JP2019142050A - Laminate, laminate precursor, and method for manufacturing laminate - Google Patents

Abstract

To provide a laminate which improves mechanical characteristics and is excellent in interlayer adhesion, and a method for manufacturing the laminate.SOLUTION: There are provided a laminate 1 in which a modified polyolefin resin layer 3 and a thermoplastic elastomer layer 4 are laminated in this order on at least one surface of one cloth-like body 2 formed of thermoplastic resin-made linear materials or a cloth laminate: and a method for manufacturing the laminate which prepares a cloth laminate 2 obtained by laminating one cloth-like body 2 formed of thermoplastic resin-made linear materials or the cloth laminate 2 obtained by laminating the plurality of cloth-like bodies, laminates a modified polyolefin layer 3 on one surface or both surfaces of the one cloth-like body 2 or the cloth laminate 2, and laminates a thermoplastic elastomer layer 4 on the upper surface of the modified polyolefin layer 3.SELECTED DRAWING: Figure 1

Description

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

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

  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, there is a demand for further improvement in mechanical properties. For example, as this means, means for laminating a wear-resistant member on the surface of the 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 adhesion.

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

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

(Claim 1)
On at least one surface of one cloth-like body made of a linear body made of thermoplastic resin, or a cross-laminated body formed by laminating a plurality of cloth-like bodies,
A laminate comprising a modified polyolefin layer and a thermoplastic elastomer layer laminated in order.
(Claim 2)
The laminate according to claim 1, wherein the thermoplastic elastomer layer is made of a hydrogenated styrene thermoplastic elastomer.
(Claim 3)
The laminate according to claim 1, wherein the modified polyolefin layer is at least one selected from acid-modified modified polypropylene or acid-modified modified polyethylene.
(Claim 4)
The laminate according to claim 1, 2, or 3, wherein the modified polyolefin layer is a film.
(Claim 5)
On one surface of a cloth-like body made of a linear body made of thermoplastic resin, or a cross-layered body obtained by laminating a plurality of cloth-like bodies,
A laminate precursor comprising a laminate of a modified polyolefin layer.
(Claim 6)
On the other surface of the one cloth-like body or the cloth laminate,
The laminate precursor according to claim 5, which is formed by laminating a modified polyolefin layer.
(Claim 7)
Prepare one cloth-like body made of a linear body made of thermoplastic resin, or a cloth laminate,
Laminating a modified polyolefin layer on one or both surfaces of the one cloth-like body or the cloth laminate,
A method for producing a laminate, comprising laminating a thermoplastic elastomer layer on an upper surface of the modified polyolefin layer.
(Claim 8)
The method for producing a laminate according to claim 7, wherein the thermoplastic elastomer layer is made of a hydrogenated styrene thermoplastic elastomer.
(Claim 9)
The modified polyolefin layer is a film;
In the mold, install the one cloth-like body or the cloth laminate,
The modified polyolefin layer is placed on one or both sides of the one cloth-like body or the cloth laminate,
The method for producing a laminate according to claim 7 or 8, wherein a resin for forming the thermoplastic elastomer layer is injected into the mold from the upper surface side of the modified polyolefin layer.
(Claim 10)
Prepare one cloth-like body made of a linear body made of thermoplastic resin, or a cloth laminate,
A method for producing a laminate precursor, wherein a modified polyolefin layer is laminated on one side or both sides of the one cloth-like body or the cloth laminate.
(Claim 11)
The method for producing a laminate precursor according to claim 10, wherein the modified polyolefin layer is a film, and is obtained by being integrated with the one cloth-like body or the cloth laminate by thermocompression bonding.
(Claim 12)
The laminate precursor obtained by the production method according to claim 10 or 11 is prepared,
Place the laminate precursor on the mold,
A method for producing a laminate, comprising injecting a resin that forms a thermoplastic elastomer layer into the mold from an upper surface side of the modified polyolefin layer of the laminate precursor.
(Claim 13)
The method for producing a laminate according to claim 12, wherein the resin forming the thermoplastic elastomer layer comprises a hydrogenated styrene-based thermoplastic elastomer.

  ADVANTAGE OF THE INVENTION According to this invention, mechanical characteristics can improve and the manufacturing method of the laminated body excellent in interlayer adhesiveness, a laminated body precursor, and a laminated body can be provided.

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

Below, the form for implementing this invention is demonstrated in detail.
First, with reference to FIG. 1, an example of the layer structure of the laminated body of this invention is demonstrated.

  A laminate 1 shown in FIG. 1 is formed by sequentially laminating a modified polyolefin layer 3 and a thermoplastic elastomer layer 4 on one surface of a 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 having improved mechanical properties can be obtained. In particular, by laminating the respective layers in the order described above, desired adhesiveness is exhibited between the respective layers, and a function that does not cause delamination is exhibited.

  The cloth laminate 2 can be suitably used by laminating a plurality of cloth-like bodies made of thermoplastic resin filaments and thermocompression bonding.

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

  Further, the thermoplastic elastomer layer 4 is made of a thermoplastic elastomer. The thermoplastic elastomer is not particularly limited, and examples thereof include a styrene thermoplastic elastomer, a vinyl chloride thermoplastic elastomer, an olefin thermoplastic elastomer, a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, and a urethane thermoplastic elastomer. It is done. Among these, a styrene thermoplastic elastomer is preferable, and a hydrogenated styrene thermoplastic elastomer is particularly preferable. Thereby, the laminated body 1 can exhibit the outstanding abrasion resistance.

  Examples of the hydrogenated styrene thermoplastic elastomer include hydrogenated derivatives of styrene-isoprene block copolymers. Such an elastomer is also available as a commercial product, and examples thereof include “Septon” manufactured by Kuraray Co., Ltd.

  In the present embodiment, the laminate 1 includes a cloth laminate 2, and the cloth laminate 2 is a thermocompression bonding by folding a single cloth-like body made of a thermoplastic resin filament. You may use what was made, or what folded the one sheet | seat body which consists of a linear body made from a thermoplastic resin, laminated | stacked this, and thermocompression-bonded may be used.

  FIG. 2 is a cross-sectional view showing an example of a cross laminate precursor 2a composed of a plurality of cloth-like bodies 21 used for thermocompression bonding.

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

  The cloth-like body can be formed using a linear body 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 cloth, or a cross-bonded cloth (SOF) in which the intersections are joined in the form of a plane by arranging a plurality of linear bodies made of thermoplastic resin so as to be orthogonal to each other. It may be a knitted fabric or a braid formed of a linear body made of the above thermoplastic resin.

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

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

  FIGS. 3B and 3C show an example of a laminated structure in which the linear member 210 is laminated on one 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. Yes.

  3D and 3E are examples in which the 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 covering the periphery of the base layer 220. FIG.

  FIG. 3F shows an example of a side-by-side structure, and FIG. 3G shows an example of a sea-island structure.

  Preferable examples of the thermoplastic resin constituting the linear body used for the cloth-like body include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate. Among these, polypropylene is particularly preferable.

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

(1) Means for forming a film to be the base layer 220 and a film to be the surface layer 230 in advance and forming a multilayer using a dry laminating method or a thermal laminating method,
(2) A method of coating the surface of the film to be the base layer 220 with the thermoplastic resin to be the surface layer 230,
(3) A method of extruding and laminating the surface layer 230 on a film to be the base layer 220 formed in advance, or (4) a method of extruding as a laminated film by a multilayer coextrusion method, or the like can be appropriately selected and used.

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

  The stretching method is not particularly limited, and can be performed by single-stage or multi-stage stretching using a hot roll, a hot plate, a hot stove, hot water, hot oil, steam, infrared irradiation, or the like. Note that the striated body does not have to be a stretched striated body, and unstretched striated bodies can be mixed within a range that does not significantly affect the strength.

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

  The intermediate layer 22 is disposed between the cloth-like body 21 and the cloth-like body 21, and adheres between the cloth-like body 21 and the cloth-like body 21 and improves the rigidity of the obtained cross-layered body. It has a function.

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

  In the present specification, the “melting point” is a temperature measured as a 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 can exhibit two melting peak temperatures derived from these resins.

  Preferable examples of the low melting point resin component used for the intermediate layer 22 include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate. Among these, polyolefin is preferable, and polypropylene is more preferable.

  The high melting point resin component used for the intermediate layer 22 may be any component having a higher melting point than that of the low melting point resin component, and preferred examples include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate. Among these, polypropylene is particularly preferable.

  When the low melting point resin component and the high melting point resin component used for the intermediate layer 22 are each 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 is other than propylene as monomer components and propylene such as α-olefin (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc. Of the α-olefin) are 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 the total monomer components. The proportion of α-olefin can be adjusted to show the desired melting point.

  As another aspect when the low melting point resin component and the high melting point resin component used for the intermediate layer 22 are each 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 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 proportion of α-olefin. Specifically, for example, a material having a smaller α-olefin ratio than the 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 a pellet of a low melting point resin component and a pellet of a high melting point resin component at a temperature equal to or higher than the melting point of both resin components and using inflation molding or the like can be used.

  A nonwoven fabric can also be used as the intermediate layer 22.

  The nonwoven 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 using a fleece forming method such as spunbond or melt blown. Alternatively, 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 high melting point resin component is preferably in the range of 5% by weight to 50% by weight, for example, and more preferably in the range of 10% by weight to 30% by weight.

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

  Although the thickness of the intermediate | middle layer 22 can be suitably set according to the thickness of a cloth-like body, the thickness of the filament which comprises this cloth-like body, etc., for example, it is not limited, but 10 micrometers-100 micrometers The range is preferable, and the range of 20 μm to 60 μm is more preferable.

  The cloth laminate 2 can be manufactured by thermocompression bonding the cloth laminate precursor 2a described above at a predetermined temperature and then cooling.

  When an intermediate layer containing a high-melting resin component is used as the low-melting resin component, a cross-layered product 2 is obtained by thermocompression bonding at a temperature not lower than the melting point of the low-melting resin component and lower than the melting point of the high-melting resin component The effect is excellent in rigidity.

  Although the method of thermocompression bonding is not particularly limited, for example, a hot press machine or the like can be used. The pressure is not particularly limited, and can be set as appropriate according to the thickness of each layer. For example, the pressure is preferably in the range of 0.5 MPa to 20 MPa, and 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.

  The cooling after thermocompression bonding may be natural cooling or forced cooling. In the case of forced cooling, it is possible to employ a technique of maintaining the pressure-bonding state during thermocompression bonding and lowering the temperature to the cooling temperature. In this case, a cooling press method can be employed.

  The pressure of the cooling press is not particularly limited and can be appropriately set according to the thickness of each layer, but is preferably in the range of 0.5 MPa to 20 MPa, and more 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 10 seconds to 20 minutes, for example.

  In the above description, the case where two cloth-like bodies 21 are laminated to form the cross laminate 2 has been mainly described, but the number of cloth-like bodies 21 to be laminated is not limited to the above.

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

  When two cloth-like bodies are laminated, a laminated structure composed of a cloth-like body / intermediate layer / cloth-like body can be formed.

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

  When four cloth-like bodies are laminated, a laminated structure consisting of cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body can be used.

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

  Further, in the above description, when the cloth-like body 21 is laminated, the aspect 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 laminate 2, The intermediate layer 22 may be omitted as appropriate.

  Furthermore, an adhesive layer (not shown) can be provided between the plurality of cloth-like bodies 21. The adhesive used for the adhesive layer is not particularly limited, and commercially available products selected within a range not impairing 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, dip coating, and brush coating.

  When using an adhesive layer, 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 surfaces of the intermediate layer 22.

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

  In the present invention, when the striatum has a laminated structure as shown in FIG. 3 (c) and a core-sheath structure as shown in FIGS. 3 (d) and 3 (e), an intermediate layer or an adhesive layer is used. 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 linear body used for the cloth body is melted, and the plurality of cloth bodies are thermocompression bonded and integrated. .

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

  A preferred embodiment of the laminate 1 is a laminate in which a modified polyolefin layer 3 and a thermoplastic elastomer layer 4 are sequentially laminated on one surface of a cross laminate 2 as shown in FIG.

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

  The polyolefin may be a homopolymer or a copolymer. Examples of the monomer include ethylene, propylene and the like, 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 this invention, these can be used individually or in mixture of 2 or more types. Among these, it is particularly preferable to use polypropylene or polyethylene as the polyolefin.

  Examples of the modification method of polyolefin include a method of acid modification. As a method for acid modification, a method of graft polymerization of an organic acid having a carboxyl group to polyolefin can be used.

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

  The type of the organic acid is not particularly limited, but is preferably a saturated or unsaturated carboxylic acid or carboxylic anhydride 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, tartaric acid, adipic acid, citric acid Carboxylic acids such as acid, pimelic 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) Carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and succinic anhydride.

  An organic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the modified polyolefin is acid-modified, it can usually be modified to contain an organic acid in an amount of 0.01 to 10% by weight based on 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 adhesion is inferior. When the content exceeds 10% by weight, the polyolefin having a molecularly-crosslinking monomer as a main component is modified with respect to the polyolefin having a molecularly-crosslinking monomer as a main component. When it is modified, the main chain breakage becomes significant and the melt viscosity decreases. As a result, when the modified polyolefin layer is laminated between the cloth laminate layer and the thermoplastic elastomer layer, the interlayer adhesion is poor.

  The modified polyolefin layer may contain, in addition to the above-described modified polyolefin, other resins such as unmodified 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. For example, the modified polyolefin layer 3 can be in a melted state for use in a film or sheet, 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 those described above can be used. Styrenic thermoplastic elastomers are preferable, and hydrogenated styrene thermoplastic elastomers are 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.

  Additives include, for example, organic phosphorus-based, thioether-based antioxidants; hindered amine-based light stabilizers; benzophenone-based, benzotriazole-based, benzoate-based ultraviolet absorbers; antistatic agents; bisamide-based, waxes Dispersants such as amides and organometallic salts; lubricants such as amides and organometallic salts; flame retardants such as bromine-containing organics, phosphates, melamine cyanurates, and antimony trioxide; low density polyethylene, wire Stretching aids such as low-density polyethylene; organic pigments; inorganic pigments; inorganic fillers; organic fillers; metal ion-based inorganic antibacterial agents, organic antibacterial agents, and the like.

  In the above description, the case where the laminated body is configured by using a cloth laminated body formed by laminating a plurality of cloth-like bodies has been described. However, the above-described cloth body made of a thermoplastic resin is used instead of the cloth laminated body. A single cloth-like body may be used alone. Thereby, the obtained laminated body can be reduced in weight suitably and the versatility of this laminated body can be improved.

In the above description, the case where the modified polyolefin layer and the thermoplastic elastomer layer are laminated only on one side (one side) of the cloth laminate or one cloth-like article has been mainly shown. It is also preferable to laminate the modified polyolefin layer and the thermoplastic elastomer layer on both the one side and the other side (both sides) of the body or one cloth-like body.
Moreover, the object laminated on the other surface of the cloth laminate or one cloth-like material is not limited to the modified polyolefin layer and the thermoplastic elastomer layer, and various layers may be laminated according to the purpose and application. Can do. For example, a PET film, a nonwoven fabric, or the like can be bonded to the other surface to increase the added value of the cloth-laminated product resulting from vision.

  Next, the manufacturing method of the laminated body of this invention is demonstrated.

  First, the cloth laminated body formed by laminating | stacking one cloth-like body which consists of a linear body made from a thermoplastic resin, or several cloth-like bodies is prepared.

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

  Next, a thermoplastic elastomer layer is laminated on the upper surface of the modified polyolefin layer. Thereby, the laminated body of this invention is obtained.

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

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

  The method for producing the laminate can be preferably exemplified mainly by the methods described in the following (1) to (3) by the method of forming the thermoplastic elastomer layer in the laminate. Among these, from the viewpoint of mass production, the following method (1) is preferable.

(1) A method of forming a thermoplastic elastomer layer by placing a lower one in a mold and injecting a molten resin into the mold from above. Here, the lower one means one obtained by laminating one cloth-like body or cloth laminate and a modified polyolefin layer, or a laminate precursor described later.

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

  At this time, interlayer heat bonding can be achieved by dissolving at least the surface of each of the lower layers by the heat of the molten resin.

As another aspect,
In the mold
Install the laminate precursor,
A resin for 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 dissolved by the heat of the molten resin to realize interlayer adhesion.

(2) A method in which when the thermoplastic elastomer layer is a film, the thermoplastic elastomer layer is laminated on the upper surface of the lower one and thermocompression bonded. Here, the lower one means one obtained by laminating one cloth-like body or cloth laminate and a modified polyolefin layer, or a laminate precursor described later.

As one aspect,
Prepare one cloth or cloth laminate,
Laminate a modified polyolefin layer on one side of a piece of cloth or cloth laminate,
A thermoplastic elastomer layer can be laminated on the upper surface side of the modified polyolefin layer and thermocompression bonded.

As another aspect,
Prepare multiple cloths,
Laminating a modified polyolefin layer 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.

As another aspect,
Prepare a laminate precursor,
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 thermocompression bonding, all layers may be thermocompression bonded at once, or several layers may be divided and thermocompression bonded step by step.

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

As one aspect,
Prepare a laminate precursor,
The resin that forms the molten thermoplastic elastomer layer can be extruded in a layered manner using a T-die or the like on 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 dissolved 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 mode of the method (1) will be described in detail with reference to FIG.

First, as shown in FIG. 4 (a), 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 formed. The modified polyolefin layer 3 is overlaid on top.
In the case where the modified polyolefin layer 3 is a film, it is preferable because an effect of excellent handleability when setting it in the mold 5 can be obtained.

  Next, as shown in FIG. 4B, the mold 5 is closed, and a resin for forming the thermoplastic elastomer layer 4 is injected into the upper surface side of the modified polyolefin layer 3 in the mold 5. 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 a thermoplastic elastomer layer 4 is laminated on a single cloth-like body or cloth laminate 2 via a 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 is not limited to this. By using the production method of (1) above, various shapes can be suitably imparted to the laminate with a high degree of freedom. Moreover, productivity can also be improved by using this method.

  In the example of FIG. 4, the manufacturing method for forming a laminated body including one cloth-like body or cloth laminated body 2, modified polyolefin layer 3, and 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 mainly configured 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 cloth laminate 2 is mainly shown. However, it is not limited to this. For example, in the laminate 1, a modified polyolefin layer 3 and a thermoplastic elastomer layer 4 are sequentially laminated on one surface of a single cloth-like body or cloth laminate 2, and the one cloth-like body or cloth laminate is formed. 2, the modified polyolefin layer 3 and the thermoplastic elastomer layer 4 may be laminated in this order on the other surface.
As a result, a laminate having further improved mechanical properties can be obtained. In particular, by laminating the respective layers in the above order, the function of firmly bonding the layers is exhibited.

  The manufacturing method of the laminated body in which the modified polyolefin layer and the thermoplastic elastomer layer are laminated on both surfaces of a single cloth-like body or cloth laminate is not particularly limited. After laminating a part of the layer constituent components constituting the laminate on one side of one cloth-like body or cloth laminate, the remaining components may be laminated on the other side, or both sides at once. May be laminated. Lamination | stacking of the layer structural component to each surface can be performed by the method similar to the lamination | stacking to the single side mentioned above.

  When thermoplastic elastomer layers are laminated on both sides of a single 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.

Release paper can also be provided on the modified polyolefin layer side of the laminate precursor. Thereby, when transporting the laminate precursor, it is possible to prevent the modified polyolefin layer 3 from adhering to other articles.

Next, the manufacturing method of the laminated body precursor of this invention is demonstrated.
The manufacturing method of the laminated body precursor of this invention is not exceptionally limited, The method as mainly described in following (1)-(3) can be illustrated preferably.

(1) After laminating a plurality of cloth-like bodies made of thermoplastic resin filaments, thermocompression bonding is performed to obtain a cloth laminate, and the resulting cloth laminate is laminated with a modified polyolefin layer and thermocompression bonded. Method

(2) A method of laminating a plurality of cloth-like bodies made of thermoplastic resin filaments, laminating a modified polyolefin layer on the upper surface, and thermocompression bonding.

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

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

  In thermocompression bonding, all layers may be thermocompression bonded at once, or several layers may be divided and thermocompression bonded step by step.

  The laminate precursor may be a laminate of a modified polyolefin layer on one side of a single cloth or cloth laminate, or a laminate of a modified polyolefin layer on both sides. A laminate precursor obtained by laminating a modified polyolefin layer on both sides can be suitably used for production of 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 production process of the laminate, a place where a laminate precursor obtained by laminating one cloth-like body or cloth laminate and a modified polyolefin layer is manufactured, and then a thermoplastic elastomer layer is laminated to obtain a laminate. It is preferable when the place to obtain is different. This is because the laminate precursor can provide a degree of freedom in the manufacturing process of the laminate.

  In the above description, the case where the modified polyolefin layer and the thermoplastic elastomer are formed independently of each other has been described. However, the present invention is not limited to this, and the target physical properties (such as wear resistance) of the laminate of the present invention are impaired. As long as there is not, the laminated body may be formed by mixing the components that form the modified polyolefin layer and the thermoplastic elastomer.

  Further, in the above description, with respect to the embodiment using the cloth laminate, the cloth laminate, the modified polyolefin layer, and the thermoplastic elastomer layer are mainly formed for each layer, and the embodiment of laminating them is mainly described. Not. For example, as described above, a cloth-like body in the process of forming a cross laminate and a film constituting the modified polyolefin layer can be laminated and thermocompression bonded at a time.

Although the use of the resin molding of the present invention is not particularly limited, for example, a use in which the surface is required to have wear resistance and a high adhesive strength between the layers of the laminate is preferable. The laminate of the present invention is excellent in abrasion resistance because the surface is composed of a thermoplastic elastomer, preferably a hydrogenated styrene-based thermoplastic elastomer, and has a cloth-like or cloth laminate and a thermoplastic. This is because by providing the modified polyolefin layer between the elastomer layers, high adhesive strength can be obtained between the layers.
For example, the following uses can be illustrated.

Chair or bench parts such as backrest, seat, frame or armrest;
Ski or snowboard parts such as ski shoes, ski shoe parts or snowboard shoes, snowboard shoe parts, skis or snowboards;
Sports protectors such as helmets, elbow pads, knee pads, shin pads or chest pads;
Motorcycle protectors such as helmets, elbow pads, knee pads, shin pads or chest pads;
Safety protectors such as helmets, elbow pads, knee pads, shin pads or chest pads;
Disaster protectors such as helmets, elbow pads, knee pads, shin pads or chest pads;
Surfboard or bodyboard;
Shoe components, soles;
Playground equipment 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 such as shoe soles and shoes. When the laminate is used for various applications, it is preferable to dispose the thermoplastic elastomer layer on the surface of the article. Particularly when the laminate is used for a shoe sole, the thermoplastic elastomer layer is disposed on the side in contact with the ground. It is preferable to arrange on the surface.

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

(Example 1)
First. Production of laminate 1. Fabrication of cross laminate
(1) Production of cloth-like body Polypropylene (MFR = 0.4 g / 10 min, weight average molecular weight Mw = 630,000, melting point 164 ° C.) as a high melting point resin component and propylene-ethylene random copolymer as a low melting point resin component Using a coalescence (MFR = 7.0 g / 10 min, 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 high melting point resin component as a base layer was obtained.

  The resulting film was slit with leather. Next, the film was stretched 7 times on a hot plate having a temperature of 110 to 120 ° C., and then subjected to a relaxation heat treatment of 10% in a hot air circulation oven having a temperature of 145 ° C. A flat yarn was obtained.

  The obtained flat yarn was woven into a twill weave of 15 warps / 25.4 mm and 15 wefts / 25.4 mm using a slewer loom to obtain a cloth-like body.

(2) Production of Intermediate Layer As the intermediate layer, a polypropylene film in which 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 was used. The content of the high melting point resin component in the intermediate layer was 15% by weight. The balance is a low melting point resin component.

(3) Thermocompression bonding / cooling The obtained cloth-like body 4 sheets and the obtained intermediate layer 3 sheets are cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body / intermediate layer / cloth-like body. The layers were alternately stacked so that

  This was set at a press temperature of 150 ° C. with a hydraulic press, heated and pressed at a pressure of 4 MPa for 2 minutes, and then cooled and pressed at a press temperature of 20 ° C. and a pressure of 4 MPa for 2 minutes with a hydraulic press, with a width of 20 cm and a long length. A cloth laminate having a thickness of 20 cm was obtained.

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

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

(Molding conditions)
Thermoplastic elastomer resin: Hydrogenated styrene thermoplastic elastomer resin (Kuraray "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 cross laminate / hydrogenated styrenic thermoplastic elastomer resin layer was obtained in the same manner as in Example 1 except that the modified polyolefin layer was omitted in the production of the laminate.

2nd. Adhesive strength confirmation test and evaluation method For the laminates 1 and 2, a test for confirming the adhesive strength between layers was performed. The test was performed by a peel strength test based on 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 obtained adhesive strength results were evaluated according to the following evaluation criteria. The results are shown in Table 1.

<Evaluation criteria>
○: Adhesive strength is 25 N / cm or more, and can be used for products that require a high degree of interlayer adhesion ×: Adhesive strength is less than 25 N / cm, and use for products that require a high degree of interlayer adhesion Can't

<Evaluation>
From the results in Table 1, it can be seen that the laminate 1 of the present invention is excellent in interlayer adhesion with an adhesive strength of 34.7 N / cm, and can therefore be used for products that require a high level of interlayer adhesion. 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: Cross laminated body (or one cloth-like body)
2a: cloth laminated body precursor 21: cloth-like body 210: linear body 220: base layer 230: surface layer 22: intermediate layer 3: modified polyolefin layer 4: thermoplastic elastomer layer 5: mold

Claims (13)

On at least one surface of one cloth-like body made of a linear body made of thermoplastic resin, or a cross-laminated body formed by laminating a plurality of cloth-like bodies,
A laminate comprising a modified polyolefin layer and a thermoplastic elastomer layer laminated in order.   The laminate according to claim 1, wherein the thermoplastic elastomer layer is made of a hydrogenated styrene thermoplastic elastomer.   The laminate according to claim 1, wherein the modified polyolefin layer is at least one selected from acid-modified modified polypropylene or acid-modified modified polyethylene.   The laminate according to any one of claims 1 to 3, wherein the modified polyolefin layer is a film. On one surface of a cloth-like body made of a linear body made of thermoplastic resin, or a cross-layered body obtained by laminating a plurality of cloth-like bodies,
A laminate precursor comprising a laminate of a modified polyolefin layer. On the other surface of the one cloth-like body or the cloth laminate,
The laminate precursor according to claim 5, which is formed by laminating a modified polyolefin layer. Prepare one cloth-like body made of a linear body made of thermoplastic resin, or a cloth laminate,
Laminating a modified polyolefin layer on one or both surfaces of the one cloth-like body or the cloth laminate,
A method for producing a laminate, comprising laminating a thermoplastic elastomer layer on an upper surface of the modified polyolefin layer.   The method for producing a laminate according to claim 7, wherein the thermoplastic elastomer layer is made of a hydrogenated styrene thermoplastic elastomer. The modified polyolefin layer is a film;
In the mold, install the one cloth-like body or the cloth laminate,
The modified polyolefin layer is placed on one or both sides of the one cloth-like body or the cloth laminate,
The method for producing a laminate according to claim 7 or 8, wherein a resin for forming the thermoplastic elastomer layer is injected into the mold from the upper surface side of the modified polyolefin layer. Prepare one cloth-like body made of a linear body made of thermoplastic resin, or a cloth laminate,
A method for producing a laminate precursor, wherein a modified polyolefin layer is laminated on one side or both sides of the one cloth-like body or the cloth laminate.   The method for producing a laminate precursor according to claim 10, wherein the modified polyolefin layer is a film, and is obtained by being integrated with the one cloth-like body or the cloth laminate by thermocompression bonding. The laminate precursor obtained by the production method according to claim 10 or 11 is prepared,
Place the laminate precursor on the mold,
A method for producing a laminate, comprising injecting a resin that forms a thermoplastic elastomer layer into the mold from an upper surface side of the modified polyolefin layer of the laminate precursor.   The method for producing a laminate according to claim 12, wherein the resin forming the thermoplastic elastomer layer is a hydrogenated styrene-based thermoplastic elastomer.

Images