the surface protective layer is crosslinked with a carbodiimide-based cross-linking agent. Examples of the carbodiimide-based cross-linking agent include dicyclohexylmethanecarbodiimide, dicyclohexylcarbodiimide, tetramethylxylylenecarbodiimide, and urea-modified carbodiimide. As the carbodiimide-based cross-linking agent, an aqueous carbodiimide-based cross-linking agent is preferable. As the carbodiimide-based cross-linking agent, only one kind may be used, or two or more kinds may be used.

In particular, the surface protective layer is preferably a water-based polycarbonate-based polyurethane resin cross-linked with an water-based carbodiimide-based cross-linking agent. Since the surface treatment layer becomes a crosslinked film having high olein acid resistance and is excellent in olein acid resistance in addition to abrasion resistance, the laminated sheet may adhere to sweat, sebum, moisturizing lotion, etc. due to contact with the human body. By the way, good wear resistance can be maintained even for use.

The content of the structural portion derived from the carbodiimide-based cross-linking agent in the surface protective layer (that is, the content of the carbodiimide-based cross-linking agent to be blended when forming the surface protective layer) is not particularly limited, but is 100 mass of the polyurethane resin. The amount is preferably 0.5 to 10.0 parts by mass, more preferably 2.0 to 5.0 parts by mass.

The surface protective layer preferably further contains a silicone-based compound. The inclusion of the silicone compound improves the smoothness of the surface and further improves the wear resistance of the laminated sheet. As the silicone-based compound, only one kind may be used, or two or more kinds may be used.

As the silicone compound, a silicone compound having a siloxane bond of 2000 or less is preferable. Examples of the silicone-based compound include silicone oil, modified silicone oil, and silicone resin.

Examples of the silicone oil (straight silicone oil) include dimethyl silicone oil and methyl phenyl silicone oil.

Examples of the modified silicone oil include 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.), and the like. Examples thereof include 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.).

Examples of the silicone resin include straight silicone resin and modified silicone resin. Examples of the straight silicone resin include methyl silicone resin and methyl phenyl silicone resin. Examples of the modified silicone resin include alkyd-modified silicone resin, epoxy-modified silicone resin, acrylic-modified silicone resin, and polyester-modified silicone resin.

When the surface protective layer contains a polyurethane resin, the content of the silicone compound in the surface protective layer is not particularly limited, but is 3.0 to 20.0 parts by mass with respect to 100 parts by mass of the polyurethane resin. Is preferable, and more preferably 6.0 to 13.0 parts by mass.

The surface protective layer may contain other components other than the above-mentioned components. Examples of the other components include those exemplified as other components that may be contained in the above-mentioned resin composition layer. As the above other components, only one kind may be used, or two or more kinds may be used.

The thickness of the surface protective layer is not particularly limited, but is preferably 5 to 40 μm, more preferably 10 to 20 μm. When the thickness is 5 μm or more, the wear resistance of the laminated sheet is further improved. When the thickness is 40 μm or less, the bending resistance of the laminated sheet is further improved.

(Backing material)
The backing material is used by being bonded to the back surface of the base fabric layer (the surface opposite to the opening surface side), and fluffing on the back surface of the base fabric layer can be suppressed.

The backing material preferably has an air permeability of 100 cc / cm ² · s or more, and more preferably 150 cc / cm ² · s or more. When the air permeability is 100 cc / cm ² · s or more, the air permeability of the laminated sheet having a plurality of openings can be maintained high. The air permeability is a value measured based on the 8.26.1A method (Frazil type method) of JIS L1096 (2010).

Examples of the backing material include fibrous fabrics such as woven fabrics, knitted fabrics and non-woven fabrics, and fibrous base materials such as natural leather. Of these, knitting is preferable from the viewpoint of having a higher degree of freedom in elongation. Examples of the fibers constituting the fibrous fabric include those exemplified and described as the fibers constituting the fibrous fabric in the above-mentioned base fabric layer. Further, as the fiber, a raw yarn is preferable from the viewpoint of suppressing bleeding and coloring of the resin composition layer. Only one type of the fiber may be used, or two or more types may be used. The backing material may be a single layer or a plurality of layers.

The backing material is preferably bonded to the back surface of the base fabric layer via an adhesive layer. It is preferable that the backing material is adhered to the back surface of the base fabric layer at a plurality of points via the adhesive layer. As a result, the laminated sheet can be adhered while ensuring the air permeability.

The adhesive for forming the adhesive layer is not particularly limited, and known or commonly used adhesives can be used. Among them, the above-mentioned adhesive has an advantage that it can travel by melting it by heat without using a solvent, and it is easy to partially develop adhesiveness even if it is applied to the entire surface. A hot-melt type (heat-melt type) adhesive is preferable because it has an advantage that a larger adhesive force can be obtained by heat-sealing.

The adhesive is preferably a curable adhesive. That is, the adhesive is preferably a curable hot melt type adhesive. Examples of the curing include curing by irradiation with active energy rays, curing by heat (heat curing), curing by moisture (moisture curing), and two-component reaction type curing (two-component reaction curing). When curing progresses at room temperature, it is not necessary to separately perform curing treatment such as irradiation with active energy rays or heating. Examples of the active energy ray include visible light, ultraviolet rays, and electron beams.

Although the embodiment of the laminated sheet has been described above with reference to FIG. 1, the laminated sheet is not limited to such an embodiment. Further, the laminated sheet does not have the protrusion 12b and the skin layer 14 as essential components, and for example, a structure without the protrusion 12b, a structure without the skin layer 14, or the protrusion 12b and the skin layer. The structure may not have 14. Further, the laminated sheet may have other layers other than the above-mentioned layers as long as the effects of the present disclosure are not impaired. Examples of the other layer include a primer layer for improving the adhesion between the foamed resin layer and the skin layer.

(Laminated sheet)
The laminated sheet has an air permeability of 50 cc / cm ² · s or more, preferably 60 cc / cm ² · s or more, and more preferably 90 cc / cm ² · s or more. When the air permeability is 50 cc / cm ² · s or more, the air permeability is excellent and the feeling of stuffiness is small when the laminated sheet is used for the seat. The air permeability is a value measured based on the 8.26.1A method (Frazil type method) of JIS L1096 (2010).

The constant load elongation of the base fabric layer or the resin composition layer and the laminate having the backing material on both end surfaces in the laminated sheet is preferably 10% or more, more preferably 15% in both the vertical and horizontal directions. That is all. When the constant load elongation is 10% or more, it becomes easy to increase the constant load elongation of the laminated sheet. The constant load elongation is measured and calculated in the same manner as the constant load elongation rate test of the laminated sheet, except that the laminate is used as the test piece. The laminated body is a laminated body in which the backing material is used as one end face and the base fabric layer or the resin composition layer is used as the other end face. When the resin composition layer has the protruding portion, the resin composition layer is the other end face, and the laminate is a laminate having the resin composition layer and the backing material as both end faces. On the other hand, when the resin composition layer does not have the protruding portion, the base fabric layer is the other end face, and the laminate is a laminate having the base fabric layer and the backing material as both end faces.

In the laminated sheet, the air permeability of the laminate having the base fabric layer or the resin composition layer and the backing material on both end faces is preferably 50 cc / cm ² · s or more, more preferably 60 cc / cm. It is ² · s or more. When the air permeability is 50 cc / cm ² · s or more, the air permeability of the laminated sheet having a plurality of openings can be maintained high. The air permeability is a value measured based on the 8.26.1A method (Frazil type method) of JIS L1096 (2010).

The laminated sheet preferably has a BLC value of 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 laminated sheet is not too hard, and when the BLC value is 6.0 or less, the texture of the laminated sheet is not too soft. It can be a texture. 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 MACHINRS INC.).

The laminated sheet is preferably used for synthetic leather, more preferably for vehicle interior synthetic leather (particularly for automobile interior synthetic leather), and more preferably for vehicle interior synthetic leather (particularly for automobile seat). Synthetic leather applications).

The laminated sheet 1 which is one embodiment of the above-mentioned laminated sheet can be manufactured, for example, as follows. First, a laminate in which the resin composition layer 12 is impregnated in the base cloth layer 11 is produced. As a resin composition for forming the resin composition layer 12, a polyvinyl chloride-based resin and, if necessary, additives such as the above-mentioned other components are added, and if necessary, dissolved in a solvent and mixed. To prepare the resin composition (I). The content of various components such as the polyvinyl chloride resin in the resin composition (I) is adjusted so that the content in the resin composition layer 12 is within the above-mentioned preferable range.

Next, the resin composition (I) forming the resin composition layer 12 is applied onto the base cloth layer 11 to impregnate the base cloth layer 11, and then heated using a heating device such as an oven. When the resin composition (I) contains a solvent, the solvent is volatilized by the above heating. The protruding portion 12b is heated after the resin composition (I) is applied and before the resin composition (I) is completely impregnated into the base fabric layer 11 to stop the impregnation, or the viscosity of the resin composition (I). Can be formed by adjusting. Further, the heating is performed after the base fabric layer 11 is impregnated to a desired depth and then left to stand. The heating is performed, for example, at a temperature of 100 to 150 ° C. for 1 to 5 minutes.

The resin composition (I) can be applied by a known or conventional method, and examples thereof include a reverse coating method, a roll coating method, a die coating method, a wire bar coating method, and a knife coating method. Further, as another method, a method of dipping the base cloth layer 11 into the resin composition (I) can be mentioned.

Next, the foamed resin layer 13 is formed on the impregnated side of the base cloth layer 11 impregnated with the resin composition (I). The foamed resin layer 13 can be formed, for example, as follows. First, a resin component such as a polyvinyl chloride resin is heated and melted and mixed, and if necessary, an additive such as a plasticizer, a filler, the above other components, a foaming agent, a foaming accelerator, or a cell adjusting agent is added. Is added and kneaded, and then cooled to prepare a resin composition (II) (pellets, etc.). The preferable contents of various components such as the polyvinyl chloride resin and the thermoplastic polyurethane elastomer in the resin composition (II) are the same as the contents in the foamed resin layer described above.

Examples of the foaming agent include supercritical fluids; inorganic foaming agents such as ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium boron hydride, and azides; azo foaming agents, nitroso foaming agents, and the like. Organic foaming agents such as hydrazide-based foaming agents, carbazide-based foaming agents, and triazine-based foaming agents; heat-expandable compounds such as isobutane and pentane; Examples thereof include heat-expandable fine particles (heat-expandable microcapsules) encapsulated in microcapsules made of a thermoplastic resin such as an acrylic acid ester. As the foaming agent, only one kind may be used, or two or more kinds may be used.

Examples of the azo-based foaming agent include azodicarbonamide, azobisisobutynitrile, diazoaminobenzene, diethylazodicarboxylate, diisopropylazodicarboxylate, and azobis (hexahydrobenzonitrile). Examples of the nitroso-based foaming agent include N, N'-dimethyl-N, N'-dinitroterephthalamine, N, N'-dinitropentamethylenetetramine and the like. Examples of the hydrazide-based foaming agent include benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, 3,3'-disulfone hydrazide phenylsulfone, toluenedisulfonylhydrazone, thiobis (benzenesulfonylhydrazide), p, p'-oxybis (benzene). Sulfonyl hydrazide) and the like. Examples of the carbazide-based foaming agent include p-toluenesulfonyl semicarbazide and 4,4'-oxybis (benzenesulfonyl semicarbazide). Examples of the triazine-based foaming agent include trihydrazinotriazine and 1,3-bis (o-biphenyltriazine).

The foamed resin layer is preferably made by using a foaming agent, and particularly preferably made by using heat-expandable microcapsules. When a foaming agent is used, the cell diameter in the foamed resin layer becomes more uniform as compared with the method of foaming by mechanical stirring or the like. Further, when the heat-expandable microcapsules are used, a foamed resin layer having a finer and more uniform cell diameter can be produced.

The content of the foaming agent in the resin composition (II) is not particularly limited, but is appropriately selected depending on the intended use of the foamed resin layer to be obtained. For example, it is 0 with respect to 100 parts by mass of the polyvinyl chloride resin. .1 to 10 parts by mass, more preferably 1 to 5 parts by mass.

Next, the foamed resin layer 13 is formed from the resin composition (II). For example, after melting or dissolving the resin composition (II) containing a foaming agent, it is processed into a sheet to form an unexpanded resin sheet (unexpanded resin layer), and the obtained unexpanded resin sheet is used as a resin composition (unfoamed resin layer). It is attached to the impregnated side of the base cloth layer 11 impregnated with I), and then heat-treated while pressurizing as necessary using a heating device such as an oven to foam the foaming agent and volatilize the solvent if it is contained. The foamed resin layer 13 can be formed. The method for molding the unfoamed resin sheet can be performed by a known or conventional method, but it is easy to form a sheet from a high-viscosity resin composition, and it is easy to produce a wide laminated sheet. Therefore, the calendar method is preferable. As another method, after melting or dissolving the resin composition (II), it is applied on a base material such as a release sheet to form a coating film (unfoamed resin layer), and the obtained coating film is used as a resin composition. The foaming agent may be formed by sticking it to the impregnated side of the base cloth layer 11 impregnated with the substance (I) and then foaming the foaming agent using a heating device such as an oven. The foamed resin layer 13 is formed by heating when the foaming agent is foamed, and the resin composition layer 12 (impregnated portion 12a and protruding portion 12b) is formed from the resin composition (I) impregnated in the base cloth layer 11. The formed and impregnated resin composition layer 12 constrains the fibers of the base fabric layer 11. Further, as another method, after foaming the unfoamed resin layer to prepare the foamed resin layer 13, the obtained foamed resin layer 13 is attached to the impregnated side of the base cloth layer 11 impregnated with the resin composition (I). You may match.

Next, the epidermis layer 14 is formed on the surface of the foamed resin layer 13. A resin composition for forming the skin layer 14 is applied to the surface of the foamed resin layer 13 to form a coating film, and then the coating film is used with a heating device such as an oven to form an isocyanate and a polyol for forming a polyurethane resin. The skin layer 14 is formed by curing by accelerating the reaction with the resin, volatilizing the solvent, and curing by a cross-linking agent. The resin composition can be applied by a known or conventional method.

Next, the surface protective layer 15 is formed on the surface of the epidermis layer 14. A resin composition for forming the surface protective layer 15 is applied to the surface of the skin layer 14 to form a coating film, and then the coating film is used with a heating device such as an oven to form an isocyanate and a polyol for forming a polyurethane resin. The surface protective layer 15 is formed by curing by accelerating the reaction with and volatilizing the solvent, curing by a cross-linking agent, and the like. The above resin composition can be applied by a known or conventional method. As described above, it is possible to prepare a laminated body 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 protection layer 15 in this order. ..

Next, the laminated body is perforated to form the opening 20. The perforation process is carried out by a known or conventional method so as to obtain a desired shape.

Next, the backing material 17 is attached to the back surface 11b of the base fabric layer 11 of the laminated body that has been perforated via the adhesive layer 16. First, the adhesive that forms the adhesive layer 16 on the back surface 11b of the base cloth layer 11 is applied by gravure coating or the like so as to be scattered on the back surface 11b of the base cloth layer 11. After that, the adhesive surface of the backing material 17 is superposed on the back surface 11b of the base fabric layer 11, and then the adhesive is heated and melted and cured by heating to form the adhesive layer 16 and the backing material 17 is bonded.

The surface of the surface protective layer 15 may be embossed to have a textured pattern. As described above, the laminated sheet 1 can be manufactured.

According to the above-mentioned laminated sheet, it is possible to provide a laminated sheet having good tension and less exposure of fluff from an opening, particularly synthetic leather. For this reason, it has an excellent appearance, and the fabric of the base fabric layer can be seen from the opening without being disturbed by fluff, and the perforation laminated sheet (especially perforation synthetic leather) with high design can be seen by changing the color and pattern of the fabric. ) Can be produced. In addition, the adhesion between the base fabric layer and other layers such as the foamed resin layer is excellent, and in particular, when the foamed resin layer contains a polyvinyl chloride resin as a main component, the adhesion is particularly excellent, so perforation processing is performed. Even if it is used, it has high adhesion and excellent wear resistance. Therefore, the laminated sheet can be used for the seat surface of an automobile seat, which is particularly prone to interlayer friction. Further, by using the polyvinyl chloride resin, the flame retardancy and the economy are excellent as compared with the case where the polyurethane resin is used. Further, according to the above-mentioned laminated sheet, since it has a plurality of openings, when it is used for synthetic leather of a seat for automobiles, it secures breathability at the chair contact surface of a passenger and provides comfort by preventing stuffiness. Obtainable. Therefore, the laminated sheet can be particularly preferably used for an automobile that sits outdoors for a long time.

The inventions of the present disclosure will be described in more detail with reference to examples below, but the inventions of the present disclosure are not limited to these examples. The addition amount shown in the table is the blending amount of each component (that is, the blending amount of the active ingredient in each raw material, so-called pure content), and is represented by "parts by mass" unless otherwise specified.

Example 1
Polyvinyl chloride (average degree of polymerization: 1300) 100 mass on one side of polyester base cloth (trade name "TU16002", manufactured by saving-textile, grain: 255 g / m ² , thickness: 800 μm, warp knitting) A paste-like resin composition consisting of 90 parts by mass of a portion and a dialkyl phthalate-based plasticizer was applied in an amount of 88 parts by mass with respect to 100 parts by mass of the base cloth, and a part was impregnated into the base cloth. Then, the resin composition was temporarily fixed by heating at 120 ° C. for 3 minutes to obtain a resin temporary fixing base cloth.

On the other hand, 100 parts by mass of polyvinyl chloride (average degree of polymerization: 2000), 10 parts by mass of thermoplastic polyurethane elastomer (shore A hardness: 75, melting point: 170 ° C.), 90 parts by mass of dialkyl phthalate plasticizer, foaming agent (azo). Add 2.5 parts by mass of (dicarbonamide) and 15 parts by mass of additives (including filler, stabilizer, light-resistant agent, pigment, and flame-retardant), knead at 160 ° C. for 5 minutes, and then cool. A resin composition was prepared. The obtained resin composition is made into a sheet by a calendar method to obtain an unfoamed resin sheet, then attached to the surface of the resin composition of the above resin temporary fixing base cloth in a heated state, and heated at 210 ° C. for 2 minutes to obtain a foaming agent. Was foamed to form a resin foam having a thickness of 500 μm, and at the same time, the temporarily fixed resin composition was solidified, the fibers of the base cloth were restrained at the impregnated portion, and a protruding portion was formed.

Next, using a reverse coater on the surface of the resin foam, 100 parts by mass of an aqueous polycarbonate polyurethane resin (trade name "Hydran WLS-210", manufactured by DIC Corporation), 10 parts by mass of a pigment, and 0 parts of a wettability improver. A composition obtained by mixing 3 parts by mass of a defoaming agent, 0.3 parts by mass of a defoaming agent, and 3 parts by mass of a cross-linking agent is applied to form a coating film, and the coating film is heated at 130 ° C. for 5 minutes. The coating film was dried and crosslinked to form a skin layer having a thickness of 30 μm. Next, using a reverse coater on the surface of the skin layer, an aqueous polycarbonate-based polyurethane resin (trade name "WF-78-143", manufactured by Stahl), a silicone-based compound (trade name "HM-54-002", Stahl). The composition obtained by mixing (manufactured by the company) and a carbodiimide-based cross-linking agent is applied to form a coating film, and the coating film is heated at 130 ° C. for 5 minutes to dry and cross-link the coating film to a thickness of 20 μm. The surface treatment layer of was formed. Then, the formed surface treatment layer was embossed to give a textured pattern.

Next, a punching plate in which punching pins having a diameter of 1.1 mm are arranged so as to be perforated in a diamond shape at intervals of 5 mm is continuously moved up and down, and the laminated sheet is passed between them to perform perforation processing. A plurality of openings penetrating all layers were provided.

Next, a urethane-based reactive hot melt type adhesive (trade name "NH128", manufactured by DIC Corporation) was heated at 90 ° C. on the non-impregnated surface (the surface on which the resin foam was not formed) of the base cloth. It is applied so that it is scattered by the gravure coat method, and a polyester backing material (trade name "CU19702", manufactured by saving-textile, circular knitting) is attached to the adhesive-coated surface of the base cloth, and left at room temperature for 24 hours. The backing material was attached to the non-impregnated surface of the base cloth. As described above, a laminated sheet was produced.

Examples 2-4, Comparative Examples 1-2
A laminated sheet was produced in the same manner as in Example 1 except that the amount of the resin impregnated was changed as shown in the table.

Comparative Example 3
A laminated sheet was produced in the same manner as in Example 1 except that a polyester base cloth (trade name “WO19401”, manufactured by saving-textile, basis weight: 202 g / m ² ) was used as the base cloth.

Comparative Example 4
A laminated sheet was produced in the same manner as in Example 1 except that a punching pin having a diameter of 0.8 mm was used in the perforation process.

Comparative Example 5
Polyurethane resin (trade name "MP-865PS", manufactured by DIC Corporation) is applied to a polyester base cloth (trade name "TU16002", manufactured by saving-textile, grain: 255 g / m ² , thickness: 800 μm, warp knitting). The base cloth was impregnated in an amount of 56 parts by mass with respect to 100 parts by mass, wet-solidified, and then dried at 120 ° C. for 3 minutes to obtain a resin-impregnated base cloth. A laminated sheet was produced in the same manner as in Example 1 except that this resin-impregnated base cloth was used.

<Evaluation>
The following evaluations were made on the laminated sheets obtained in Examples and Comparative Examples. The results are shown in Table 1.

(1) Tensile strength Three test pieces having a width of 50 mm and a length of 150 mm were collected from the base fabrics used in Examples and Comparative Examples from the warp direction and the weft direction, respectively. Under the conditions of room temperature 20 ± 2 ° C and humidity 65 ± 5% RH, pinch both ends of the test piece with a gripping tool so that there is no slack, and use a tensile tester (trade name "Autograph", manufactured by Shimadzu Corporation). The test piece was pulled at a grip width of 50 mm, a grip interval of 100 mm, and a movement speed of the grip tool of 200 mm / min to break the test piece. Then, in each of the vertical direction and the horizontal direction, the maximum load (N / cm) per unit width until the test piece broke was measured, and the average value of the three test pieces was obtained.

(2) Constant load elongation rate (base cloth, backing material, laminated body (A))
From the base cloth, the backing material, and the laminated body (A) used or prepared in Examples and Comparative Examples, three test pieces having a width of 50 mm and a length of 250 mm were collected from the warp direction and the weft direction, respectively. Next, two marking lines were attached to the central portion of the test piece so that the distance between the marking lines was 100 mm. With this as a gripping interval of 150 mm, it was attached to a test device (trade name "Autograph", manufactured by Shimadzu Corporation), and a load of 78.4 N (8 kgf) was gently applied. It was left for 10 minutes with the load applied, and then the distance between the marked lines was calculated. Then, the constant load elongation rate was calculated by the following formula in each of the vertical direction and the horizontal direction, and the average value of the three test pieces was obtained. The laminated body (A) is a laminated body obtained by peeling the surface protective layer, the skin layer, and the resin foam from the laminated sheets produced in Examples and Comparative Examples.
Constant load elongation rate (%) = A-100
A: Distance between marked lines (mm) 10 minutes after applying a load

(3) Air permeability With respect to the backing material and the laminated body (A) used or manufactured in Examples and Comparative Examples, JIS L1096 (2010) 8. The air permeability was measured under the conditions of the 26.1A method (Frazil type method).

(4) Tensioning The laminated sheets obtained in the examples and comparative examples were visually evaluated by five people for the presence or absence of tension when used as the overlay (skin material) for automobile seats, and the tension of the laminated sheets was evaluated. Was determined according to the following criteria.
[criterion]
○ (Good): 3 or more people evaluated “Tension and no wrinkles” × (Defective): 2 or less people evaluated “Tension and no wrinkles”

(5) Appearance The vicinity of the openings of the laminated sheets obtained in Examples and Comparative Examples was visually evaluated by five people, and the appearance was judged according to the following criteria.
[criterion]
○ (Good): 3 or more people evaluated as "a beautiful opening without fluff" × (Poor): 2 or less evaluated as "a beautiful opening without fluff"

(6) Fluffing (front side)
The backing surface of the laminated sheet obtained in Examples and Comparative Examples was used with a wear wheel of CS # 10 using a Daver wear tester (trade name "Taber type ablation tester", manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Then, it was worn 100 times under the condition of a load of 4.9 N. Then, it was sucked from the surface protective layer side with a vacuum cleaner, the vicinity of the opening was visually observed, and the fluffing on the front side was judged according to the following criteria.
[criterion]
○ (Good): No fluff can be seen in the opening on the surface protection layer side × (Defective): No fluff can be seen in the opening on the surface protection layer side

(7) Flame Retardant With respect to the laminated sheets obtained in Examples and Comparative Examples, a 350 mm × 100 mm test piece was cut out from the vertical direction and the horizontal direction, and FMVSS No. By the method of 302 combustibility test, the test piece is held horizontally, the 38 mm flame is indirectly flamed for 15 seconds, the combustion rate is measured from the A mark line to the B mark line 254 mm, and the flame retardancy of the laminated sheet is as follows. Judgment was made according to the judgment criteria.
[criterion]
○ (Good): Combustion speed is 80 mm / min or less × (Defective): Combustion speed is 81 mm / min or more

(8) Gakushin wear resistance From the laminated sheets obtained in Examples and Comparative Examples, one test piece having a width of 10 mm and a length of 150 mm was collected from the vertical direction (longitudinal direction), and the back surface (lining material) was taken. A urethane foam having a width of 10 mm, a length of 15 mm, and a thickness of 3 mm was attached to the surface). A friction test with JIS L3102 No. 6 cotton cloth was carried out using a "Gakushin-type dyeing friction stiffness tester" (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) specified in JIS L0849. It was worn 30,000 times with a load of 1 kg. Then, the test piece (surface of the surface protective layer) after wear was visually observed, and the Gakushin wear property was judged according to the following criteria.
[criterion]
○ (Good): The surface protective layer remains without being scraped off due to wear, and the epidermis layer is not exposed. △ (Available): The surface protective layer is scraped off due to wear, but the base cloth layer is not exposed. Thing × (defective): Thing with exposed base cloth layer

(9) BLC value (texture)
From the laminated sheets obtained in Examples and Comparative Examples, one test piece having a size of 150 mm square was taken and pushed in with a load of 500 g using "GT303 Leather Softness Tester" (manufactured by GOTECH TESTING MACHINRS INC.). The strain measurement value (BLC value) at that time was measured. The larger the strain measurement value, the softer the texture.

(10) Depth of Impregnated Part With respect to the laminated sheet obtained in Example, the cross section in the thickness direction was observed using an electron microscope (trade name "VHX-5000", manufactured by KEYENCE CORPORATION). A cross-sectional photograph of Example 1 is shown in FIG. As a result, the depth of the impregnated portion in any of the laminated sheets was in the range of 30 to 70% with respect to the thickness of the base cloth. The laminated sheet shown in FIG. 2 has no backing material bonded to the laminated sheet.

The laminated sheets of Examples 1 to 4 had good tension and good appearance, and fluffing on the front side was less likely to occur and fluff was not exposed. It was also excellent in breathability, flame retardancy, and vibration wear resistance. On the other hand, when the amount of the resin composition was small (Comparative Example 1), the restraint of the base cloth layer was insufficient, the appearance was inferior, and fluffing on the front side was observed. When the amount of the resin composition was large (Comparative Example 2), the elongation of the base fabric layer was reduced, the tension was inferior, and the appearance was also inferior. When the low load elongation of the base fabric layer was low (Comparative Example 3), the tension was inferior and the appearance was also inferior. When the air permeability of the laminated sheet was low (Comparative Example 4), the air permeability was inferior. When a polyurethane-based resin was used as the resin to be impregnated in the base cloth layer (Comparative Example 5), the flame retardancy and the school vibration wear resistance were inferior.

1 Laminated sheet 11 Base cloth layer 11a Front surface 11b Back surface 12 Resin composition layer 12a Impregnated part 12b Protruding part 13 Foamed resin layer 14 Skin layer 15 Surface protection layer 16 Adhesive layer 17 Backing material 20 Opening 20a Opening surface

Claims (12)

A laminated sheet including a base cloth layer and a resin composition layer containing a polyvinyl chloride resin as a main component.
The resin composition layer has an impregnated portion impregnated in the base fabric layer and has an impregnated portion.
It has a plurality of openings that penetrate the base fabric layer and the resin composition layer in the thickness direction.
The mass of the resin composition layer is 30 to 100 parts by mass with respect to 100 parts by mass of the base fabric layer.
The base fabric layer has a tensile strength of 100 N / cm or more and a constant load elongation of 20% or more in both the vertical and horizontal directions.
A laminated sheet having an air permeability of 50 cc / cm ² · s or more. The laminated sheet according to claim 1, wherein the impregnated portion is exposed on one surface of the base fabric layer and is not exposed on the other surface. In the impregnated portion, the resin composition layer is impregnated into the base cloth layer from one surface of the base cloth layer to a depth of 10 to 90% with respect to the thickness of the base cloth layer. The laminated sheet according to claim 2. The laminated sheet 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. The laminated sheet according to any one of claims 1 to 4, further comprising a backing material having an air permeability of 100 cc / cm ² · s or more on the back surface of the base cloth layer. The laminated sheet according to claim 5, wherein the backing material is provided on the back surface of the base fabric layer via an adhesive layer. The laminated sheet according to claim 5 or 6, wherein the opening does not penetrate the backing material. The claim that the constant load elongation of the base fabric layer or the resin composition layer and the laminate having the backing material on both end surfaces is 10% or more in both the vertical and horizontal directions, and the air permeability is 50 cc / cm ² · s or more. The laminated sheet according to any one of 5 to 7. The laminated sheet according to any one of claims 1 to 8, further comprising a foamed resin layer containing a polyvinyl chloride resin as a main component on one surface of the base cloth layer. The laminated sheet according to claim 9, wherein the foamed resin layer contains a thermoplastic polyurethane elastomer. The laminated sheet according to claim 9 or 10, further comprising a skin layer containing a polyurethane resin on the side of the foamed resin layer opposite to the side on which the base fabric layer is located. The laminated sheet according to any one of claims 1 to 11, which is used for synthetic leather.

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