JP2003071988A - Laminated sheet and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which develops good touch (soft touch) when used as a sheet for seat and is suitable for obtaining a laminate excellent in appearance and light resistance and the laminate using the laminated sheet. SOLUTION: In the laminated sheet, a surface layer containing a thermoplastic polyurethane elastomer as a main component and a base material layer containing a polyolefin resin as a main component are laminated, the 10% modulus of elasticity at 23 deg.C of the sheet measured based on JIS K-7311 is 1-6 MPa, and a foundation is laminated on the side of the base material layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminated sheet (including a laminated film) and a laminated body using the same.

[0002]

2. Description of the Related Art Conventionally, in order to give a good contact feeling (soft touch feeling) to a portion, such as an automobile interior material, which is contacted by a person, for example, a polyvinyl chloride resin whose surface is embossed. A laminated sheet obtained by laminating a sheet layer, a foam sheet layer and the like is widely used as a covering sheet. However, among automobile interior materials and the like, a polyvinyl chloride resin sheet tends to lack flexibility in a seat for a seat that requires particularly good contact feeling (soft touch feeling), Further, in the production, there is a problem that a plurality of steps are required at the time of stacking and the production steps are complicated.

To address these problems, for example,
JP-A-6-246812 discloses a sheet-like laminate obtained by co-extruding a composition as a soft touch layer containing a thermoplastic elastomer and elastic fine particles as main components, and a thermoplastic resin as a base layer. Is stretched to obtain a soft touch sheet, and then a foam layer is laminated on the base material layer side of the soft touch sheet.

However, the covering sheet produced by the above-mentioned manufacturing method has a problem that when it is used as a seat sheet by laminating it with a base cloth, the touch feeling (soft touch feeling) tends to be insufficient.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide an excellent contact feeling (soft touch feeling) even when used as a seat for a seat, and to improve appearance and light resistance. Another object is to provide a laminated sheet suitable for obtaining an excellent laminated body, and a laminated body using the laminated sheet.

[0006]

The laminated sheet of the present invention comprises:
A surface layer containing a thermoplastic polyurethane-based elastomer as a main component and a base material layer containing a polyolefin-based resin as a main component are laminated, and the 10% modulus at 23 ° C. is 1 to 6 MPa. Incidentally, the 10% modulus referred to in the present invention means JIS K-7331.
It means 10% modulus (10% tensile stress) measured in accordance with "Testing method for polyurethane-based thermoplastic elastomer".

The laminated body of the present invention is characterized in that a base cloth is laminated on the base layer side of the laminated sheet of the present invention.

The thermoplastic polyurethane elastomer constituting the surface layer of the laminated sheet of the present invention is one which exhibits rubber elasticity at room temperature and is plasticized at high temperature to enable various molding processes. They often share a soft segment (rubber component) with entropy elasticity and a hard segment (molecular restraint component) to prevent plastic deformation, and have a partially crosslinked structure in the moldable range. In some cases, it does not have a wide range of three-dimensional crosslinked structure (mesh structure).

The thermoplastic polyurethane elastomer is not particularly limited, but for example, a block copolymer having a soft segment such as polyether, polyester and polycarbonate and a hard segment including polyurethane (urethane bond). A thermoplastic polyurethane-based elastomer made of coalesced and the like is preferably used. Among them, it is excellent in heat resistance and light resistance, and by using a non-yellowing isocyanate compound, discoloration occurs even when used outdoors for a long period of time. A thermoplastic polyurethane elastomer composed of a block copolymer having a polycarbonate as a soft segment and a (non-yellowing) polyurethane (urethane bond) as a hard segment is more preferable because it has the advantage of not causing deterioration such as Used . These thermoplastic polyurethane elastomers may be used alone or in combination of two or more kinds.

The thermoplastic polyurethane elastomer is not particularly limited, but one having a weight average molecular weight (Mw) of 20,000 to 3,000,000 is preferable. When the Mw of the thermoplastic polyurethane elastomer is less than 20,000, the mechanical strength such as rigidity of the obtained surface layer or laminated sheet may be insufficient, and when it exceeds 3 million, the obtained surface may be insufficient. The flexibility of the layer or laminated sheet may be impaired.

The thermoplastic polyurethane elastomer is not particularly limited, but one having a glass transition temperature (Tg) of -50 ° C to + 20 ° C is preferable. Tg of thermoplastic polyurethane elastomer is -5
If it is lower than 0 ° C, the resulting surface layer or laminated sheet may have insufficient scratch resistance. Conversely, if it exceeds + 20 ° C, the obtained surface layer or laminated sheet may have poor impact resistance at low temperatures. May be sufficient.

The thermoplastic polyurethane elastomer is not particularly limited, but one having a 10% modulus at 23 ° C. of 1 to 25 MPa is preferable. If the 10% modulus of the thermoplastic polyurethane elastomer at 23 ° C. is less than 1 MPa, the mechanical strength of the resulting surface layer or laminated sheet may be insufficient, and conversely if it exceeds 25 MPa, the resulting surface layer will be obtained. The flexibility of the laminated sheet may be impaired.

Further, the thermoplastic polyurethane elastomer differs depending on the hardness and thickness of other layers to be laminated, and is not particularly limited, but JIS K-
It is preferable that the hardness measured by a type A durometer according to 7311 is 50 to 98.

Elastic fine particles may be added to the above-mentioned thermoplastic polyurethane elastomer used in the present invention in order to impart an excellent matte feeling to the surface layer of the obtained laminated sheet.

The elastic fine particles have a shape that elastically recovers when the pressure is released after pressing until the shape is deformed, and is generally made of synthetic resin.

The synthetic resin constituting the elastic fine particles is not particularly limited, but has a higher melting temperature than that of the thermoplastic polyurethane elastomer and is plasticized or decomposed under molding conditions such as extrusion molding. A resin that does not give rise to is preferable, and a crosslinked synthetic resin is generally used. If the elastic fine particles melt with the thermoplastic polyurethane-based elastomer when melt-kneading or extruding, it is possible to obtain a laminated sheet comprising a surface layer having an excellent matting feeling and a touch feeling (soft touch feeling). It can be difficult.

The synthetic resin is not particularly limited, but examples thereof include polyurethane resins, polystyrene resins, polyacrylate resins, acryl-urethane copolymers, styrene-isoprene copolymers, and these. The cross-linked resin and the like can be mentioned and are preferably used. These synthetic resins may be used alone or in combination of two or more kinds.

The shape of the elastic fine particles is not particularly limited, and may be solid or hollow.

The size of the elastic fine particles is not particularly limited, but those having an average particle diameter of 1 to 50 μm are preferable. If the average particle diameter of the elastic fine particles is less than 1 μm, the matte feeling of the surface layer may not be sufficiently obtained. The layers may be easily broken.

Further, the addition amount of the elastic fine particles to the thermoplastic polyurethane elastomer is not particularly limited, but 20 to 120 parts by weight of the elastic fine particles to 100 parts by weight of the thermoplastic polyurethane elastomer is used. Is preferred. The amount of elastic fine particles added is 20 per 100 parts by weight of the thermoplastic polyurethane elastomer.
If it is less than parts by weight, the matte feeling of the surface layer may not be sufficiently obtained, and if it exceeds 120 parts by weight, cracks may occur in the surface layer during the manufacturing process of the laminated sheet, such as during stretching. It may occur easily.

The thermoplastic polyurethane elastomer used in the present invention is, for example, an inorganic filler or an acrylonitrile, for example, in order to have a change in the feeling of contact, if necessary, within a range not hindering the achievement of the object of the present invention. An organic filler such as particles of butadiene-styrene copolymer (ABS) or polymethylmethacrylate resin (PMMA) may be added, or a softening agent (plasticizer), coupling agent, Matting agent, colorant, antioxidant, heat stabilizer,
Light stabilizer, ultraviolet absorber, lubricant, antistatic agent, flame retardant,
Photochromic compound, anti-condensation agent, anti-rust agent, anti-bacterial
One kind or two or more kinds of various additives such as an antifungal agent may be added.

The surface layer constituting the laminated sheet of the present invention may be embossed with a leather grain pattern, a perch grain pattern or a satin finish in order to further improve the contact feeling (soft touch feeling). The embossing method is not particularly limited and may be any known method,
Generally, a method of pressing with an embossing roll is simple and preferable. Further, the surface layer may be decorated by printing or the like, if necessary.

The thickness of the surface layer may be appropriately set according to the performance desired to be imparted to the surface layer or the laminated sheet, and is not particularly limited, but generally 5 to 100 μm.
Is preferred.

The polyolefin resin constituting the base material layer of the laminated sheet of the present invention is not particularly limited, and examples thereof include polyethylene resin, polypropylene resin and thermoplastic polyolefin elastomer. These polyolefin resins may be used alone or in combination of two or more kinds.

The above-mentioned thermoplastic polyolefin-based elastomer is one which exhibits rubber elasticity at room temperature and is plasticized at high temperature to enable various molding processes. Generally, a soft segment (rubber having entropy elasticity in a molecule) is used. Component) and a hard segment (molecular restraint component) for preventing plastic deformation in many cases, and in some cases it has a partially crosslinked structure in the moldable range, but a wide range of three-dimensional It does not have a crosslinked structure (mesh structure).

The thermoplastic polyolefin-based elastomer is not particularly limited, but for example,
Examples of the thermoplastic polyolefin-based elastomer include polyethylene as a soft segment, a copolymer of ethylene and a small amount of diene, or a partially cross-linked product thereof, and a block copolymer having polypropylene or the like as a hard segment. To be

Specific examples of such a thermoplastic polyolefin-based elastomer are not particularly limited, but for example, trade name "MILASTOMA 80" manufactured by Mitsui Chemicals, Inc.
Commercial products such as "30N" and "Milastoma 5030N" can be mentioned. These thermoplastic polyolefin-based elastomers may be used alone or in combination of two or more.

The above polyolefin resin is not particularly limited, but it is preferable that the 10% modulus at 23 ° C. is 0.1 to 10 MPa. The 10% modulus of the polyolefin resin at 23 ° C. is 0.
If it is less than 1 MPa, the mechanical strength of the obtained base material layer or laminated sheet may be insufficient, and conversely 10 MPa.
When it exceeds, the flexibility of the obtained base material layer or laminated sheet may be impaired.

The above-mentioned polyolefin resin may be crosslinked, if necessary, within a range not hindering the achievement of the object of the present invention.

The cross-linking method is not particularly limited. For example, a method of adding a cross-linking agent to a polyolefin resin and heating to cross-link it (chemical cross-linking method), and ionizing radiation such as electron beam are used. Examples thereof include a method of irradiating to crosslink (electron beam crosslinking method or ionizing radiation crosslinking method), a method of irradiating with ultraviolet light to crosslink (ultraviolet crosslinking method), and the like. These crosslinking methods may be used alone,
Two or more types may be used in combination.

The cross-linking agent is not particularly limited, but for example, dicumyl peroxide, t-butylperoxycumene, di (t-butylperoxy)-
m-diisopropylbenzene, 2,5-dimethyl-2,
Examples include organic peroxides such as 5-dibutylperoxyhexene-3,1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, and polyfunctional monomers such as divinylbenzene. . These cross-linking agents may be used alone or in combination of two or more kinds.

The above polyolefin resin may be foamed, if necessary, within a range that does not impair the achievement of the object of the present invention. The expansion ratio may be appropriately set according to the performance to be imparted to the base material layer and is not particularly limited, but it is generally preferably 1.1 to 5 times. The expansion ratio means the reciprocal of the apparent density measured according to JIS K-6767 "Expanded plastic-polyethylene-Test method".

The above-mentioned foaming method is not particularly limited, but for example, a method of adding a pyrolytic foaming agent to a polyolefin resin and heating to foam it (heat foaming method), or evaporation to a polyolefin resin. Mold blowing agent,
Examples thereof include a method of foaming at the same time as extrusion (extrusion foaming method) and a bead foaming method. These foaming methods may be used alone or in combination of two or more.

The thermal decomposition type foaming agent is not particularly limited, but examples thereof include baking soda, azodicarbonamide (ADCA), N, N'-dinitrosopentamethylenetetramine (DPT) and the like. These thermal decomposition type foaming agents may be used alone or in combination of two or more kinds.

The evaporative foaming agent is not particularly limited, but examples thereof include CFC gas, water, carbon dioxide gas, nitrogen gas and the like. These evaporative foaming agents may be used alone or in combination of two or more kinds. Further, the thermal decomposition type foaming agent and the evaporation type foaming agent may be used alone or in combination.

The above-mentioned polyolefin-based resin may be, for example, an inorganic filler, an organic filler, a softening agent (plasticizer), a coupling agent, a coloring agent, if necessary, within a range not hindering the achievement of the object of the present invention. One of various additives such as antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, flame retardants, photochromic compounds, anti-condensation agents, anticorrosive agents, antibacterial and antifungal agents. Alternatively, two or more kinds may be added.

The thickness of the base material layer constituting the laminated sheet of the present invention may be appropriately set according to the performance desired to be imparted to the base material layer or the laminated sheet and is not particularly limited.
Generally, it is preferably 100 to 1000 μm.

The laminated sheet of the present invention is formed by laminating the surface layer and the base material layer. The method for laminating the surface layer and the base material layer is not particularly limited, but for example,
Examples include a method of directly laminating the surface layer and the base material layer (direct method), a method of laminating the surface layer and the base material layer via an adhesive layer (adhesion method), and whichever method is adopted. However, it is preferable to use an adhesion method because the adhesion between the surface layer and the base material layer is further improved.

The adhesive for forming the above-mentioned adhesive layer is not particularly limited, but for example, polyolefin resin such as polypropylene resin, ethylene-vinyl acetate copolymer, chlorinated polyolefin resin and the like. ,
Adhesives containing thermoplastic synthetic resins such as vinyl acetate-based resins, polyvinyl alcohol-based resins, vinyl chloride-based resins, poly (meth) acrylic-based resins, polystyrene-based resins, etc. as main components, natural rubber, and styrene-butadiene copolymer Coalesce, chloroprene rubber, acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer,
Examples of the adhesive include a rubber (elastomer) such as a synthetic rubber such as a styrene-butadiene-styrene block copolymer and a hydrogenated product thereof, a styrene-isoprene-styrene block copolymer and a hydrogenated product thereof, and the like as a main component. Among these, an adhesive containing a polypropylene resin as a main component is more preferably used. These adhesives may be used alone or in combination of two or more. Further, the adhesive containing the thermoplastic synthetic resin as the main component and the adhesive containing the rubber (elastomer) as the main component may be used alone or in combination.

The polypropylene-based resin is not particularly limited, but for example, ordinary polypropylene-based resins such as homopolypropylene, block copolymerized polypropylene and random copolymerized polypropylene, and these are, for example, (anhydrous) maleic acid. , (Meth) acrylic acid,
A modified polypropylene resin modified with methylene succinic acid, citraconic acid or the like can be mentioned, and preferably used. These polypropylene resins may be used alone or in combination of two or more kinds.

The form of the above-mentioned adhesive is not particularly limited, and it is a solvent-type adhesive, an emulsion-type adhesive, a hot-melt-type adhesive, a film form (including a sheet form).
Any form such as an adhesive may be used. The adhesive may be a non-crosslinking type adhesive, a crosslinkable type adhesive, a one-pack type adhesive, or a two- or more-pack multi-pack type adhesive. May be

If necessary, the above-mentioned adhesives may include tackifiers, inorganic fillers, organic fillers, softeners (plasticizers) and coupling agents, as long as they do not impair the achievement of the present invention. Agents, surfactants, cross-linking agents, colorants, antioxidants, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents, flame retardants, antibacterial and antifungal agents, antifoaming agents, etc. One kind or two or more kinds of additives may be added.

The adhesive layer formed from the above adhesive agent is not particularly limited, but it is preferable that the 10% modulus at 23 ° C. is 1 to 25 MPa. When the 10% modulus of the adhesive layer at 23 ° C. is less than 1 MPa, the mechanical strength of the obtained adhesive layer or laminated sheet may be insufficient, and when it exceeds 25 MPa, the obtained adhesive layer or laminated sheet may be insufficient. May be less flexible.

The thickness of the adhesive layer may be appropriately set according to the performance desired to be given to the adhesive layer or the laminated sheet,
Although not particularly limited, it is generally 5 to 100.
It is preferably μm.

The method for producing the laminated sheet of the present invention by the above-mentioned direct method without interposing an adhesive layer is not particularly limited, but, for example, on a surface layer prepared in advance or in advance. A method of extrusion laminating a polyolefin resin (composition) for the base layer or a thermoplastic polyurethane elastomer (composition) for the surface layer onto the base layer (extrusion laminating method) prepared in advance. A method of thermally laminating the surface layer and a base material layer prepared in advance (thermal lamination method), a polyolefin resin (composition) for the base material layer, and a thermoplastic polyurethane elastomer (composition) for the surface layer. A method of coextruding two layers (coextrusion method) and the like can be mentioned, and any method may be adopted.
The coextrusion method is preferred because it is excellent in productivity.

The method for producing the laminated sheet of the present invention by the above-mentioned adhesive method via an adhesive layer is not particularly limited, but for example, on a surface layer prepared in advance and / or On the base material layer prepared in advance, the above-mentioned various forms of adhesives are applied at room temperature or under heating, and if necessary, the adhesive layer is formed through steps such as drying and cooling, and then the adhesive layer is formed. A method of laminating and adhering the surface layer and the base material layer via the intermediary (direct coating method), or on the prefabricated surface layer, or on the prefabricated base material layer, the adhesive of the above various forms After coating at room temperature or under heating and forming an adhesive layer through steps such as drying and cooling, if necessary, a polyolefin resin (composition) for a base material layer on the adhesive layer, or
A method of extrusion laminating a thermoplastic polyurethane elastomer (composition) for the surface layer (extrusion laminating method),
A method of coextruding three layers of a polyolefin resin (composition) for a substrate layer, an adhesive for an adhesive layer, and a thermoplastic polyurethane elastomer (composition) for a surface layer (coextrusion method)
Etc., and any method may be adopted, but it is preferable to adopt the coextrusion method because it is excellent in productivity.

The coextrusion method is a method of simultaneously laminating a plurality of layers by using a plurality of extruders and integrating them, and is not particularly limited. For example, thermoplastic polyurethane immediately before entering a die. -Based elastomer (composition), an adhesive and a polyolefin resin (composition) are combined in a feed block method, a multi-manifold method in which a manifold for a plurality of minutes is provided in the die, and they are not combined in the die and immediately after leaving the die. A multi-throttle die method for laminating and the like can be mentioned, and any method may be adopted. The temperature of each layer during coextrusion differs depending on the thermoplastic polyurethane elastomer (composition) used, the adhesive, the polyolefin resin (composition), etc. and is not particularly limited, but is generally Is preferably 170 to 230 ° C. for the surface layer, the adhesive layer and the base material layer.

The laminated sheet of the present invention thus obtained is
It is necessary that the 10% modulus at 23 ° C. be 1 to 6 MPa. 10% of laminated sheet at 23 ℃
If the modulus is less than 1 MPa, the mechanical strength of the laminate of the present invention described below will be insufficient, and conversely if it exceeds 6 MPa, the flexibility of the laminate will be impaired.

The thickness of the laminated sheet of the present invention may be appropriately set according to the desired performance of the laminated sheet or laminated body, and is not particularly limited, but generally 1
It is preferably 10 to 1200 μm.

Next, the laminate of the present invention comprises a base fabric laminated on the base layer side of the above-mentioned laminated sheet of the present invention.

The base cloth is not particularly limited, but for example, cotton, flax, Manila hemp, koir, silk,
Natural fiber base cloth such as wool and feather, rayon, acetate, metal fiber, carbon fiber, glass fiber, boron fiber, nylon, polyester, polyurethane, polyolefin, polyvinyl chloride, Teflon (registered trademark), acrylic, polyacetal, protein , Artificial fiber base fabrics such as carbon fiber, boron fiber, glass fiber, metal fiber, and foam base fabrics made of various synthetic resins are preferably used. These base fabrics may be composed of a single layer or may be composed of two or more layers. or,
These base fabrics may be used alone or in combination of two or more.

The above-mentioned natural fiber base cloth and artificial fiber base cloth are
It may be a single spinning or a mixed spinning. The shape of the above-mentioned natural fiber base fabric or artificial fiber base fabric is not particularly limited, and examples thereof include woven fabric, knitted fabric, braided fabric, twisted fabric, net fabric, felt, non-woven fabric, spunlace and spunbond. The shape may be any of these shapes, or a composite shape of these shapes.

The foam made of the synthetic resin is not particularly limited, but examples thereof include polyolefin resins such as polypropylene resin and polyethylene resin, polystyrene and styrene-maleic anhydride copolymer. Examples of the foamed material include polystyrene-based resins, polyurethane-based resins, polyvinyl chloride-based resins, and various thermoplastic elastomers, and are preferably used. These foams may be used alone or in combination of two or more. Further, the expansion ratio of these foams is not particularly limited, but in order to give the obtained laminate a soft feel, it is generally preferably 5 to 50 times, and more preferably Is 10 to 30 times.

The above-mentioned base cloth is not particularly limited, but preferably has a 10% modulus at 23 ° C. of 5 MPa or less. If the 10% modulus at 23 ° C. of the base fabric exceeds 5 MPa, the flexibility of the obtained laminate may be impaired.

The thickness of the above-mentioned base fabric may be appropriately set according to the performance to be imparted to the base fabric or the laminate, and is not particularly limited, but generally 100 to 10,000.
It is preferably μm. Further, the pore volume of the above-mentioned base fabric may be appropriately set according to the performance to be imparted to the base fabric or the laminate, and is not particularly limited, but it is generally 50 to 99%. preferable.

The method of laminating the base layer side of the laminated sheet of the present invention and the above-mentioned base cloth is not particularly limited, but for example, extrusion laminating method, thermal laminating method, adhesive bonding method and the like can be used. And any method may be adopted.

As the above-mentioned adhesive, various known adhesives may be used and are not particularly limited. For example, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl chloride resin, poly (meth) acrylic resin, etc. Resins, polystyrene-based resins, polyolefin-based resins, chlorinated polyolefin-based resins, adhesives containing thermoplastic resins such as saturated polyester-based resins and their modified products as main components, epoxy-based resins, phenol-based resins, polyurethane-based resins, Adhesives containing thermosetting resins such as unsaturated polyester resins and their modified products as main components, adhesives containing rubber (elastomer) such as natural rubber and various synthetic rubbers and their modified products as main components, starch and Adhesives mainly composed of natural substances such as glue and its modified products, adhesives mainly composed of inorganic substances such as sodium silicate (water glass), etc. Gerare suitably used. These adhesives may be used alone or in combination of two or more.

FIG. 1 shows an example in which the laminated sheet of the present invention is produced by the coextrusion method, and the base material layer side thereof is extrusion-laminated on a foam (base cloth) to produce the laminated body of the present invention. FIG. 2 shows a schematic view, and FIG. 2 shows a sectional view taken along the line AB in FIG.

The laminate of the present invention thus obtained is not particularly limited, but preferably has a 10% modulus at 23 ° C. of 0.9 to 5.9 MPa.
The 10% modulus at 23 ° C. of the laminate is 0.9.
If it is less than MPa, the mechanical strength becomes insufficient, and even if it is lightly touched, stretch or unevenness may be partially generated, and the appearance may be impaired. Conversely, if it exceeds 5.9 MPa, the contact feeling (soft Touch feeling may deteriorate.

The method for setting the 10% modulus at 23 ° C. of the above laminated body to 0.9 to 5.9 MPa is not particularly limited, but, for example, the base cloth may be preliminarily 1-2.
A method of laminating in a state of 0% extension can be mentioned. When the stretch of the base fabric is less than 1%, wrinkles and unevenness of 10% modulus may easily occur in the laminate, and when it exceeds 20%, the 10% modulus of the laminate may become too large. .

The modulus of the laminate is defined by 10% tensile (elongation) stress, which is defined by 50% tensile stress or 100%.
When specified by% tensile stress, depending on the type of base cloth, 50
This is because the stress may rapidly increase in the vicinity of% tensile (elongation) and the correlation with the contact feeling (soft touch feeling) may not be seen.

In the laminated body, the 10% modulus at 23 ° C. of the base material layer and the base cloth constituting the laminated body, or the adhesive layer, the base material layer and the base cloth constituting the laminated body becomes smaller in this order. It is preferable. By decreasing the 10% modulus at 23 ° C. of the base material layer and the base fabric constituting the laminate or the adhesive layer, the base material layer and the base fabric constituting the laminate in this order, the laminate has a better contact. It provides a feeling (soft touch feeling).

If desired, the surface layer of the above-mentioned laminate may be decorated with printing or embossing. The embossed pattern is not particularly limited, and may be a general embossed pattern such as a leather embossed pattern, a Perka embossed pattern, and a satin finish. For example, when the base material layer side of the laminated sheet of the present invention is extrusion-laminated on a base fabric, the surface pattern of the laminate can be provided with the above-mentioned grain pattern by using a grain roll machine or the like.

The thickness of the above-mentioned laminate may be appropriately set according to the performance desired to be imparted to the laminate and the intended use of the laminate,
Although not particularly limited, in general, the surface layer and the adhesive layer provided as necessary have a thickness of 5 to 100 μm, the base material layer has a thickness of 100 to 1000 μm, and the base fabric has a thickness of 1 μm.
It is preferably from 00 to 10000 μm.

[0065]

The laminated sheet of the present invention comprises a surface layer containing a thermoplastic polyurethane elastomer as a main component and a base material layer containing a polyolefin resin as a main component, and has a 10% modulus at 23 ° C. Since it has a specific range, it is suitable for obtaining a laminate that exhibits an excellent contact feeling (soft touch feeling) and is excellent in appearance and light resistance.

Further, since the laminated body of the present invention has a base cloth laminated on the base material layer side of the laminated sheet of the present invention, for example, even when it is used as a seat for a seat, an excellent contact feeling (soft touch feeling) is obtained. ), And is excellent in appearance and light resistance.

[0067]

BEST MODE FOR CARRYING OUT THE INVENTION The following examples are given to illustrate the present invention in more detail, but the present invention is not limited to these examples. In addition, "part" in an Example means a "weight part."

The following raw materials were used in this example. 1. Thermoplastic polyurethane-based elastomer (for surface layer) (1) Product name "L431-171" (manufactured by Toyo Morton) (2) Thermoplastic polyurethane-based elastomer composed of polycarbonate polyol, polycarbonate diol and hydrogenated diphenylmethane diisocyanate (hereinafter,
"Polycarbonate-based urethane elastomer" is noted) 2. Elastic fine particles (for surface layer) Product name "Bernock CFB101-40", average particle diameter: 8 μm (manufactured by Dainippon Ink and Chemicals, Inc.) Acid-modified polypropylene resin (for adhesive layer) Product name "Admer QF500" (manufactured by Mitsui Chemicals, Inc.) 4. Polyolefin resin (for base material layer) (1) Thermoplastic polyolefin elastomer (trade name "KS353P", manufactured by Sun Allomer) (2) Thermoplastic polyolefin elastomer (trade name "KS021P", manufactured by Sun Allomer) (3) 4. Thermoplastic polyolefin-based elastomer (trade name "Tuftec L515", manufactured by Asahi Kasei Corp.) Cotton knit (for base cloth)

(Example 1) As a surface layer, a thermoplastic polyurethane elastomer "L431-171" 100
Parts and elastic fine particles "Bernock CFB101-40" 5
A composition consisting of 0 parts was prepared. Also, for the adhesive layer,
Acid-modified polypropylene resin "Admer QF50"
0 ”was used alone. Furthermore, as a base material layer, a composition comprising 80 parts of a thermoplastic polyolefin-based elastomer "KS353P" and 20 parts of a thermoplastic polyolefin-based elastomer "Tuftec L515" was prepared. The hardness of the composition for the surface layer (type A durometer) was 60.

Using a multi-layer feed block type extruder,
Under the following extrusion conditions, the composition for the surface layer, the acid-modified polypropylene resin for the adhesive layer, and the composition for the base material layer were coextruded so as to be laminated in this order, and then the cotton for the base cloth. The substrate layer side is extrusion-laminated on the knitted surface, and an average depth of 100 μm is formed on the surface layer by using a chevoroll.
The surface of the adhesive layer is 2 each with the skin texture pattern of
A laminate having a thickness of 0 μm, a base material layer of 460 μm and a base fabric of 500 μm was produced. The thickness of the base cloth was converted to the thickness when the pore volume was set to 0% according to JIS L-1018 "Test method for knit fabric". [Extrusion Conditions] Extruder A (for surface layer): φ40 mm extruder, L / D = 2
6, compression ratio = 3 Extruder B (for adhesive layer): φ40 mm extruder, L / D = 2
6, compression ratio = 3 Extruder C (for base material layer): φ40 mm extruder, L / D = 2
6, compression ratio = 3 Die: 500 mm with 5 channel feed block, width epoch 3201 (manufactured by Krollen) Extrusion temperature: surface layer 190 ° C., adhesive layer 190 ° C., base material layer 1
90 ℃, mold 190 ℃ Pickup speed: 5m / min

Example 2 A laminate was prepared in the same manner as in Example 1 except that the thermoplastic polyolefin elastomer "KS353P" was used alone for the base material layer.

Example 3 Example 1 was repeated except that a composition comprising 80 parts of a thermoplastic polyolefin-based elastomer "KS021P" and 20 parts of a thermoplastic polyolefin-based elastomer "Tuftec L515" was used as a base material layer. A laminate was prepared in the same manner as in the case.

Example 4 In the same manner as in Example 1, except that a composition comprising 100 parts of a polycarbonate-based urethane elastomer and 50 parts of elastic fine particles "Bernock CFB101-40" was used for the surface layer. A laminated body was produced. The hardness of the composition for the surface layer (type A durometer) was 85.

Example 5 A composition comprising 100 parts of a polycarbonate-based urethane elastomer and 50 parts of elastic fine particles "Bernock CFB101-40" was used for the surface layer, and a thermoplastic polyolefin-based elastomer "KS353P" was used for the substrate layer. A laminate was prepared in the same manner as in Example 1 except that "" was used alone.
The hardness of the composition for the surface layer (type A durometer) was 85.

(Example 6) A composition comprising 100 parts of a polycarbonate-based urethane elastomer and 50 parts of elastic fine particles "Bernock CFB101-40" was used for the surface layer, and a thermoplastic polyolefin elastomer "KS021P" was used for the substrate layer. 80 parts and thermoplastic polyolefin-based elastomer "Tuftec L515" 20
A laminate was prepared in the same manner as in Example 1 except that the composition consisting of parts was used. The hardness of the composition for the surface layer (type A durometer) was 85.

(Comparative Example 1) A composition comprising 100 parts of a polycarbonate-based urethane elastomer and 50 parts of elastic fine particles "Bernock CFB101-40" was used for the surface layer, and a thermoplastic polyolefin-based elastomer "KS353P" was used for the substrate layer. 50 parts and thermoplastic polyolefin-based elastomer "Tuftec L515" 50
A laminate was prepared in the same manner as in Example 1 except that the composition consisting of parts was used. The hardness of the composition for the surface layer (type A durometer) was 85.

(Comparative Example 2) A composition comprising 100 parts of a polycarbonate-based urethane elastomer and 50 parts of elastic fine particles "Bernock CFB101-40" was used for the surface layer, and a thermoplastic polyolefin-based elastomer "KS021P" was used for the substrate layer. A laminate was prepared in the same manner as in Example 1 except that "" was used alone.
The hardness of the composition for the surface layer (type A durometer) was 85.

The 10% modulus at 23 ° C. of each layer constituting the laminates obtained in Examples 1 to 6 and Comparative Examples 1 and 2 was measured according to JIS K-7311. The results are shown in Table 1.

Further, the performances {contact feeling (soft touch feeling), appearance (presence / absence of unevenness), light resistance} of the laminates obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated. The following method evaluated. The results are shown in Table 1.

Touch sensation (soft touch sensation): Ask 10 persons to evaluate the contact sensation (soft touch sensation) of the laminate, and pass a score of 40 or more on a total of 50 points according to the following criteria (5-point method). And [Judgment Criteria (5-point method)] 5 points ... Excellent contact feeling (soft touch feeling). 4 points: Good contact feeling (soft touch feeling). 3 points: Normal contact feeling (soft touch feeling). 2 points: The contact feeling (soft touch feeling) was a little bad. 1 point: The contact feeling (soft touch feeling) was poor.

Appearance (presence or absence of irregularities): Ask 10 people to visually observe the appearance (presence or absence of irregularities) of the surface of the laminate, and according to the following judgment criteria (5-point method), 40 points or more in total of 50 points Was accepted. [Judgment criteria (5-point method)] 5 points ... No irregularities were observed on the surface. 4 points: Almost no irregularities were observed on the surface. 3 points: Some small irregularities were observed on the surface. 2 points: Many small irregularities were recognized on the surface. 1 point: Many large irregularities were recognized on the surface.

Light resistance: JIS K-7350-2 "Plastics-Exposure test method with laboratory light source (Part 2:
Xenon arc light source) ", the laminate was subjected to an exposure test with a xenon arc light source under the following irradiation conditions, and the color difference (ΔE) before and after the exposure test was measured. [Irradiation conditions] Illuminance: 68 W / m ² (wavelength 300 to 400 nm) Filter: Outdoor exposure light-dark cycle: light 3.8 hours, dark 1 hour Black panel temperature and humidity: light 89 ° C-50% RH, dark ...
38 ° C-95% RH Water spray: None

[0083]

[Table 1]

As is clear from Table 1, the laminates of Examples 1 to 6 according to the present invention are all excellent in touch feeling (soft touch feeling), appearance (presence or absence of unevenness) and light resistance. Was there.

On the other hand, the 10% modulus at 23 ° C. of the laminated sheet is less than 1 MPa, and
The laminate (Comparative Example 1) having a 10% modulus at 0 ° C. of less than 0.9 MPa had a poor appearance (presence / absence). Further, the 10% modulus at 23 ° C. of the laminated sheet exceeds 6 MPa, and the laminated body has a 10% modulus at 23 ° C.
The laminate of Comparative Example 2 having a% modulus of more than 5.9 MPa had a bad contact feeling (soft touch feeling).

[0086]

As described above, the laminated sheet of the present invention exhibits an excellent touch feeling (soft touch feeling), and
It is preferably used as a sheet material for obtaining a laminate having excellent appearance and light resistance. Further, since the laminate of the present invention is produced by using the above-mentioned laminate sheet of the present invention, it exhibits an excellent contact feeling (soft touch feeling) and is excellent in appearance and light resistance. It is preferably used as a constituent material for seats for seats.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a method for producing a laminate of the present invention.

FIG. 2 is a sectional view taken along the line AB in FIG.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F100 AJ04 AK03B AK03J AK45A                       AK45J AK51A AK62B AK66B                       AL02A AL09A AR00C AT00B                       BA02 BA03 BA04 BA07 BA10A                       BA10B BA10D BA26 DE01                       DG11D EH20 EH23 EJ40                       GB33 JB16A JK01A JK01B                       JK01C JK01D JK07 JK13                       JK13A JL11C JN30 YY00A                       YY00B YY00C YY00D                 4J034 BA03 BA07 DA01 DB03 DB04                       DB05 DB07 DF02 HA07 HA11                       HC22 HC46 HC52 HC64 QB15                       QD04 RA05 SA02 SB05

Claims (7)

[Claims] 1. A surface layer containing a thermoplastic polyurethane elastomer as a main component and a base material layer containing a polyolefin resin as a main component are laminated, and a 10% modulus at 23 ° C. is 1 to 6 MPa. Laminated sheet characterized by. 2. The laminated sheet according to claim 1, wherein the soft segment of the thermoplastic polyurethane elastomer is made of polycarbonate. 3. The laminated sheet according to claim 1, wherein the surface layer and the base material layer are laminated via an adhesive layer. 4. The surface layer and the base material layer, or the surface layer, the adhesive layer and the base material layer, which are laminated by a coextrusion method, according to any one of claims 1 to 3. Laminated sheet. 5. A laminate comprising a base sheet laminated on the base material layer side of the laminated sheet according to any one of claims 1 to 4. 6. The 10% modulus at 23 ° C. is 0.
It is 9-5.9 MPa, The laminated body of Claim 5 characterized by the above-mentioned. 7. The 10% modulus at 23 ° C. of the base material layer and the base fabric, or the adhesive layer, the base material layer and the base fabric, decreases in this order. The laminate described.