JP6977229B2 - Thermoplastic resin composition and cloth laminated molded article using it - Google Patents

Description

The present invention relates to a thermoplastic resin composition having excellent flexibility, light weight, adhesiveness to a cloth, and waterproofness, and a cloth laminated molded product using the same.

Tent, sheet, canvas, etc. are manufactured by spraying or coating hydrophobic rubber, thermoplastic resin solution, emulsion, etc. on the cloth, and natural rubber and vinyl chloride resin are known as resin materials (for example). , Patent Document 1). However, when natural rubber is used, a vulcanization treatment is required, which complicates the manufacturing process. In addition, if vinyl chloride resin is used, dioxins may be generated during the combustion treatment after use. In addition, the corrosive gas generated by halogens during the combustion treatment is one of the causes of aging the incineration facility itself.

In order to solve the above-mentioned problems, a cloth laminated molded body using an olefin resin has been proposed. Specifically, an adhesive resin intermediate layer having high frequency induced heat generation is formed on a fiber base cloth, and an olefin resin is formed therein. An olefin-based resin molded product in which a resin layer is laminated is disclosed (see, for example, Patent Document 2). Patent Document 2 provides an adhesive resin intermediate layer having high-frequency induced heat-generating properties such as an isocyanate compound, an aziridine compound, and a coupling agent, which enables fusion by high-frequency welder treatment and is an olefin resin having sufficient heat-resistant creep characteristics. It is intended to obtain a molded product.

Further, an intermediate layer containing a flame retardant and a cross-linking agent such as an aziridine compound, a carbodiimide compound, an oxazolidin compound, an isocyanate compound, and a coupling agent is formed on the fiber base cloth, and an olefin-based compound containing a flame retardant aid is formed therein. A flame-retardant olefin-based resin laminate in which a resin composition is laminated is disclosed (see, for example, Patent Document 3). According to Patent Document 3, a flame-retardant olefin system that is less damaged by peeling or desorption of the resin layer even under harsh usage conditions such as outdoors, has no deterioration in flame retardancy over time, and is easy to dispose of and incinerate. It provides a resin laminate. However, since the olefin resin generally has a high hardness, a laminated cloth using the olefin resin cannot obtain a laminated cloth having excellent flexibility.

Further, in order to improve waterproofness and flexibility, the olefin resin has two or more polymer blocks (A) made of an aromatic vinyl compound in the molecule, and a polymer block (B) made of a conjugated diene compound. A thermoplastic elastomer composition containing a hydrogenated block copolymer obtained by hydrogenating a block copolymer having one or more of) is disclosed (see, for example, Patent Document 4). However, the composition described in Patent Document 4 has a low adhesive strength to the fabric, so that its use is limited.

General methods for adhering the thermoplastic elastomer composition to the fabric include (1) an extrusion coating method and (2) a method of heating and welding the molded product after molding. The method (1) is a manufacturing method in which the cloth is coated with the resin composition at the same time as extrusion molding. On the other hand, as the method (2), there is a manufacturing method in which a resin composition is formed into a sheet or tube shape, then laminated on a cloth by, for example, hot air or a hot plate, and heat-welded at a low temperature. In the method (1) by extrusion coating, since the resin is coated at the time of molding, the outer surface of the fabric molded product can be coated with the resin, but the inner surface cannot be coated with the resin, and the usage is limited. .. In recent years, the method (2) tends to be used rather than the method (1) in order to coat the resin regardless of the inner surface or the outer surface of the molded product. The method (2) is a method of heating with hot air, and a urethane-based elastomer is generally used because a material that can be adhered at a low temperature is required. However, when a urethane-based elastomer is used, the specific gravity is large and the product is produced. Since the weight of the product itself is heavy, it is inferior in handleability. On the other hand, although the composition disclosed in Patent Document 4 has a low specific gravity, there is a problem that the adhesive strength is inferior when it is adhered to a fabric by a welding method using hot air.

Japanese Unexamined Patent Publication No. 52-018995 Japanese Unexamined Patent Publication No. 10-100330 Japanese Unexamined Patent Publication No. 2000-0087276 Japanese Unexamined Patent Publication No. 2003-136643

Therefore, an object of the present invention is that it is lightweight, has excellent waterproofness and flexibility, does not generate corrosive gas or toxic gas during the final disposal combustion treatment, and has adhesive strength to the fabric at low temperature welding. It is an object of the present invention to provide an excellent thermoplastic resin composition and a cloth laminated molded article using the thermoplastic resin composition.

As a result of diligent studies to achieve the above object, the present inventors have laminated a resin containing a specific amount of an olefin resin having a specific range of melting point and a specific structure of a thermoplastic elastomer, and further laminating the resin and the cloth. We have found that the molded product is excellent in waterproofness, lightweight, and has an excellent balance between flexibility and adhesive strength, and has completed the present invention.

That is, in the present invention, at least two or more polymer blocks (A) made of styrene are contained in the molecule with respect to 100 parts by mass of the olefin resin (a) having a melting point of 110 to 120 ° C. measured by differential scanning calorimetry. It contains 110 to 230 parts by mass of a hydrogenated block copolymer (b) obtained by hydrogenating a block copolymer having one or more polymer blocks (B) made of isoprene in the molecule. It is a thermoplastic resin composition.

Further, the present invention is preferably a cloth laminated molded body in which the above-mentioned thermoplastic resin composition and cloth are laminated, and more preferably a waterproof article or a fire hose using the cloth laminated molded body.

When the resin composition of the present invention is molded into a cloth laminated molded body laminated with a cloth, it retains sufficient waterproofness, flexibility and lightness, and is excellent in adhesiveness to the cloth. Further, since the resin composition of the present invention does not contain a halogen substance, it does not generate corrosive gas or toxic gas during the final disposal combustion treatment.

The thermoplastic resin composition of the present invention is a polymer block (A ) made of at least styrene in the molecule with respect to 100 parts by mass of an olefin resin (a) having a melting point of 110 to 120 ° C. measured by a differential scanning calorific value measurement method. ), And the hydrogenated block copolymer (b) obtained by hydrogenating a block copolymer having one or more polymer blocks (B) made of isoprene in the molecule is 110 to 10. It is a thermoplastic resin composition containing 230 parts by mass.

<Olefin resin (a)>
The olefin-based resin (a) of the present invention has a differential scanning calorimetry device (manufactured by SHIMADZU; DSC-60) with a heat quantity on the vertical axis and a temperature on the horizontal axis, and has a measurement temperature range of 40 to 200 ° C. and a temperature rise rate. It is important that the olefin resin has a melting point of 110 to 120 ° C. , which is represented by the temperature at the peak position of the absorption curve obtained when measured at 10 ° C./min. The olefin-based resin (a) is a polymer mainly composed of α-olefins having 2 to 8 carbon atoms such as ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and homopolymerization thereof. In addition to the product, any one obtained by copolymerizing two or more kinds of α-olefins can be preferably used. In particular, in the present invention, polyethylene such as low-density polyethylene and linear low-density polyethylene; a resin obtained by copolymerizing two or more kinds of α-olefins; an ethylene / α-olefin copolymer and the like can be mentioned. Further, in addition to olefins such as ethylene, those obtained by copolymerizing a small amount of vinyl-based monomers can also be used. Examples of such examples include ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid derivative copolymers, and conjugated dienes such as butadiene and isoprene. It also contains a hydrogenated additive of a polymer of the system monomer. It is also possible to mix and use two or more of these resins.

The olefin resin (a), which is particularly preferable in consideration of processability and mechanical properties of the obtained composition, is a polymer containing ethylene as a main single component, and specifically, low-density polyethylene, linear low-density polyethylene, and the like. Ethylene-based random copolymers such as ethylene-vinyl acetate random copolymers, ethylene (meth) acrylic acid random copolymers, ethylene-glycidyl methacrylate random copolymers, ethylene-octene random copolymers, and even these. The mixture is preferably used. As the olefin resin (a), a commercially available product can also be used. For example, there is a trade name "Novatec HE30" (low density polyethylene) manufactured by Japan Polyethylene Corporation. When a material having a melting point higher than 120 ° C. is used as the olefin, the material does not melt during the bonding step, so that the bonding strength is significantly reduced. Further, among these, particularly when linear low-density polyethylene is used, the tensile strength is remarkably improved, and as a result, excellent adhesive strength can be obtained.

<Hydrogenated block copolymer (b)>
The hydrogenated block copolymer (b) used in the present invention has at least two or more polymer blocks (A) made of styrene in the molecule, and the polymer block (B) containing isoprene in the molecule. It is obtained by hydrogenating a block copolymer containing one or more .

The weight average molecular weight of the polymer block (A) is preferably in the range of 2,500 to 40,000, more preferably 3,000 to 35,000, and particularly preferably 4,000 to 30,000. If it is less than 2500, the mechanical strength of the obtained thermoplastic resin composition may decrease, while if it exceeds 40,000, the melt viscosity becomes too high and the mixability with other components of the present invention is poor. The moldability of the thermoplastic resin composition may be inferior.

It is preferable that 50% or more of the carbon-carbon double bond derived from the conjugated diene compound of the polymer block (B) is hydrogenated, more preferably 75% or more is hydrogenated, and 95%. It is particularly preferable that the above is hydrogenated.

The weight average molecular weight of the polymer block (B) is preferably in the range of 1000 to 20000, more preferably 20000 to 180000, and particularly preferably 30,000 to 160000. If it is less than 10,000, the elastic properties of the obtained thermoplastic resin composition may be impaired, while if it exceeds 200,000, the fluidity may be lowered.

The microstructure of the polymer block (B) is not particularly limited. Accordingly, the vinyl bond content in the unhydrogenated of polymer block (B), i.e., not limiting in 1,2-bond content and 3,4-bond content is one of the range when using the Lee isoprene.

Further, in the polymer block (B), the mass ratio of the following polymer X and the following polymer Y is more preferably X / Y = 10/90 to 90/10, and 20/80 to 80/20. It is preferably in the range of. If the mass ratio of X and Y is out of the above range, the adhesive strength is inferior. It is considered that this is because the strength due to the anchor effect cannot be exhibited from the viewpoint of fluidity when the resin and the base cloth are adhered to each other.
Polymer X: A composition of a block polymer having an aromatic vinyl polymer block and a conjugated diene polymer block, wherein the content of the aromatic vinyl polymer block is 25% or less;
Polymer Y: A composition of a block polymer having an aromatic vinyl polymer block and a conjugated diene polymer block, wherein the content of the aromatic vinyl polymer block is 25% or more;

The hydrogenated block copolymer (b) of the present invention contains two or more polymer blocks (A) and one or more polymer blocks (B) from the viewpoint of heat resistance, mechanical properties, and the like. is required. The bonding mode of the polymer block (A) and the polymer block (B) may be linear, branched or any combination thereof, but the polymer block (A) is A and the polymer block (A). when representing the B) in B, and triblock structure represented by _{a-B-a, (a} -B) n, (a-B) n -A, n represents an integer of 2 or more (here) Among these, the multi-block copolymer represented by ABA has a triblock structure, which is particularly preferable in terms of heat resistance, mechanical properties, handleability and the like.

The proportion of the polymer block (A) composed of the aromatic vinyl compound in the hydrogenated block copolymer (b) is 5 to 70% by mass, more preferably 10 to 40% by mass of the hydrogenated block copolymer (b). %, Especially preferably in the range of 10 to 30% by mass. If it exceeds 70% by mass, the hydrogenated block copolymer (b) becomes hard, the flexibility of the thermoplastic resin composition is impaired and becomes brittle, while if it is less than 5% by mass, the polymer block (A) The content is low, and the mechanical strength of the molded product obtained from the thermoplastic resin composition is not sufficient.

The weight average molecular weight of the hydrogenated block copolymer (b) is in the range of 40,000 to 350,000, more preferably 40,000 to 250,000, and particularly preferably 40,000 to 200,000. When the weight average molecular weight of the hydrogenated block copolymer (b) is less than 40,000, the mechanical strength of the obtained cloth laminated molded article is not sufficient, while the weight average molecular weight of the hydrogenated block copolymer is 350,000. If it exceeds, the fluidity of the obtained thermoplastic resin composition deteriorates, and the moldability of the obtained cloth laminated molded product deteriorates. The number average molecular weight referred to in the present specification is a polystyrene-equivalent molecular weight obtained under the following measurement conditions by a gel permeation chromatography (GPC) method.

Measurement condition:
GPC; LC Solution (manufactured by SHIMADZU)
Detector: Differential refractometer RID-10A (manufactured by SHIMADZU)
Column: Two TSKgelG4000Hxl in series (manufactured by TOSOH)
Guard column: TSKguardcolumnHxl-L (manufactured by TOSOH)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 1 ml / min
Concentration: 2 mg / ml

Further, the shape of the hydrogenated block copolymer (b) may be linear, branched, or star-shaped, and the bonding order of each block and the number of bonded blocks are not particularly limited. Further, in order to control the microstructure of the polymer block (B), a cocatalyst may be used during the polymerization. Examples of this co-catalyst include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, triethylamine, N, N, N', N'-tetramethylethylenediamine and N-. Examples thereof include amine compounds such as methylmorpholine. These may be used alone or in combination of two or more.

The hydrogenated block copolymer (b) used in the present invention further contains a carboxyl group, a hydroxyl group, an acid anhydride, an amino group, and an epoxy group in the molecular chain or at the molecular end as long as the gist of the present invention is not impaired. It may contain a functional group such as. Therefore, as the hydrogenated block copolymer (b) used in the present invention, in addition to the case where one type having such a functional group is used alone, the hydrogenated block copolymer having such a functional group is co-weighted. It is also possible to use two or more types of coalescing together. Further, a hydrogenated block copolymer having a functional group at the molecular terminal and / or a molecular chain can be used in combination with a hydrogenated block copolymer having no such functional group.

As a method for producing a hydrogenated block copolymer (b), a known method can be used without particular limitation, a method of hydrogenating a polymer obtained by anionic polymerization, an ionic polymerization method such as cationic polymerization. , Ziegler polymerization method, single site polymerization method, radical polymerization method and the like may be used. For example, an aromatic vinyl compound or a conjugated diene compound is sequentially polymerized in an inert organic solvent such as n-hexane, cyclohexane, or octane using an alkyllithium compound such as methyllithium, ethyllithium, butyllithium, or pentyllithium as an initiator. Then, the block copolymer is formed, and then the block copolymer is hydrogenated in the presence of a hydrogenation catalyst in an inert organic solvent such as n-hexane, cyclohexane, or octane according to a known method. Then, 70 mol% or more, more preferably 90 mol% or more of the carbon-carbon double bond derived from the conjugated diene compound is hydrogenated to obtain a hydrogenated block copolymer (b). Here, if the hydrogenation rate is less than 70 mol%, the improvement in heat resistance and weather resistance expected by hydrogenation may be insufficient. From the viewpoint of heat resistance and weather resistance, it is particularly preferable to hydrogenate 95 mol% or more of the unsaturated double bond derived from the conjugated diene compound in the block copolymer before hydrogenation. The amount of carbon-carbon double bond derived from the conjugated diene compound in the hydrogenated block copolymer (b) can be determined by iodine value measurement, an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like.

The hydrogenation catalyst includes, for example, a solid catalyst in which a metal such as nickel, platinum, palladium, ruthenium or rhodium is supported on a single substance such as carbon, silica or diatomaceous earth, an organometallic compound such as nickel or cobalt, and triethylaluminum or triisobutyl. Examples thereof include a homogeneous catalyst composed of an organic aluminum compound such as aluminum, or a homogeneous catalyst composed of a transition metal cyclopentadienyl compound such as titanium and haunium and an organometallic compound such as lithium, potassium, aluminum, zinc and magnesium. ..

As such a hydrogenated block copolymer (b), a commercially available product can also be used. For example, the product name "Clayton" of Clayton Polymer Japan Co., Ltd., the product name "Tough Tech" of Asahi Kasei Kogyo Co., Ltd., etc. The product names of Kuraray Co., Ltd., such as "High Blur" and "Septon", can be mentioned.

In the thermoplastic resin composition of the present invention, the blending ratio of the olefin resin (a) and the hydrogenated block copolymer (b) is the same as that of the hydrogenated block with respect to 100 parts by mass of the olefin resin (a). The polymer (b) needs to be 110 to 230 parts by mass, preferably in the range of 120 to 170 parts by mass. When the compounding ratio of the hydrogenated block copolymer (b) exceeds 230 parts by mass, the adhesive strength between the thermoplastic resin composition and the fabric is inferior. On the other hand, if the compounding ratio of the hydrogenated block copolymer (b) to 100 parts by mass of the olefin resin (a) is less than 110 parts by mass, the flexibility of the laminate obtained from the thermoplastic resin composition and the fabric is inferior. ..

<Other ingredients>
Other components such as a plasticizer can be added to the thermoplastic resin composition used in the present invention as long as the effects of the present invention are not impaired. As the plasticizer, known ones can be used without particular limitation. For example, paraffin-based, naphthen-based, aromatic, liquid paraffin and other hydrocarbon-based oils, peanut oil, rosin and other vegetable oils, phosphoric acid esters, etc. There are liquid polymers having plasticizing ability such as chlorinated paraffin, silicon oil, liquid polyisoprene or hydrocarbons, liquid polybutadiene, liquid polyisobutylene, or modified products thereof. In addition to using one type of plasticizer, two or more types may be used in combination. As such a plasticizer, a commercially available product can also be used. For example, a paraffin-based oil manufactured by Idemitsu Kosan Co., Ltd., trade names "Diana Process Oil PW-90" and "Diana Process Oil PW-380" , "Diana Process Oil PW-32" and the like can be used.

The amount of the plasticizer added is 0 to 100 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the olefin resin (a). If the amount of the plasticizer exceeds 100 parts by mass, the plasticizer may bleed out from the thermoplastic resin laminated cloth molded product composed of the thermoplastic resin composition and the cloth, which is not preferable.

Further, in the present invention, a modified product of the hydrogenated block copolymer (b), a styrene resin, an olefin resin, a polyoxymethylene resin, a polyphenylene ether resin and the like can be blended as long as the characteristics are not impaired. In addition, an inorganic filler may be added for the purpose of cost reduction. Specific examples of such an inorganic filler include talc, calcium carbonate, kaolin, titanium oxide and the like.

For the purpose of modifying the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, flame retardant agents (polyammonium phosphate compounds, phosphoric acid esters, condensed phosphoric acid esters, etc.), foaming agents (azodicarboxylic amides, dinitroso). Pentamethylenetetramine, etc.), antioxidants and heat-stabilizing agents (hindered phenol-based, hydroquinone-based, phosphite-based and their substitutes, etc.), light stabilizers, ultraviolet absorbers and weather-resistant agents (resorcinol-based, salicylate-based, etc.) Bentotriazole-based, benzophenone-based, hindered amine-based, etc.), antistatic agents and antistatic agents (montanoic acid and its metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, etc.), pigments ( Cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (niglocin, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cations, etc.) Antistatic agents, non-ionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine-based amphoteric antistatic agents, etc.) can be added.

As a method for producing the thermoplastic resin composition of the present invention, a method usually used for producing a resin composition or an elastomer composition can be adopted, and each of the above components is heated by a single-screw extruder, a twin-screw extruder, a Banbury mixer, or a heater. Mix using a melt kneader such as a roll or various kneaders. If melting and kneading are possible, the melting temperature is not particularly limited, but is generally 150 to 240 ° C, more preferably 180 to 230 ° C.

The cloth laminated molded article of the present invention is obtained by laminating the above-mentioned thermoplastic resin composition on a cloth. The fabric is not particularly limited, but for example, a knitted fabric, a non-woven fabric, or the like can be used. The material of the fabric is natural materials such as cotton and linen, nylon, polyester, aromatic polyamide, acrylic, polyolefin, vinylon, viscose rayon, cupra, diacetate, synthetic fibers such as triacetate, and inorganic fibers such as glass fiber. Can be mentioned. These fibers may be formed in the shape of short fiber spun yarn, long fiber yarn, split yarn, tape yarn or the like. The knitting structure of the fabric is not particularly limited, and a coarse knitted fabric composed of threads including warp threads and weft threads arranged in parallel at intervals of threads can be used, and the basis weight, thickness, etc. of the fabric can be used. There are no particular restrictions on.

In order to produce a cloth laminated molded body using the above-mentioned thermoplastic resin composition and cloth, a conventionally known method for producing a cloth laminated body, for example, the thermoplastic resin composition is heated and melted, or the thermoplastic resin composition is obtained. Emulsions and solutions containing substances can be prepared and molded by coating or impregnating the fabric, or by laminating and molding a calendar-molded film. In addition, an injection molding method in which a molten resin is flowed after the fabric is attached to the inside of a mold, laminating extrusion of the fabric and the molten resin by an extruder, welding of the molded product to the fabric by hot air, and other blow molding. It can be molded by any method such as press molding or press molding.

The cloth laminated molded product of the present invention is lightweight and has sufficient flexibility, and is excellent in adhesiveness between the cloth and the thermoplastic resin composition. Taking advantage of these features, materials for rain gear such as umbrellas, feathers, rain shoes, waterproof shoes, waterproof clothing, waterproof sheets, fire hoses, outdoor eaves tents, automobile hood sheets, industrial mesh sheets, table covers, carpets, etc. It can be used for mats, automobile interior materials, etc.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, the physical characteristics of the resin composition and the cloth laminated molded product were evaluated by the following methods.

(1) Melting point (° C) of olefin resin
A 10 mg olefin resin sample is sealed in an aluminum cell, and a differential scanning calorimetry device (manufactured by SHIMADZU; DSC-60) is used to measure the calorific value on the vertical axis and the temperature on the horizontal axis, and the measurement temperature range is 40 to 200 ° C. The temperature represented by the peak position of the absorption curve obtained when the temperature was measured at a heating rate of 10 ° C./min was measured as the melting point.

(2) The thermoplastic resin composition melted by a press molding machine (NF-37H manufactured by Shinto Metal Industry Co., Ltd.) set to a hardness temperature of 230 ° C. is cooled by a water-cooled press molding machine to form a press sheet having a thickness of 2 mm. The durometer hardness of the prepared test piece was measured based on the JIS K 6253 test method.

(3) Relative Density Measurement was performed based on the JIS K 7112 test method using an electronic hydrometer.

(4) Adhesive strength (N / 20 mm)
It was measured by the 180 ° peeling test specified in the JIS K6256 test method. That is, a sheet having a thickness of 0.7 mm formed by a press molding machine is cut into a length x width = 20 mm x 80 mm, a polyester cloth is placed on the cut sheet, and a weight is applied so that a load of 0.05 MPa is applied from above. Was heated for 5 minutes on a plate set at 125 ° C., and then cooled by a cooling plate set at a surface temperature of 10 ° C. to obtain an adhesive sample having an adhesive portion of 20 mm × 80 mm. Using the sample, a peeling test was performed with an Instron universal tester at a tensile speed of 5 cm / min, and the adhesive strength (N / 20 mm) was measured.

(5) Waterproofness A sheet with a thickness of 0.7 mm formed by a press molding machine is cut out to a length x width = 20 mm x 80 mm, a polyester cloth is placed on the cut out sheet, and a load of 0.05 MPa is applied from above. With the weight placed on it, it was heated for 5 minutes on a plate set at 125 ° C., and then cooled by a cooling plate set at a surface temperature of 10 ° C. to obtain a sample having an bonded portion of 20 mm × 80 mm.
Then, in accordance with the JIS L1092 test method, ^{an acrylic cylinder with a tip diameter of 1 cm 2} is covered with the above sample and fixed, and water is poured into the cylinder until the water surface height is 1000 mm. The leak was visually observed. As a result of visual confirmation, if the leakage of water droplets was within 3 drops, it was judged as acceptable.

<Example 1>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of linear low density polyethylene (LLDPE1) having a melting point of 115 ° C. and an MFR of 5 g / 10 min, and the conjugated diene monomer is isoprene. A twin-screw extruder (TOSHIBA) with 150 parts by mass of a hydrogenated block polymer (TPS1; content of aromatic vinyl polymer block is 20%, weight average molecular weight is 110,000, hydrogenation rate is 90% or more). Using a TEM-26SS manufactured by Machinery Co., Ltd.), the mixture was melt-kneaded at 230 ° C. and pelletized. The obtained pellets are formed into a sheet having a thickness of 0.7 mm by a press molding machine, cut out to a length x width = 20 mm x 80 mm, a polyester cloth is placed on the cut out sheet, and 0.05 MPa is further applied from above. A cloth laminated molded product was obtained by heating at a plate temperature of 125 ° C. for 5 minutes with a weight placed so that a load was applied, and then cooling with a cooling plate having a surface temperature of 10 ° C. The performance evaluation results are shown in Table 1.

<Example 2>
As an olefin resin, 100 parts by mass of linear low-density polyethylene (LLDPE1) having a melting point of 115 ° C. and an MFR of 5 g / 10 min has an aromatic vinyl polymer block and a conjugated diene polymer block, and the conjugated diene monomer is isoprene. 70 parts by mass of the hydrogenated block polymer (TPS1; the content of the aromatic vinyl polymer block is 20%, the weight average molecular weight is 110,000, and the hydrogenation rate is 90% or more), and the aromatic vinyl polymer. It has a block and a conjugated diene polymer block, and the conjugated diene monomer is isoprene. The content of the hydrogenated block polymer (TPS2; aromatic vinyl polymer block is 30%, and the weight average molecular weight is 50,000. Pellets and cloth laminated molded products were obtained under the same conditions as in Example 1 except that 80 parts by mass (that is, a total of 150 parts by mass of the hydrogenated block copolymer) was used. The performance evaluation results are shown in Table 1.

<Example 3>
As an olefin resin, 100 parts by mass of low-density polyethylene (LDPE1) having a melting point of 110 ° C. and an MFR of 3 g / 10 min has an aromatic vinyl polymer block and a conjugated diene polymer block, and the conjugated diene monomer is isoprene. 70 parts by mass of a hydrogenated block polymer (TPS1; content of aromatic vinyl polymer block is 20%, weight average molecular weight is 110,000, hydrogenation rate is 90% or more), and aromatic vinyl polymer block. And a hydrogenated block polymer (TPS2; aromatic vinyl polymer block content of 30%, weight average molecular weight of 50,000, water) having a conjugated diene polymer block and the conjugated diene monomer being isoprene. Pellets and cloth laminated molded products were obtained under the same conditions as in Example 1 except that 80 parts by mass (that is, a total of 150 parts by mass of the hydrogenated block copolymer) was used. The performance evaluation results are shown in Table 1.

<Example 4>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of linear low-density polyethylene (LLDPE1) having a melting point of 115 ° C. and an MFR of 5 g / 10 min, and the conjugated diene monomer is isoprene. Examples except that 110 parts by mass of the hydrogenated block polymer (TPS1; the content of the aromatic vinyl polymer block is 20%, the weight average molecular weight is 110,000, and the hydrogenation rate is 90% or more) is used. Pellets and a cloth laminated molded body were obtained under the same conditions as in 1. The performance evaluation results are shown in Table 1.

<Example 5>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of linear low-density polyethylene (LLDPE1) having a melting point of 115 ° C. and an MFR of 5 g / 10 min, and the conjugated diene monomer is isoprene. Examples except that 230 parts by mass of the hydrogenated block polymer (TPS2; the content of the aromatic vinyl polymer block is 30%, the weight average molecular weight is 50,000, and the hydrogenation rate is 90% or more) is used. Pellets and a cloth laminated molded body were obtained under the same conditions as in 1. The performance evaluation results are shown in Table 1.

<Comparative Example 1>
As an olefin resin, it has an aromatic vinyl polymer block and a conjugated diene polymer block in 80 parts by mass of an ethylene-octene copolymer having a melting point of 100 ° C., an MFR of 30 g / 10 min, and a total crystallinity of 25%. Hydrogenated block copolymer in which the conjugated diene monomer is isoprene / butadiene (TPS3; content of aromatic vinyl polymer block is 30%, weight average molecular weight is 90,000, hydrogenation rate is 90% or more). Pellets and cloth laminated molded products were obtained under the same conditions as in Example 1 except that 20 parts by mass and 20 parts by mass of a paraffin-based oil having a kinematic viscosity of 95 mm2 / s at 40 ° C. were used as the plasticizing agent. The performance evaluation results are shown in Table 2.

<Comparative Example 2>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of low density polyethylene (LDPE1) having a melting point of 110 ° C. and an MFR of 3 g / 10 min, and the conjugated diene monomer is butadiene. Example 1 except that 70 parts by mass of a certain hydrogenated block polymer (TPS4; content of aromatic vinyl polymer block is 30%, weight average molecular weight is 100,000, hydrogenation rate is 90% or more) is used. Pellets and cloth laminated molded products were obtained under the same conditions as above. The performance evaluation results are shown in Table 2.

<Comparative Example 3>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of linear low-density polyethylene (LLDPE1) having a melting point of 115 ° C. and an MFR of 5 g / 10 min, and the conjugated diene monomer is isoprene. Examples except that 70 parts by mass of the hydrogenated block polymer (TPS1; the content of the aromatic vinyl polymer block is 20%, the weight average molecular weight is 110,000, and the hydrogenation rate is 90% or more) is used. Pellets and a cloth laminated molded body were obtained under the same conditions as in 1. The performance evaluation results are shown in Table 2.

<Comparative Example 4>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of linear low-density polyethylene (LLDPE1) having a melting point of 115 ° C. and an MFR of 5 g / 10 min, and the conjugated diene monomer is isoprene. Examples except that 250 parts by mass of a hydrogenated block polymer (TPS1; content of aromatic vinyl polymer block is 20%, weight average molecular weight is 110,000, hydrogenation rate is 90% or more) is used. Pellets and a cloth laminated molded body were obtained under the same conditions as in 1. The performance evaluation results are shown in Table 2.

<Comparative Example 5>
As an olefin resin, an aromatic vinyl polymer block and a conjugated diene polymer block are provided in 100 parts by mass of a high-density polyethylene (HDPE1) having a melting point of 123 ° C. and an MFR of 3 g / 10 min, and the conjugated diene monomer is isoprene. 70 parts by mass of a hydrogenated block polymer (TPS1; content of aromatic vinyl polymer block is 20%, weight average molecular weight is 110,000, hydrogenation rate is 90% or more), and aromatic vinyl polymer block. And a hydrogenated block polymer (TPS2; aromatic vinyl polymer block content is 30%, weight average molecular weight is 50,000, water) having a conjugated diene polymer block and the conjugated diene monomer being isoprene. Pellets and cloth laminated molded products were obtained under the same conditions as in Example 1 except that 80 parts by mass was used. The performance evaluation results are shown in Table 2.

<Comparative Example 6>
Water having an aromatic vinyl polymer block and a conjugated diene polymer block in 100 parts by mass of polypropylene (PP1) having a melting point of 130 ° C. and an MFR of 10 g / 10 min as an olefin resin, and the conjugated diene monomer being isoprene. Addition block polymer (TPS1; content of aromatic vinyl polymer block is 20%, weight average molecular weight is 110,000, hydrogenation rate is 90% or more) 90 parts by mass, and aromatic vinyl polymer block and conjugate Hydrolyzed block polymer (TPS2; aromatic vinyl polymer block content of 30%, weight average molecular weight of 50,000, hydrogenation rate) having a diene polymer block and the conjugated diene monomer being isoprene. 90% or more) Pellets and cloth laminated molded products were obtained under the same conditions as in Example 1 except that 90 parts by mass was used. The performance evaluation results are shown in Table 2.

<Comparative Example 7>
Pellets and cloth laminated molded products were obtained under the same conditions as in Example 1 except that a polyurethane elastomer (aromatic ether urethane elastomer, hardness 75A, specific density 1.1, melting point 77 ° C.) was used. The performance evaluation results are shown in Table 2.

The cloth laminated molded products obtained in Examples 1 to 5 have a durometer hardness of 85 or less and have sufficient flexibility, and have a strong adhesive strength of 40 N / 20 mm or more in the adhesive strength test. At the same time, it is also excellent in waterproofness.
On the other hand, the compositions (Comparative Examples 1 and 2) described in Examples of JP-A-2003-136634 do not have sufficient adhesive strength and are also inferior in flexibility. Further, the adhesive strength is not sufficient in the composition having a hydrogenated block copolymer (b) lower than 110 and a ratio higher than 230 with respect to 100 parts by mass of the olefin resin (a), and the ratio is further lower than 110. The composition is also inferior in flexibility (Comparative Examples 3 and 4). Further, the adhesive strength is not sufficient in the composition using a material having a melting point higher than 120 ° C. as the olefin resin (Comparative Examples 5 and 6). Further, when a urethane-based elastomer is used, the specific gravity is large and the product weight is heavy, which causes a problem in handleability (Comparative Example 7).

Since the thermoplastic resin composition of the present invention and the cloth laminated molded product obtained by laminating the composition and the cloth are excellent in flexibility, light weight, adhesive strength and the like, they are used as interior / exterior materials for automobiles in addition to the above-mentioned applications. Parts, home appliances, office equipment parts, furniture, building materials, sporting goods, pharmaceutical goods, industrial materials, elastic materials such as sanitary materials, clothing, films, sheets, mats, non-slip materials, tubes, hoses, pipes, stationery, toys , Can be used for a wide range of purposes such as daily necessities.

Claims (4)

With respect to 100 parts by mass of the olefin resin (a) having a melting point of 110 to 120 ° C. measured by differential scanning calorimetry, at least two or more polymer blocks (A) made of styrene are contained in the molecule, and the molecule. A thermoplastic resin composition containing 110 to 230 parts by mass of a hydrogenated block copolymer (b) obtained by hydrogenating a block copolymer having one or more polymer blocks (B) made of isoprene. A cloth laminated molded body obtained by laminating the thermoplastic resin composition according to claim 1 and a cloth. A waterproof product using the cloth laminated molded product according to claim 2. A fire hose using the cloth laminated molded body according to claim 2.