JP6816048B2 - Laminated body, laminate precursor and method for manufacturing the laminate - Google Patents

Description

The present invention relates to a method for producing a laminate, a laminate precursor, and a laminate, and more particularly, to a method for producing a laminate, a laminate precursor, and a laminate having improved mechanical properties and excellent interlayer adhesiveness. ..

Patent Document 1 discloses a method of laminating a plurality of woven fabrics made of oriented polymer strands and thermocompression bonding to produce a laminated polymer product.

Patent Document 1 states that the obtained laminated polymer product has good mechanical properties.

Japanese Patent No. 5138222

Even if the above-mentioned laminated polymer product has good mechanical properties, further improvement in mechanical properties is required. For example, as this means, a means of laminating a wear-resistant member on the surface of a laminated polymer product can be considered. However, it has not been easy to obtain such a laminate. In particular, when members having different compositions are laminated, it is difficult to obtain interlayer adhesiveness.

Therefore, an object of the present invention is to provide a laminate, a laminate precursor, and a method for producing a laminate having improved mechanical properties and excellent interlayer adhesiveness.

Further, other problems of the present invention will be clarified by the following description.

The above problems are solved by the following inventions.

(Claim 1)
Prepare a single cloth-like body or cloth laminate made of thermoplastic resin striatum.
Wherein on one side or both sides of a sheet of cloth-like member or the cross laminate of the modified polyolefin layer prepared product Sotai precursor obtained by laminating,
The laminate precursor is installed in the mold,
A method for producing a laminate, which comprises injecting a hydrogenated styrene-based thermoplastic elastomer forming a thermoplastic elastomer layer into the mold from the upper surface side of the modified polyolefin layer of the laminate precursor.
(Claim 2)
The method for producing a laminate according to claim 1, wherein the modified polyolefin layer is a film, and the modified polyolefin layer is obtained by thermocompression bonding to be integrated with the one cloth-like body or the cloth laminate.

According to the present invention, it is possible to provide a laminate, a laminate precursor, and a method for producing a laminate having improved mechanical properties and excellent interlayer adhesiveness.

The figure explaining an example of the layer structure of the laminated body of this invention Sectional drawing which shows an example of the cloth laminated body precursor for obtaining a cloth laminated body Diagram explaining the structure of the striatum The figure explaining an example of the formation of a laminated body

Hereinafter, embodiments for carrying out the present invention will be described in detail.
First, an example of the layer structure of the laminated body of the present invention will be described with reference to FIG.

The laminate 1 shown in FIG. 1 is formed by laminating a modified polyolefin layer 3 and a thermoplastic elastomer layer 4 in this order on one surface of the cloth laminate 2.

In the present invention, by providing the modified polyolefin layer 3 between the cloth laminate 2 and the thermoplastic elastomer layer 4, a laminate with improved mechanical properties can be obtained. In particular, by laminating the layers in the above-mentioned order, the desired adhesiveness is exhibited between the layers, and the function of not causing delamination is exhibited.

As the cloth laminate 2, one in which a plurality of cloth-like bodies made of thermoplastic resin striatum are laminated and thermocompression bonded can be preferably used.

The modified polyolefin layer 3 is made of modified polyolefin. The modified polyolefin layer 3 not only adheres firmly to the cloth laminate 2, but also adheres firmly to the thermoplastic elastomer layer 4. As a result, the mechanical strength of the laminated body 1 is remarkably improved.

Further, the thermoplastic elastomer layer 4 is made of a thermoplastic elastomer. The thermoplastic elastomer is not particularly limited, and examples thereof include styrene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and urethane-based thermoplastic elastomers. Be done. Among these, styrene-based thermoplastic elastomers are preferable, and hydrogenated styrene-based thermoplastic elastomers are particularly preferable. As a result, the laminated body 1 can exhibit excellent wear resistance and the like.

Examples of the hydrogenated styrene-based thermoplastic elastomer include hydrogenated derivatives of styrene-isoprene block copolymers. Such an elastomer is also available as a commercially available product, and examples thereof include "Septon" manufactured by Kuraray.

In the present embodiment, the laminate 1 is configured to include the cloth laminate 2, and the cloth laminate 2 is obtained by folding a single cloth-like body made of a thermoplastic resin striatum and thermocompression bonding. It may be used, or a single cloth body made of a thermoplastic resin striatum may be folded, and a plurality of these may be laminated and thermocompression bonded.

FIG. 2 is a cross-sectional view showing an example of a cross-laminated precursor 2a composed of a plurality of cloth-like bodies 21 to be subjected to thermocompression bonding.

In the aspect of FIG. 2, two cloth-like bodies 21 and 21 are laminated, and an intermediate layer 22 is interposed between the two cloth-like bodies 21 and 21 to form a cross laminated body precursor 2a. doing. In the aspect of FIG. 2, the cloth-like body 21 is a woven fabric.

The cloth-like body can be formed by using a striatum made of a thermoplastic resin made of a stretched thermoplastic resin monofilament, tape, yarn, split yarn, multifilament, staple fiber or the like.

The cloth-like body may be a woven woven cloth, or a cross-bonded cloth (sof) in which the intersections are joined as a surface shape by arranging striatums made of a large number of thermoplastic resins in parallel at right angles. It may be a knitted fabric or a braid formed of a striatum made of the above-mentioned thermoplastic resin.

The striatum is mainly composed of a high melting point resin component having a melting point higher than the thermocompression bonding temperature, but can also contain a low melting point resin component having a melting point lower than the thermocompression bonding temperature.

The structure of the striatum can be exemplified as shown in FIG. FIG. 3A is an example in which the striatum 210 is a single layer having only the base layer 220. In the case of this example, the resin constituting the striatum is composed of a high melting point resin component, but can contain a low melting point resin component as long as the effect of the present invention is not impaired.

FIGS. 3 (b) and 3 (c) show an example of a laminated structure in which the striatum 210 is laminated on one side or both sides of the base layer 220 with a surface layer 230 made of a thermoplastic resin having a melting point lower than that of the base layer 220. There is.

3 (d) and 3 (e) show an example in which a surface layer 230 made of a thermoplastic resin having a melting point lower than that of the base layer 220 has a core-sheath structure that covers the periphery of the base layer 220.

FIG. 3 (f) is an example of a side-by-side structure, and FIG. 3 (g) is an example of a sea-island structure.

As the thermoplastic resin constituting the striatum used for the cloth-like body, for example, polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate and the like can be preferably mentioned. Of these, polypropylene is particularly suitable.

When a laminated structure is used as the striatum 210, as a means for molding the laminated film as the molding material,

(1) A means for forming a film to be a base layer 220 and a film to be a surface layer 230 in advance and forming them into multiple layers by using a dry laminating method or a thermal laminating method.
(2) A method of coating the surface of a film serving as a base layer 220 with a thermoplastic resin serving as a surface layer 230.
It can be appropriately selected and used from (3) a method of extruding and laminating the surface layer 230 on a film to be a base layer 220 formed in advance, or (4) a method of extrusion molding as a laminated film by a multilayer coextrusion method.

As the stretching means, for example, uniaxial stretching can be adopted. In this case, after stretching the film to be the base layer 220 in the uniaxial direction, the thermoplastic resin to be the surface layer 230 is laminated, and this is slit in a tape shape to obtain the striatum 210. Alternatively, the striatum 210 can be obtained by slitting the laminated film in which the base layer 220 and the surface layer 230 are laminated and then stretching the laminated film in the uniaxial direction.

The stretching method is not particularly limited, and can be carried out by one-step or multi-step stretching using a hot roll, a hot plate, a hot air furnace, hot water, hot oil, steam, infrared irradiation, or the like. The striatum does not have to be all stretched striatum, and non-stretched striatum may be mixed as long as the strength is not so affected.

The thickness of the striatum can be arbitrarily selected according to the purpose, but in general, in the case of a laminated structure, a range of 50 to 10,000 decitex (dt) is desirable, and in FIG. 3 (d) and In the case of a core-sheath structure (coating structure) as shown in (e), a range of 1 to 10000 decitex (dt) is desirable.

The intermediate layer 22 is arranged between the cloth-like body 21 and the cloth-like body 21, adheres between the cloth-like body 21 and the cloth-like body 21, and improves the rigidity of the obtained cloth laminate. Has a function.

The intermediate layer 22 is made of a thermoplastic resin. As this thermoplastic resin, a resin containing a high melting point resin component in a low melting point resin component can be used. When the low melting point resin component contains the high melting point resin component, the intermediate layer can function as a rigidity improving layer.

As used herein, the term "melting point" is the temperature measured as the melting peak temperature by DSC measurement (Differential scanning calorimetry).

In other words, the high melting point resin component has a higher melting peak temperature than the low melting point resin component. The intermediate layer 22 may show two melting peak temperatures derived from these resins.

As the low melting point resin component used in the intermediate layer 22, polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate and the like can be preferably mentioned. Among them, polyolefin is preferable, and polypropylene is more preferable.

The high melting point resin component used in the intermediate layer 22 may have a higher melting point than the low melting point resin component, but polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably mentioned. Of these, polypropylene is particularly suitable.

When the low melting point resin component and the high melting point resin component used for the intermediate layer 22 are selected from polypropylene, for example, random polypropylene can be used as the low melting point resin component and homopolypropylene can be used as the high melting point resin component. ..

Random polypropylene includes propylene as a monomer component and propylene such as α-olefin (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like. (Α-olefin) is randomly copolymerized.

The α-olefin can be used, for example, in a proportion of preferably 20% by weight or less, more preferably 10% by weight or less, based on all the monomer components. The proportion of α-olefins can be adjusted to show the desired melting point.

In another embodiment when the low melting point resin component and the high melting point resin component used for the intermediate layer 22 are selected from polypropylene, a relatively low melting point random polypropylene is used as the low melting point resin component, and the high melting point resin component is used. Random polypropylene having a relatively high melting point can also be used.

As described above, the melting point of random polypropylene can be set, for example, by adjusting the ratio of α-olefin. Specifically, for example, a material having a smaller proportion of α-olefin than random polypropylene used as the low melting point resin component can be used as the high melting point resin component.

As the intermediate layer 22, a film formed by kneading pellets of a low melting point resin component and pellets of a high melting point resin component at a temperature equal to or higher than the melting points of both resin components and inflation molding or the like can be used.

A non-woven fabric can also be used as the intermediate layer 22.

The non-woven fabric may be formed by kneading pellets of a low melting point resin component and pellets of a high melting point resin component at a temperature equal to or higher than the melting points of both resin components and forming a fleece by a fleece forming method such as spunbonding or melt blowing. Alternatively, those formed by a thermal bond, a chemical bond, a needle punch, a spunlace fleece bonding method or the like may be used.

In the intermediate layer 22, the content of the refractory resin component is preferably in the range of, for example, 5% by weight to 50% by weight, and more preferably in the range of 10% by weight to 30% by weight.

The weight ratio of the low melting point resin component to the high melting point resin component in the intermediate layer 22 is preferably in the range of 5:95 to 50:50, and more preferably in the range of 10:90 to 30:70. ..

The thickness of the intermediate layer 22 can be appropriately set according to, for example, the thickness of the cloth-like body, the thickness of the striatum constituting the cloth-like body, and the like, and is not limited, but is 10 μm to 100 μm. It is preferably in the range, more preferably in the range of 20 μm to 60 μm.

The cloth laminate 2 can be produced by thermocompression bonding the above-mentioned cloth laminate precursor 2a at a predetermined temperature and then cooling it.

When an intermediate layer containing a high melting point resin component is used as the low melting point resin component, the cloth laminate 2 obtained by hot-pressing at a temperature equal to or higher than the melting point of the low melting point resin component and lower than the melting point of the high melting point resin component 2 It has an excellent effect on the rigidity of.

The method of thermocompression bonding is not particularly limited, but for example, a thermocompression press can be used. The pressure is not particularly limited and can be appropriately set according to the thickness of each layer and the like, but is preferably in the range of 0.5 MPa to 20 MPa, more preferably in the range of 2 MPa to 15 MPa.

The thermocompression bonding time is not particularly limited as long as it can be thermocompression bonded, but is preferably in the range of 1 minute to 20 minutes, for example.

Further, the cooling after thermocompression bonding may be natural cooling or forced cooling. In the case of forced cooling, a method of lowering the temperature to the cooling temperature by maintaining the crimped state at the time of thermocompression bonding can also be adopted. In this case, the cooling press method can be adopted.

The pressure of the cooling press is not particularly limited and can be appropriately set according to the thickness of each layer and the like, but for example, it is preferably in the range of 0.5 MPa to 20 MPa, and further preferably in the range of 2 MPa to 15 MPa. preferable.

The cooling time is not particularly limited as long as it can be cooled, but is preferably in the range of, for example, 10 seconds to 20 minutes.

In the above description, the case where two cloth-like bodies 21 are laminated to form the cloth laminated body 2 is mainly shown, but the number of the cloth-like bodies 21 to be laminated is not limited to the above.

For example, the number of cloth-like bodies 21 to be laminated can be appropriately set so that the cloth laminated body 2 has a desired thickness according to the intended use. The number of the cloth-like bodies 21 to be laminated can be, for example, in the range of 2 to 50.

When two cloth-like bodies are laminated, a laminated structure including the cloth-like body / intermediate layer / cloth-like body can be obtained.

When three cloth-like bodies are laminated, a laminated structure including the cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body can be formed.

When four cloth-like bodies are laminated, the laminated structure may be composed of a cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body.

When increasing the number of cloth-like bodies to 5 or more, an intermediate layer is arranged between the cloth-like bodies and the cloth-like bodies according to the example of the above-mentioned three or four sheets. Are arranged so that the number of sheets is a predetermined number.

Further, in the above description, when the cloth-like bodies 21 are laminated, the mode in which the intermediate layer 22 is interposed between the cloth-like bodies 21 and 21 is mainly shown, but depending on the rigidity required for the cloth laminated body 2, the intermediate layer 22 is mainly shown. The intermediate layer 22 may be omitted as appropriate.

Further, an adhesive layer (not shown) may be provided between the plurality of cloth-like bodies 21. The adhesive used for the adhesive layer is not particularly limited, and a commercially available product selected within a range that does not impair the effects of the present invention can be used.

The method of providing the adhesive layer is not particularly limited, and examples thereof include spraying, dipping coating, and brush coating.

When an adhesive layer is used, the intermediate layer 22 and the adhesive layer may be used in combination. When the intermediate layer 22 and the adhesive layer are used in combination, the adhesive layer can be formed on one surface or both sides of the intermediate layer 22.

The intermediate layer 22 and the adhesive layer described above may be omitted as appropriate depending on the strength and rigidity required for the cloth laminate 2.

In the present invention, when the striatum has a laminated structure as shown in FIG. 3 (c) or a core-sheath structure as shown in FIGS. 3 (d) and 3 (e), an intermediate layer or an adhesive layer is provided. Even if omitted, high adhesive strength can be obtained. In this case, at the time of thermocompression bonding of the cloth laminate precursor, the low melting point resin component constituting the surface layer of the striatum used for the cloth-like body is melted, and the plurality of cloth-like bodies are thermocompression-bonded to be integrated. ..

In the present invention, the method for forming the cloth laminate is not limited to the embodiment described above.

As shown in FIG. 1, a preferred embodiment of the laminated body 1 is one in which a modified polyolefin layer 3 and a thermoplastic elastomer layer 4 are laminated in this order on one surface of the cloth laminated body 2.

The modified polyolefin layer 3 is preferably made of a modified polyolefin obtained by modifying the polyolefin.

The polyolefin may be a homopolymer or a copolymer. Examples of the monomer include ethylene and propylene, and these can be used alone or in combination of two or more.

The copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.

In the present invention, these can be used alone or in combination of two or more. Above all, it is particularly preferable to use polypropylene or polyethylene as the polyolefin.

Examples of the method for modifying polyolefin include an acid modification method. As a method for acid denaturation, a method of graft-polymerizing an organic acid having a carboxyl group on polyolefin can be used.

By such graft polymerization, an acid-modified polyolefin in which an organic acid component is grafted on a polyolefin is obtained. The polymerization method is not limited to graft polymerization, and any method can be appropriately selected and used.

The type of organic acid is not particularly limited, but is preferably a saturated or unsaturated carboxylic acid or anhydrous carboxylic acid having at least one carboxyl group.

Examples of organic acids include (1) maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, aconitic acid, crotonic acid, succinic acid, oxalic acid, malonic acid, malic acid, thiomarinic acid, tartrate acid, adipic acid, and citrus. Carboxylic acids such as acids, pimeric acid, suberic acid, azelaic acid, acrylic acid, tetrahydrophthalic acid, isocrotonic acid, endocis-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid and sebacic acid ;
(2) Examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride and other carboxylic acids.

One type of organic acid may be used alone, or two or more types may be used in combination.

When the modified polyolefin is acid-modified, it can usually be modified to contain 0.01 to 10% by weight of an organic acid with respect to the polyolefin. When the content of the organic acid is less than 0.01% by weight, when the modified polyolefin layer is laminated between the cloth laminate layer and the thermoplastic elastomer layer, the interlayer adhesiveness is poor, which is not preferable. If it exceeds 10% by weight, when the polyolefin is modified with a molecularly crosslinked monomer as a main component, the melt viscosity increases due to significant crosslinking of the polyolefin, and the polyolefin containing a molecularly cleaved monomer as a main component increases. However, when modified, the melt viscosity decreases because the main chain breaks become significant. As a result, when the modified polyolefin layer is laminated between the cloth laminate layer and the thermoplastic elastomer layer, the interlayer adhesiveness is inferior.

In addition to the modified polyolefin described above, the modified polyolefin layer may contain other resins such as non-modified polyolefin as long as the effects of the present invention are not impaired.

The form of the modified polyolefin layer 3 is not particularly limited, and for example, it can be in the form of a film or sheet, or in a molten state for use in extrusion lamination or the like. From the viewpoint of versatility, a film or sheet is preferable.

The thermoplastic elastomer layer 4 is made of a thermoplastic elastomer. The thermoplastic elastomer is not particularly limited, and the above-mentioned ones can be used, a styrene-based thermoplastic elastomer is preferable, and a hydrogenated styrene-based thermoplastic elastomer is particularly preferable.

Various additives can be added to the striatum, intermediate layer, modified polyolefin layer, and thermoplastic elastomer layer used in the cloth laminate, depending on the purpose.

Examples of the additive include an antioxidant such as an organic phosphorus type and a thioether type; a light stabilizer such as a hindered amine type; an ultraviolet absorber such as a benzophenone type, a benzotriazole type and a benzoate type; an antioxidant; a bisamide type and a wax. Dispersants such as based and organic metal salt type; amide type, organic metal salt type and other lubricants; bromine-containing organic type, phosphoric acid type, melamine cyanurate type, flame retardant such as antimony trioxide; low density polyethylene, wire Stretching aids such as low-density polyethylene; organic pigments; inorganic pigments; inorganic fillers; organic fillers; inorganic antibacterial agents such as metal ion-based agents, organic antibacterial agents and the like.

In the above description, the case where the laminated body is formed by using the cloth laminated body formed by laminating a plurality of cloth-like bodies has been described, but the above-mentioned described is made of a striatum made of a thermoplastic resin instead of the cloth laminated body. The cloth-like body may be used alone. Thereby, the weight of the obtained laminate can be suitably reduced, and the versatility of the laminate can be enhanced.

Further, in the above description, the case where the modified polyolefin layer and the thermoplastic elastomer layer are laminated only on one surface (one side) of the cloth laminate or one cloth-like body has been mainly described. It is also preferable to laminate the modified polyolefin layer and the thermoplastic elastomer layer on both one surface and the other surface (both sides) of the body or one cloth-like body.
Further, the object to be laminated on the other surface of the cloth laminate or one cloth-like body is not limited to the modified polyolefin layer and the thermoplastic elastomer layer, and various layers are laminated according to the purpose, application, and the like. Can be done. For example, a PET film, a non-woven fabric, or the like can be attached to the other surface to increase the added value of the cloth laminate product caused by vision.

Next, a method for producing the laminate of the present invention will be described.

First, a single cloth-like body made of a thermoplastic resin striatum or a cloth laminated body made by laminating a plurality of cloth-like bodies is prepared.

Next, the modified polyolefin layer is laminated on one side or both sides of one cloth-like body or cloth laminated body.

Next, a thermoplastic elastomer layer is laminated on the upper surface of the modified polyolefin layer. As a result, the laminate of the present invention can be obtained.

In the method for producing a laminate described above, it is preferable to perform injection molding using a mold as a means for forming the thermoplastic elastomer layer.

The method for producing the laminate of the present invention will be described in more detail below with specific examples.

As a method for producing the laminated body, the methods described in the following (1) to (3) can be preferably exemplified by a method for forming a thermoplastic elastomer layer in the laminated body. Above all, the following method (1) is preferable from the viewpoint of mass production.

(1) A method in which the lower one is installed in a mold, and the molten resin is injected into the mold from above to form a thermoplastic elastomer layer. Here, the lower one refers to a product in which one cloth-like body or cloth laminate and a modified polyolefin layer are laminated, or a laminate precursor described later.

As one aspect
In the mold
Install one cloth-like body or cloth laminate,
A modified polyolefin layer is placed on one side of one cloth-like body or cloth laminate,
The resin forming the thermoplastic elastomer layer can be injected into the mold from the upper surface side of the modified polyolefin layer.

At this time, the surface of each layer of at least the lower layer can be melted by the heat of the molten resin to realize interlayer adhesion.

Also, as another aspect,
In the mold
Install the laminate precursor and
The resin forming the thermoplastic elastomer layer can be injected into the mold from the upper surface side of the modified polyolefin layer in the laminate precursor.

At this time, at least the surface of the laminate precursor can be melted by the heat of the molten resin to realize interlayer adhesion.

(2) When the thermoplastic elastomer layer is a film, a method of laminating the thermoplastic elastomer layer on the upper surface of the lower one and thermocompression bonding. Here, the lower one refers to a product in which one cloth-like body or cloth laminate and a modified polyolefin layer are laminated, or a laminate precursor described later.

As one aspect
Prepare one cloth-like body or cloth laminate,
A modified polyolefin layer is laminated on one side of one cloth-like body or cloth laminated body.
A thermoplastic elastomer layer can be laminated on the upper surface side of the modified polyolefin layer and thermocompression bonded.

Also, as another aspect,
Prepare multiple cloth-like bodies,
A modified polyolefin layer is laminated on one side of a plurality of cloth-like bodies,
A thermoplastic elastomer layer can be laminated on the upper surface side of the modified polyolefin layer and thermocompression bonded.

Also, as another aspect,
Prepare a laminate precursor and
A thermoplastic elastomer layer can be laminated on the upper surface side of the modified polyolefin layer in the laminate precursor and thermocompression bonded.

In the thermocompression bonding, all the layers may be thermocompression bonded at one time, or several layers may be divided and thermocompression bonded in stages.

(3) A method of forming a thermoplastic elastomer layer by extruding a molten resin into a layer on the lower one. Here, the lower one refers to a laminate precursor described later.

As one aspect
Prepare a laminate precursor and
The resin forming the molten thermoplastic elastomer layer can be extruded into a layer on the upper surface side of the modified polyolefin layer in the laminate precursor with a T-die or the like.

At this time, at least the surface of the laminate precursor can be melted by the heat of the molten resin to realize interlayer adhesion.

In the production methods (1) to (3) above, it is preferable that the modified polyolefin layer is a film.

Here, one aspect of the method (1) above will be described in detail with reference to FIG.

First, as shown in FIG. 4A, one cloth-like body or cloth laminate 2 is arranged on a part of the inner surface of the mold 5, and the one cloth-like body or cloth laminate 2 is used. The modified polyolefin layer 3 is overlaid on top of it.
When the modified polyolefin layer 3 is a film, it is preferable because an effect of excellent handleability when setting the modified polyolefin layer 3 in the mold 5 can be obtained.

Next, as shown in FIG. 4B, the mold 5 is closed, and the resin forming the thermoplastic elastomer layer 4 is injected into the mold 5 on the upper surface side of the modified polyolefin layer 3. At this time, the resin forming the thermoplastic elastomer layer 4 is melted.

Next, the mold 5 is released to obtain a laminate 1 in which the thermoplastic elastomer layer 4 is laminated on one cloth-like body or cloth laminate 2 via the modified polyolefin layer 3.

In the example of FIG. 4, the thermoplastic elastomer layer 4 is provided with an uneven shape based on the inner surface shape of the mold 5, but the present invention is not limited to this. By using the manufacturing method (1) described above, various shapes can be suitably imparted to the laminate with a high degree of freedom. In addition, productivity can be improved by using this method.

In the example of FIG. 4, a manufacturing method for forming a laminated body including one cloth-like body or cloth laminated body 2, a modified polyolefin layer 3, and a thermoplastic elastomer layer 4 at a time has been described, but the present invention is not limited thereto.

In the above description, the case where the laminate 1 is formed by laminating the modified polyolefin layer 3 and the thermoplastic elastomer layer 4 in this order on one surface of one cloth-like body or the cloth laminate 2 is mainly shown. However, it is not limited to this. For example, in the laminate 1, the modified polyolefin layer 3 and the thermoplastic elastomer layer 4 are laminated in this order on one surface of one cloth-like body or cloth laminate 2, and the one cloth-like body or cloth laminate 1 is laminated. The modified polyolefin layer 3 and the thermoplastic elastomer layer 4 may be laminated in this order on the other surface of 2.
Thereby, a laminated body having further improved mechanical properties can be obtained. In particular, by laminating each layer in the above-mentioned order, the function of firmly adhering the layers is exhibited.

The method for producing a laminate in which a modified polyolefin layer and a thermoplastic elastomer layer are laminated on both sides of one cloth-like body or cloth laminate is not particularly limited. A part of the layer constituents constituting the laminate may be laminated on one surface of one cloth-like body or cloth laminate, and then the remaining components may be laminated on the other surface, or both sides at once. It may be laminated on. Lamination of the layer constituents on each surface can be performed in the same manner as the above-mentioned lamination on one surface.

When the thermoplastic elastomer layers are laminated on both sides of one cloth-like body or cloth laminate, the thermoplastic elastomer layers on both sides may have the same composition or different compositions.

Next, the laminate precursor of the present invention will be described in detail.
The laminate precursor is formed by laminating one cloth-like body or cloth laminate and a modified polyolefin layer, and can be suitably used when producing the laminate of the present invention.

A release paper may be provided on the modified polyolefin layer side of the laminate precursor. This makes it possible to prevent the modified polyolefin layer 3 from adhering to other articles when transporting the laminate precursor.

Next, the method for producing the laminate precursor of the present invention will be described.
The method for producing the laminate precursor of the present invention is not particularly limited, and the methods described in the following (1) to (3) can be preferably exemplified.

(1) A plurality of cloth-like bodies made of thermoplastic resin striatum are laminated and then thermocompression bonded to obtain a cloth laminate, and a modified polyolefin layer is laminated and thermocompression bonded to the obtained cloth laminate. Method

(2) A method in which a plurality of cloth-like bodies made of thermoplastic resin striatum are laminated, and a modified polyolefin layer is laminated on the upper surface thereof and thermocompression bonded.

(3) A method in which a modified polyolefin layer is laminated on the upper surface of a single cloth-like body made of a thermoplastic resin striatum and thermocompression bonded.

In the methods (1) to (3) above, it is preferable that the modified polyolefin layer is a film.

In the thermocompression bonding, all the layers may be thermocompression bonded at one time, or several layers may be divided and thermocompression bonded in stages.

Further, the laminate precursor may be one in which a modified polyolefin layer is laminated on one side of one cloth-like body or a cloth laminate, or one in which modified polyolefin layers are laminated on both sides. A laminate precursor obtained by laminating a modified polyolefin layer on both sides can be suitably used for producing a laminate having a thermoplastic elastomer layer on both sides.

The laminate precursor described above is useful for obtaining the laminate of the present invention.
In particular, in the manufacturing process of the laminated body, a place for producing a laminated body precursor in which one cloth-like body or a cloth laminated body and a modified polyolefin layer are laminated, and then a laminated body in which a thermoplastic elastomer layer is laminated. It is preferable when the place where the product is obtained is different. This is because the laminate precursor can give a degree of freedom to the manufacturing process of the laminate.

In the above description, the case where the modified polyolefin layer and the thermoplastic elastomer are individually layered has been described, but the present invention is not limited to this, and the desired physical properties (wear resistance, etc.) of the laminate of the present invention are impaired. To the extent that it does not exist, the components forming the modified polyolefin layer and the thermoplastic elastomer may be mixed to form a laminate.

Further, in the above description, regarding the embodiment using the cloth laminate, the embodiment in which the cloth laminate, the modified polyolefin layer, and the thermoplastic elastomer layer are formed for each layer and laminated thereof is mainly described, but the present invention is limited thereto. Not done. For example, as described above, the cloth-like body in the process of forming the cloth laminate and the film constituting the modified polyolefin layer can be laminated and thermocompression bonded at once.

The application of the resin molded product of the present invention is not particularly limited, but for example, an application in which abrasion resistance is required on the surface and high adhesive strength is required between layers of the laminate is preferable. The laminate of the present invention has an excellent abrasion resistance because the surface is composed of a thermoplastic elastomer, preferably a hydrogenated styrene-based thermoplastic elastomer, and is thermoplastic with a single cloth-like or cloth laminate. This is because a high degree of adhesive strength can be obtained between the layers by providing the modified polyolefin layer between the elastomer layer and the layer.
For example, the following uses can be exemplified.

Chair or bench parts such as backrests, seats, frames or armrests;
Ski or snowboard equipment such as ski boots, ski boot parts or snowboard shoes, snowboard shoe parts, skis or snowboard boards;
Sports protectors such as helmets, elbow pads, knee pads, shin pads or breastplates;
Motorcycle protectors such as helmets, elbow pads, knee pads, shin pads or breastplates;
Safety protectors such as helmets, elbow pads, knee pads, shin pads or breastplates;
Disaster prevention protectors such as helmets, elbow pads, knee pads, shin pads or breastplates;
Surfboard or bodyboard;
Shoe components, soles;
Playground equipment materials for skateboards, roller skates, etc.

Among the uses exemplified above, for example, components constituting shoes, sports equipment, protectors and the like are preferable, and for example, they can be particularly preferably used as components of shoe soles and shoes. When the laminate is used for various purposes, it is preferable to arrange the thermoplastic elastomer layer on the surface of the article, and especially when it is used for the sole, the thermoplastic elastomer layer is placed on the side in contact with the ground. It is preferably placed on the surface.

Examples of the present invention will be described below, but the present invention is not limited to such examples.

(Example 1)
1. Preparation of laminate 1. Fabrication of cloth laminate
(1) Preparation of cloth-like body Polypropylene (MFR = 0.4 g / 10 minutes, weight average molecular weight Mw = 630,000, melting point 164 ° C.) as a high melting point resin component and propylene-ethylene random common weight as a low melting point resin component Using a coalescence (MFR = 7.0 g / 10 minutes, weight average molecular weight Mw = 220,000, melting point 125 ° C.), a low melting point resin component as shown in FIG. A three-layer film (layer thickness ratio 1/8/1) having a melting point resin component as a base layer was obtained.

The resulting film was slit with leather (razor). Then, after stretching 7 times on a hot plate having a temperature of 110 to 120 ° C., a relaxation heat treatment of 10% was performed in a hot air circulation type oven having a temperature of 145 ° C., and the yarn width was 4.5 mm and the fineness was 1700 desidex (dt). Got a flat yarn.

The obtained flat yarn was woven into a twill weave of 15 warp threads / 25.4 mm and 15 weft threads / 25.4 mm using a sulzer loom to obtain a cloth-like body.

(2) Preparation of Intermediate Layer As the intermediate layer, a polypropylene film obtained by containing polypropylene having a melting point of 125 ° C. (low melting point resin component) and polypropylene having a melting point of 161 ° C. (high melting point resin component) was used. The content of the refractory resin component in the intermediate layer was 15% by weight. The rest is a low melting point resin component.

(3) Thermocompression bonding / cooling The obtained 4 cloth-like bodies and the obtained 3 intermediate layers are combined with the cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body. They were laminated alternately so as to be.

This is set to a press temperature of 150 ° C. with a hydraulic press machine, heat-pressed at a pressure of 4 MPa for 2 minutes, and then cooled and pressed with a hydraulic press machine at a press temperature of 20 ° C. and a pressure of 4 MPa for 2 minutes. A 20 cm cross laminate was obtained.

2. 2. Preparation of Modified Polyolefin Layer As the modified polyolefin layer, an acid-modified modified polypropylene film (melting point 134 ° C.) obtained by grafting maleic acid was used.

3. 3. Preparation of laminate (1) Set the press temperature to 145 ° C. with a hydraulic press machine, heat press at a pressure of 1 MPa for 2 minutes, and then cool press at a press temperature of 20 ° C. and pressure 5 MPa for 2 minutes with a hydraulic press machine. A laminate precursor was obtained in which the cross laminate layer and the modified polyolefin layer were laminated in this order.
(2) Next, the laminate precursor was installed in the mold. A thermoplastic elastomer resin was injected into the upper surface side of the modified polyolefin layer of the laminate precursor, and molding was performed under the following conditions to obtain a laminate 1.

(Molding conditions)
Thermoplastic Elastomer Resin: Hydrogenated styrene-based thermoplastic elastomer resin (Kuraray's "Septon SS190CT")
Cylinder temperature: 230 ° C
Cycle time: 1 minute Mold temperature: 40 ° C
Cooling time: 20 seconds

(Comparative Example 1)
In Example 1, the above 3. A laminate 2 to be a cloth laminate / hydrogenated styrene-based thermoplastic elastomer resin layer was obtained in the same manner as in Example 1 except that the modified polyolefin layer was omitted in the preparation of the laminate.

2. Adhesive strength confirmation test and evaluation method A test was conducted to confirm the adhesive strength between the laminated bodies 1 and 2. The test was performed by a peel strength test conforming to the standard JIS K 6854-3.
At this time, the sample width was 10 mm and the test speed was 100 mm / min. The laminates 1 and 2 were tested, and the results of the obtained adhesive strength were evaluated according to the following evaluation criteria. The results are shown in Table 1.

<Evaluation criteria>
◯: Can be used for products that have an adhesive strength of 25 N / cm or more and require a high degree of interlayer adhesion ×: Used for products that have an adhesive strength of less than 25 N / cm and require a high degree of interlayer adhesiveness. Can't

<Evaluation>
From the results in Table 1, it can be seen that the laminate 1 of the present invention has an adhesive strength of 34.7 N / cm and is excellent in interlayer adhesiveness, so that it can be used for products that require a high degree of interlayer adhesiveness. Although the laminate 2 has low to moderate adhesive strength, it cannot be used as a laminate for products that require high adhesive strength.

1: Laminated body 2: Cloth laminated body (or one cloth-like body)
2a: Cross laminate precursor 21: Cloth-like body 210: Striatum 220: Base layer 230: Surface layer 22: Intermediate layer 3: Modified polyolefin layer 4: Thermoplastic elastomer layer 5: Mold

Claims (2)

Prepare a single cloth-like body or cloth laminate made of thermoplastic resin striatum.
Wherein on one side or both sides of a sheet of cloth-like member or the cross laminate of the modified polyolefin layer prepared product Sotai precursor obtained by laminating,
The laminate precursor is installed in the mold,
A method for producing a laminate, which comprises injecting a hydrogenated styrene-based thermoplastic elastomer forming a thermoplastic elastomer layer into the mold from the upper surface side of the modified polyolefin layer of the laminate precursor. The method for producing a laminate according to claim 1, wherein the modified polyolefin layer is a film, and the modified polyolefin layer is obtained by thermocompression bonding to be integrated with the one cloth-like body or the cloth laminate.

Images