JP6681824B2 - Composite and method for producing the same - Google Patents

Description

  The present invention relates to a composite having bending resistance and vibration damping property.

  Composites such as shoes, bags, and suitcases are often obtained by subjecting a part of a sheet material such as synthetic leather to a resin such as a bottom material by insert injection processing. In this case, the resin may be a styrene-based thermoplastic elastomer (hereinafter, also referred to as TPS) from the viewpoint of flexibility, lightness, waterproofness, and price. However, there is a problem that bending around the joint between the sheet material and the resin causes creases (kinks) in the single portion of the sheet material, pinholes (bending resistance) due to this, poor appearance, and discomfort in mounting.

  Patent Document 1 proposes a method of integrally molding a shoe by insert-injecting TPS as a shoe sole into a cloth or a cover of synthetic leather or the like.

  Patent Document 2 proposes a method of integrally molding shoes by using polypropylene resin (PP) -containing cloth and / or TPS resin as a cover and injecting TPS resin into the bottom material by insert injection.

  Patent Document 3 proposes to use a blended resin of TPS and PU for artificial leather or a shoe sole.

Japanese Patent No. 2524930 JP, 2002-177007, A Japanese Patent No. 2986690

  However, in Patent Document 1, a vinyl chloride resin (PVC) or a polyurethane resin (PU) is used as the synthetic leather, and when TPS is used, the adhesive is not adhered to the synthetic leather due to poor adhesion with the synthetic leather. Need to be applied, and there are problems in cost and quality.

  In Patent Document 2, there is a problem that a fold wrinkle (kink) of a cover from around the joint portion of both base materials and a pinhole (bending resistance) due to the crease, poor appearance, dirt, discomfort in mounting, and the like occur.

  The thermoplastic polyurethane composition described in Patent Document 3 is characterized by good mold releasability from a mold or the like. In Patent Document 3, artificial leather is used as a cover, and the thermoplastic polyurethane composition is used as a sole. There is no disclosure of insert injection molding and integration.

  Therefore, in a composite body integrally molded by insert-injecting a resin composition into a base material, when the composite body is bent, a fold wrinkle (kink) generated around the joint between the base material and the resin composition, and this It is required to reduce pinholes (bending resistance), poor appearance, and discomfort due to mounting.

As a problem to be solved by the present invention, a composite material obtained by insert-injecting a resin composition into a part of a sheet-shaped material obtained by impregnating or laminating a resin composition on a base fabric, wherein a sheet-shaped material and a resin composition are used. It is to reduce creases (kinks) in the sheet-shaped material due to bending that occurs around the joint, and pinholes (bending resistance), poor appearance, and uncomfortable feeling while maintaining adhesiveness with objects. .

As a result of earnest studies to achieve the above object, the present inventors have made a sheet-shaped material (D) and a resin layer (C), and the sheet-shaped material (D) is a base cloth layer (A) and a resin layer (B). ), The adhesiveness between the sheet-shaped material (D) and the resin layer (C) is secured, and the sheet-shaped material (D) is bent due to the bending around the joint portion. Further, they have found that pinholes (bending resistance), poor appearance, stains, and discomfort due to this can be reduced, and have completed the present invention.
That is, the present invention includes the following preferred embodiments.
[1] A composite comprising a sheet material (D) and a resin layer (C), wherein the sheet material (D) comprises a base cloth (A) and a resin layer (B),
The resin layer (B) and the resin layer (C) are respectively
(A) a polymer block (X) composed of structural units derived from at least one vinyl aromatic compound and a polymer block (Y) composed of structural units derived from at least one conjugated diene compound A block copolymer comprising and / or a thermoplastic elastomer which is a hydrogenated product of the block copolymer,
(B) containing at least an olefin resin and (c) a softening agent,
The resin layer (B) has a content of the olefin resin (b) in the resin layer (B) of 10% by mass or less, a content of the softening agent (c) of 30% by mass or less, and a loss factor. (Η) is 0.1 or more, and the resin layer (C) has a content of the olefin resin (b) in the resin layer (C) of more than 10% by mass and a content of the softening agent (c). Is more than 30% by mass, and the loss factor (η) is 0.1 or more.
[2] The thermoplastic elastomer (a) has a content of 3,4-bond units and 1,2-bond units in the structural unit derived from isoprene and / or butadiene in the thermoplastic elastomer (a) (hereinafter, A thermoplastic elastomer (a1) having a vinyl bond content of 45 mol% or more, or the thermoplastic elastomer (a1) and a thermoplastic elastomer (a2) having a vinyl bond content of less than 45 mol%. The composite according to [1], wherein the vinyl bond content in the mixture is 35 mol% or more.
[3] The composite according to [1] or [2], wherein the base fabric (A) is at least one selected from the group consisting of woven fabric, non-woven fabric, and composite fabric.
[4] The composite according to any one of [1] to [3], which is an insert injection molded product.
[5] A method for producing a composite according to any one of [1] to [4],
1) a step of obtaining a sheet material (D) by impregnating or laminating the resin composition (B) constituting the resin layer (B) on the base fabric (A), and 2) at least one of the sheet material (D) A method, which comprises a step of insert-injecting a resin composition (C) constituting the resin layer (C) into the part.

  According to the present invention, it is possible to provide a composite of shoes, a bag, a suitcase or the like, which has excellent bending resistance and has improved adhesiveness, vibration damping property, antifouling property and the like.

<Complex>
The composite of the present invention comprises a sheet material (D) and a resin layer (C). The composite of the present invention can be obtained by insert-injecting the resin composition (C) forming the resin layer (C) into the sheet-shaped material (D).

<Sheet material (D)>
The sheet material (D) comprises a base cloth (A) and a resin layer (B). The sheet material (D) can be obtained by impregnating or laminating the base fabric (A) with the resin composition (B) constituting the resin layer (B).

<Base cloth (A)>
As the base fabric (A) used in the present invention, any sheet-like fibrous base material having an appropriate thickness and a sense of fulfillment and having a soft texture can be used, and the shape is short. Woven and non-woven fabrics and composite fabrics using one or more types of fibers, long fibers, composite fibers (core-sheath fibers, etc.), spunbonds, etc. are preferable, and the materials include natural fibers, artificial fibers, synthetic fibers and paper materials. Used. Among them, non-woven fabrics and paper materials are effective in terms of shape stability, air permeability and workability.

  Further, various fibrous base materials that have been conventionally used for producing a leather-like laminate are preferably used. Although not limited, examples of the fibrous base material that can be used in the present invention include ultrafine fibers or bundled fibers thereof, special porous fibers, ordinary synthetic fibers, semi-synthetic fibers, natural fibers, inorganic fibers, etc. A fibrous sheet such as an entangled non-woven sheet or a knitted woven sheet formed by using.

  Among the above-mentioned fibrous base materials, a fibrous sheet formed by using ultrafine fibers or an ultrafine fiber bundle is preferably used, and the single fiber fineness of the ultrafine fibers constituting the fibrous sheet is 0.5 denier or less. Is preferable, and 0.1 denier or less is more preferable. When the fibrous base material is formed from an ultrafine fiber bundle, the total denier of the ultrafine fiber bundle is preferably 0.5 to 10 denier from the viewpoint of the feel of the laminate. The ultrafine fibers constituting the fibrous base material are preferably formed of polyester fibers and / or nylon fibers from the viewpoint of strength, feel, cost, etc. of the resulting laminate.

  Further, in order to obtain ultrafine fibers or ultrafine fiber bundles, a resin soluble in hot water or an organic solvent, for example, polyethylenes (hereinafter abbreviated as PE), polyvinyl alcohols (hereinafter abbreviated as PVA), etc. After being blended with a resin of a nylon resin and / or a fibrous sheet such as a fibrous or entangled non-woven sheet or a knitted woven sheet, and optionally impregnated or laminated with a resin layer (B), hot water or an organic solvent In some cases, PE or PVA may be removed.

  In order to improve the adhesion between the base fabric (A) and the resin layer (B), a coating layer of a surface treatment agent containing a polymer having a high affinity for the resin layer (B) is provided on the surface of the base fabric (A). It may be formed, and the thickness of the coating layer in that case is preferably 5 μm or less. When the thickness of the coating layer is large, it is difficult to obtain a composite having a soft and cohesive feeling.

Further, in order to obtain a laminate having a soft texture and a feeling of waist, the apparent specific gravity of the base fabric (A) is preferably 0.25 to 0.5 g / cm ³ , and the apparent specific gravity is preferably 0. More preferably, it is ³ to 0.35 g / cm ³ . If the apparent specific gravity of the base cloth (A) is too large, the composite tends to have a rubber-like texture, while if the apparent specific gravity of the base cloth (A) is too small, the texture tends to be flat.

  The thickness of the base fabric (A) can be determined according to the application of the composite to be produced, but is preferably about 0.3 to 3 mm, and about 0.5 to 2.0 mm. It is more preferable.

<Resin layer (B) and resin layer (C)>
The resin layers (B) and (C) and the resin compositions (B) and (C) include at least (a) a polymer block (X) composed of a structural unit derived from at least one vinyl aromatic compound and A thermoplastic elastomer, which is a block copolymer comprising a polymer block (Y) composed of structural units derived from one conjugated diene compound and / or a hydrogenated product of the block copolymer, and (b) an olefin. At least a system resin and (c) a softening agent.

<Thermoplastic elastomer (a)>
The thermoplastic elastomer (a) used in the present invention comprises a polymer block (X) composed of at least one structural unit derived from a vinyl aromatic compound and a structural unit derived from at least one conjugated diene compound. A block copolymer comprising a polymer block (Y) composed of and / or a hydrogenated product of this block copolymer.

<Block copolymer>
Since the block copolymer contains at least one polymer block (X) and at least one polymer block (Y) composed of a conjugated diene compound, good flexibility can be exhibited. The block copolymer preferably contains two or more polymer blocks (X) and one or more polymer blocks (Y) from the viewpoint of heat resistance, mechanical properties and the like. The bonding mode of the polymer block (X) and the polymer block (Y) may be linear, branched or any combination thereof. The structure of the block copolymer when the polymer block (X) is represented by X and the polymer block (Y) is represented by Y is, for example, a diblock structure represented by XY or XYX. The triblock structure shown, the multiblock copolymer shown by (X-Y) _n , (X-Y) _n- X (Here, n represents an integer greater than or equal to 2) etc. are mentioned. Among them, the triblock structure represented by X-Y-X is a diblock structure represented by X-Y in terms of vibration damping property, heat resistance, mechanical properties, antifouling property, handleability and the like. The thing of the thing of vibration damping and adhesiveness is preferable.

  In addition, a block portion in which a vinyl aromatic compound which is a constituent component of the polymer block (X) and a conjugated diene compound which is a constituent component of the polymer block (Y) are copolymerized in a random and / or tapered shape, It can be contained in a range that does not impair the effects of the present invention. When the block copolymer includes a block portion copolymerized in a random and / or taper shape, it is preferable to coordinate to the random or / and taper-containing block in the vicinity of the connection portion of the XY structure portion. . The phrase “containing a block portion randomly copolymerized” means that there is a portion in which the monomers constituting X and Y are randomly bonded between the blocks X and Y, respectively. Including a block portion copolymerized in a taper shape means that, between blocks X and Y, the number of monomers constituting X decreases at a constant rate and the number of monomers constituting Y increases at a constant rate. It means that a part exists.

Examples of the vinyl aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, and vinylanthracene. Among these, styrene and α
-Methylstyrene is preferred. The aromatic vinyl compounds may be used alone or in combination of two or more.

  The content of the structural unit derived from the vinyl aromatic compound in the thermoplastic elastomer (a) is preferably 5 to 75% by mass, more preferably 5 to 50% by mass. When the content of the structural unit derived from the vinyl aromatic compound is within this range, the resin layer (B) and the resin layer (C) tend to have good heat resistance and mechanical properties.

  The polymer block (X) may contain a small amount of structural units derived from other copolymerizable monomers together with structural units derived from vinyl aromatic compounds. Examples of other copolymerizable monomers include ion-polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene and methyl vinyl ether. These other copolymerizable monomers can be used alone or in combination of two or more kinds. When the polymer block (A) has a structural unit derived from another copolymerizable monomer such as a vinyl aromatic compound in addition to the structural unit derived from a vinyl aromatic compound, the bonding form thereof is random, It may be in any form such as a tapered shape. In this case, the proportion of structural units derived from another copolymerizable monomer is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the mass of the polymer block (X). preferable.

  Examples of the conjugated diene compound include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The conjugated diene compounds may be used alone or in combination of two or more.

  The polymer block (Y) composed of a structural unit derived from at least one conjugated diene compound in the thermoplastic elastomer (a) is a resin layer (B) and (C) and a resin composition from the viewpoint of damping property. The components (B) and (C) are suitably composed of structural units derived from isoprene alone or a mixture of isoprene and butadiene. The thermoplastic elastomer (a) has a content of 3,4-bond units and 1,2-bond units of structural units derived from isoprene and / or butadiene which are conjugated diene compounds in the polymer block (Y) (hereinafter, The vinyl bond content) is preferably 45 mol% or more, more preferably 50 mol% or more.

  Further, the thermoplastic elastomer (a) is the thermoplastic elastomer (a1) alone having a vinyl bond content of 45 mol% or more in the thermoplastic elastomer (a), or is a vinyl bond with the thermoplastic elastomer (a1). A mixture with the polymer (a2) having a content of less than 45 mol%, preferably the thermoplastic elastomer (a1) alone having a vinyl bond content of 50 mol% or more in the thermoplastic elastomer (a), A mixture of the thermoplastic elastomer (a1) and the polymer (a2) having a vinyl bond content of less than 40 mol% may be used. The vinyl bond content in the mixture is preferably 35 mol% or more, more preferably 37 mol% or more, still more preferably 40 mol% or more.

<Hydrogen of block copolymer>
From the viewpoint of heat resistance and light resistance, the thermoplastic elastomer (a) may be a block copolymer hydrogenated product, or a mixture of a block copolymer and its hydrogenated product. In this case, 50% or more of the carbon-carbon double bonds derived from the conjugated diene in the structural unit constituting the polymer block (Y) is preferably hydrogenated, and 75% or more is hydrogenated. It is more preferable that 95% or more be hydrogenated.

<Active group-containing thermoplastic elastomer>
Further, in order to increase the compatibility of the thermoplastic elastomer (a) with the olefin resin (b) and, where appropriate, the non-olefin resin (c), the thermoplastic elastomer (a) is provided with a hydrosyl group or a carbonyl group. In some cases, it is preferable to use an active group-containing thermoplastic elastomer in which an active group such as an amide group or an ester group is copolymerized, graft-polymerized, or grafted inside the melt extruder.

  The weight average molecular weight Mw of the thermoplastic elastomer (a) is preferably 40,000 to 500,000, more preferably 80,000 to 400,000, and still more preferably 160,000 to 300,000. If the molecular weight is smaller than the above range, the mechanical properties of the obtained resin composition are deteriorated, which is not preferable. On the other hand, if it is too large, the viscosity increases remarkably and the molding processability is impaired. The weight average molecular weight Mw can be measured by gel permeation chromatography and calculated in terms of polystyrene.

  The resin layer (B) and the resin composition (B) each contain the thermoplastic elastomer (a), preferably 40 to 90% by mass, more preferably 45% by mass, based on the resin layer (B) or the resin composition (B). To 85% by mass, and more preferably 50 to 80% by mass.

  The resin layer (C) and the resin composition (C) are each preferably a thermoplastic elastomer (a), preferably 20 to 65% by mass, more preferably 25% by mass based on the resin layer (C) or the resin composition (C). -60 mass%, more preferably 30-55 mass%.

<Olefin resin (b)>
Examples of the olefin resin (b) used in the present invention include a propylene polymer and an ethylene polymer for the purpose of improving strength, moldability, chemical resistance, heat resistance and non-adhesiveness. As the propylene-based polymer, for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene and the like can be used. Of these, it is preferable to use random polypropylene or block polypropylene. Examples of the ethylene-based polymer include ethylene homopolymers such as medium density polyethylene, low density polyethylene (LDPE), and high density polyethylene (HDPE); ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, Ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, etc. An ethylene / α-olefin copolymer or the like can be used.

  Further, in order to increase the compatibility with the thermoplastic elastomer (a) and, where appropriate, the non-olefin resin (c), the olefin resin (b) may be added with a hydrosyl group, a carbonyl group, an amide group, an ester group, or the like. In some cases, it is preferable to use an active group-containing olefin resin in which active groups are copolymerized, graft-polymerized, or grafted inside the melt extruder.

<Softening agent (c)>
Examples of the softening agent (c) include process oils such as paraffinic oils, naphthenic oils and aromatic oils, and softening agents for hydrocarbon rubber such as liquid paraffin. Among them, paraffinic oils, naphthenic oils, etc. Process oil, or ethylene, a conjugated diene compound and / or a copolymer of α-olefins having 4 or more carbon atoms, and the like can be mentioned. Among them, paraffin oil, process oil such as naphthene oil, or the copolymer, A polyisobutylene resin (PIB) is more suitable. These may be used alone or in combination of two or more.

The softening agent (c) preferably has a kinematic viscosity at 40 ° C. of 50 to 500 mm ² / s.

  The weight average molecular weight Mw of the softening agent (c) is preferably 700 or more, more preferably 750 or more. The weight average molecular weight Mw of the softening agent (c) is preferably 1500 or less, more preferably 1400 or less. When the weight average molecular weight Mw of the softening agent (c) is 700 or more, the oil bleeding is very small, and when the weight average molecular weight Mw is 1500 or less, the moldability is good.

  The softening agent (c) is not particularly limited in its production, and can be produced by a conventionally known method, for example. Examples of typical commercial products of the softening agent (c) include Diana Process Oil PW series (paraffin oil) manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil NR series (naphthenic oil) manufactured by Idemitsu Kosan Co., Ltd. , NOBEL process oil AB series (aroma-based oil) manufactured by NIKKO OIL PRODUCTS Co., Ltd., and the like.

Each of the resin layer (B) and the resin composition (B) has a content of the olefin resin (b) in the resin layer (B) or the resin composition (B) of 10% by mass or less, and the softener (c ) Content is 30 mass% or less, and the loss coefficient (η) is 0.1 or more. From the viewpoint of vibration damping property, the loss coefficient (η) is preferably 0.12 or more.
When the content of the olefin resin (b) in the resin layer (B) or the resin composition (B) is 10% by mass or less, good flexibility and flex resistance are obtained, and the softening agent (c When the content of () is 30% by mass or less, good adhesion is obtained, and when the loss coefficient (η) is less than 0.1, the vibration damping property deteriorates. In particular, when the composite is shoes, ankle fatigue occurs when the vibration damping property deteriorates, which is not preferable.

  Further, the thermoplastic elastomer (a) contained in the resin layer (B) and the resin composition (B) is a thermoplastic elastomer (a1) in which the vinyl bond content in the thermoplastic elastomer (a) is 45 mol% or more. Alone or a mixture of the thermoplastic elastomer (a1) and the thermoplastic elastomer (a2) having a vinyl bond content of less than 45 mol%, wherein the vinyl bond content in the mixture is 35 mol% or more. Preferably. When the vinyl bond content in the thermoplastic elastomer (a) is less than 35 mol%, the vibration damping property is deteriorated, and when the composite is a shoe, fatigue of the ankle is deteriorated, which is not preferable.

In the resin layer (C) and the resin composition (C), the content ratio of the olefin resin (b) in the resin layer (C) or the resin composition (C) exceeds 10% by mass, and the softening agent (c) is used. Content ratio exceeds 30 mass%, and the loss coefficient (η) is 0.1 or more. From the viewpoint of vibration damping property, the loss coefficient (η) is preferably 0.12 or more.
When the content of the olefin resin (b) in the resin layer (C) or the resin composition (C) exceeds 10% by mass, good moldability is obtained, and the content ratio of the softening agent (d) is high. When it exceeds 30% by mass, good flexibility and flexibility are obtained, and when the loss coefficient (η) is less than 0.1, the vibration damping property deteriorates.

  Further, the thermoplastic elastomer (a) contained in the resin layer (C) and the resin composition (C) is a thermoplastic elastomer (a1) in which the vinyl bond content in the thermoplastic elastomer (a) is 45 mol% or more. Alone or a mixture of the thermoplastic elastomer (a1) and the thermoplastic elastomer (a2) having a vinyl bond content of less than 45 mol%, wherein the vinyl bond content in the mixture is 35 mol% or more. Preferably. When the vinyl bond content in the thermoplastic elastomer (a) is less than 35 mol%, the vibration damping property deteriorates.

<Other ingredients>
The resin layers (B) and (C) and the resin compositions (B) and (C) of the present invention are, if necessary, other components such as a non-olefin resin, as long as the effects of the present invention are not significantly impaired. Resin, tackifier, etc. may be included.

<Non-olefin resin>
The non-olefin resin used in the present invention is a thermoplastic polyurethane elastomer, a thermoplastic acrylic elastomer, a thermoplastic polyester elastomer, a thermoplastic polyamide elastomer, etc. for the purpose of improving flex resistance, non-adhesiveness, adhesiveness and flexibility. Can be used alone or as a blend of two or more. Among them, thermoplastic polyurethane elastomers, thermoplastic acrylic elastomers, thermoplastic polyester elastomers, and thermoplastic polyamide elastomers are preferable, and thermoplastic polyurethane elastomers are more preferable.

  As the thermoplastic polyurethane elastomer, it is preferable to use, for example, one or more kinds of polyester polyurethane, polyether polyurethane, polycarbonate polyurethane, polycaprolactone polyurethane, and the like. Further, as the polyurethane-based copolymer elastomer, both isocyanate group terminal oligomers obtained by a polyaddition reaction of a diisocyanate compound and a polyol compound containing two or more hydroxyl groups in the molecular structure, and both isocyanate group having a molecular weight of about 2000 to 10,000. Polyurethane having a terminal polyurethane prepolymer, a dicarboxylic acid having 4 to 12 carbon atoms, and a carboxylic acid group- or amine group-terminated oligomer obtained by polycondensation of a diamine having 4 to 14 carbon atoms, and a carboxylic acid having a molecular weight of about 2,000 to 10,000. Polyurethane-polyamide copolymer resin obtained by copolymerization with acid group- or amine group-terminated polyamide prepolymer, the above-mentioned isocyanate group-terminated oligomer, and isocyanate group-terminated polyamine having a molecular weight of about 2000 to 10,000. Retan prepolymer, two or more dicarboxylic acids having 4 to 12 carbon atoms of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid, and a carboxylic acid group- or hydroxyl group-terminated oligomer obtained by polycondensation with a diol, and a molecular weight of 2000 to A polyurethane-polyester copolymer resin obtained by copolymerization with a polyester prepolymer having about 10,000 carboxylic acid groups or hydroxyl groups can also be used.

  As the thermoplastic acrylic elastomer, examples of the thermoplastic acrylic elastomer include ethylene-methyl methacrylic acid ester copolymer resin, ethylene-methyl acrylate ester copolymer resin, ethylene-ethyl acrylate ester copolymer resin, ethylene-methyl (meth ) Acrylic acid ester- (anhydrous) maleic acid copolymer resin and the like can be mentioned.

  As the thermoplastic polyester elastomer, for example, a polyester-polyether type polyester elastomer obtained by block copolymerizing an aromatic polyester segment such as polybutylene terephthalate and a polyether segment such as polytetramethylene glycol, or the above aromatic polyester. Examples thereof include polyester-polyester type polyester elastomers obtained by block copolymerization of a segment and an aliphatic polyester segment.

  As the thermoplastic polyamide elastomer, it is preferable to use, for example, a polyamide elastomer obtained by block copolymerization of 6-nylon and 12-nylon segments and an aliphatic polyether or an aliphatic polyether polyester segment.

  When the resin layers (B) and (C) and the resin compositions (B) and (C) contain a non-olefin resin, the content thereof is preferably 30% by mass or less. When the content of the non-olefin resin (c) is 30% by mass or less, good adhesiveness and moldability can be obtained.

<Tackifier>
The resin composition of the present invention may contain a tackifier, if necessary, as long as the effect of the present invention is not significantly impaired. Examples of the tackifier include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin-based resins such as glycerin esters thereof, rosin esters such as pentaerythritol ester; α-pinene, Terpene resins such as β-pinene and dipentene, aromatic modified terpene resins, hydrogenated terpene resins, terpene phenolic resins and other terpene resins: (hydrogenated) aliphatic (C5) petroleum resin, (hydrogenated) Aromatic (C9) petroleum resin, (hydrogenated) copolymer (C5-C9 copolymer) petroleum resin, (hydrogenated) dicyclopentadiene petroleum resin, alicyclic saturated hydrocarbon, etc. May be petroleum resin; poly α-methyl styrene, α-methyl styrene-styrene copolymer, styrene monomer-aliphatic monomer copolymer Body, styrenic monomers - (excluding styrene monomer) aromatic monomer copolymer such as styrene-based resins; phenolic resins; xylene resin; coumarone - synthetic resin such as indene resins. Among these, hydrogenated terpene resins, alicyclic saturated hydrocarbon resins, and (hydrogenated) aliphatic (C5) petroleum resins are preferable from the viewpoint of suppressing coloring of the resin composition. These may be used alone or in combination of two or more.
When the resin layer (B) and / or (C) and the resin composition (B) and / or (C) contain a tackifier, the content is 100 parts by mass of the thermoplastic elastomer (a), It is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less from the viewpoint of heat resistance.

  The resin layers (B) and (C) and the resin compositions (B) and (C) are clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide, mica, graphite, and hydroxide. Flake shaped inorganic additives such as aluminum, various metal powders, wood chips, glass powders, ceramics powders, granular or powdered solid fillers such as granular or powdered polymers, and other various natural or artificial short fibers, long fibers Fibers (for example, straw, wool, glass fiber, metal fiber, other various polymer fibers, etc.) can be blended.

  Further, it is possible to reduce the weight by blending a hollow filler, for example, an inorganic hollow filler such as a glass balloon or a silica balloon, an organic hollow filler made of polyvinylidene fluoride, a polyvinylidene fluoride copolymer or the like. Among them, polyvinyl short fibers, polyarylate short fibers, graphite, mica, titanium oxide, aluminum powder, carbon black and the like are more preferable because they have the effect of greatly improving the vibration damping property.

  The resin layers (B) and (C) and the resin compositions (B) and (C) are, in addition to the above components, various antiblocking agents, heat stabilizers, antioxidants, and light stabilizers depending on the application. It is also possible to contain an ultraviolet absorber, a lubricant, a crystal nucleating agent, a foaming agent, a coloring agent and the like. Here, as the antioxidant, for example, 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′- Dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9 -Bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro-5, Phenol-based antioxidants such as 5-undecane, phosphite-based antioxidants, thioether-based antioxidants and the like can be used. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferable. When the resin layer (B) and / or (C) and the resin composition (B) and / or (C) contain an antioxidant, the antioxidant is the resin layer (B) or (C) of the present invention. Also, it is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the components (a) to (d) contained in the resin composition (B) or (C), and 0.05 More preferably, it is from 1.0 to 1.0 part by mass.

  Further, in the case where the composite of the present invention is additionally provided with sound deadening property and / or impact resistance, it is added to the resin layer (B) and / or (C) or the resin composition (B) and / or (C). If necessary, a foaming agent may be added to foam. The method of foaming is not particularly limited, but may be a method of chemical foaming or physical foaming, for example, addition of an inorganic foaming agent, an organic foaming agent, heat-expandable fine particles, critical foaming of carbon dioxide, or hollow. Examples thereof include the addition of glass balloons.

  Further, for the purpose of further improving the slip property and the antifouling property of the resin layer (B) and / or the resin layer (C) positioned at the outermost layer of the composite, a fluorine-based, acrylic-based, silicon-based, etc. antifouling layer (E) can be applied.

  In the composite of the present invention, the sheet material (D) may have an uneven pattern from the viewpoint of non-adhesiveness and / or designability. The concavo-convex pattern can be provided by the concavo-convex treatment described below.

  The composite of the present invention in which the resin composition (B) is insert-molded in a part of the sheet material (D) is excellent in bending resistance, flexibility, adhesiveness, vibration damping property, and antifouling property. Therefore, it is effective for everyday items such as shoes, bags, and bags, and daily necessities. More specific examples include sports shoes, sports shoes, infant shoes, boots, rain shoes, school bags, school bags, travel bags, travel suitcases, sports equipment bags, and the like. The composite of the present invention is preferably an insert injection molded article.

<Method for producing composite>
The method for producing a composite of the present invention comprises 1) a step of impregnating or laminating a resin composition (B) constituting a resin layer (B) on a base fabric (A) to obtain a sheet material (D), and 2 ) A step of insert-injecting the resin composition (C) constituting the resin layer (C) into at least a part of the sheet material (D) is included.

  In order to prepare the resin compositions (B) and (C), the respective components are blended in the above-mentioned blending ratios, and they are obtained by uniformly mixing them, and they are not particularly limited. It can be melt-kneaded by a pressure kneader, a single-screw extruder, a twin-screw extruder or the like to prepare pellets. In some cases, the following post-processing may be carried out in a solution state by dissolving under heating with an organic solvent such as toluene.

  The obtained pellet-shaped resin is not particularly limited, but for example, a single layer in a hot press machine, injection molding machine, insert injection machine, sheet molding machine, coextrusion sheet molding machine, extrusion laminating machine, etc. A sheet and a multilayer sheet are obtained. In the case of a single layer sheet, a hot press machine, a hot roll laminating machine, an extrusion laminating machine or the like is used to form a multilayer.

  The method for impregnating or laminating the resin layer (B) on the base cloth (A) is not particularly limited, but 1) a solution obtained by dissolving the resin composition (B) in an organic solvent such as toluene under heating is used. Using a method of impregnating and drying the base fabric (A), or 2) using a single-layer extrusion film forming machine or a coextrusion film forming machine, while extruding and laminating the resin composition on the base fabric (A) while heat melting. A method of molding with a cooling roll, or 3) using an extrusion film forming machine or a coextrusion film forming machine to form a film while heat-melting the resin composition B), and then using a heat roll or a heat press machine. 4) a method of laminating under heating and / or pressure, 4) a method of laminating a molten resin composition (B) onto a base fabric (A) under melting using a calendering heating roll, or 1) to 4) Examples include a method of using two or more methods in combination.

  In order to impart non-adhesiveness and / or designability to the outermost layer side of the sheet material (D), when performing the unevenness treatment, when using the above methods 1) to 4), the cooling roll or the heat roll is uneven. It is effective to use a patterned embossing roll. In addition, as an alternative method, a solution of the resin composition (B) is applied to a paper or plastic sheet having an uneven pattern, and then the base cloth (A) is impregnated or laminated and dried, or a paper having an uneven pattern or There is a method of performing extrusion lamination between the plastic sheet and the base fabric (A) to form a multilayer.

  The method of insert injection molding the resin composition (C) into a part of the sheet material (D) is not particularly limited, but the sheet material (D) is placed at a predetermined position in a mold for insert injection molding. After fitting and sealing the mold, pellets of the resin composition (C) are charged and melted in an extruder for injection molding, and, for example, insert injection is performed at a resin temperature of 250 ° C., followed by cooling and removal from the mold. and so on.

  Although the preferred embodiments of the present invention have been described above, various additions, changes, or deletions are possible without departing from the spirit of the present invention, and such things are also included in the scope of the present invention. Be done.

  Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The physical properties of the following examples and comparative examples were evaluated by the methods described below.

(1) Measurement of loss coefficient (η) Flat plates (thickness 1.0 mm, width 15.0 mm, length 250 mm) of resin layers (B) and (C) used in Examples and Comparative Examples described later are injection-molded. Made with a machine and attached with double-sided adhesive tape (SPCC steel plate with thickness 1.0 mm, width 15.0 mm, length 250 mm) and constraining layer (thickness 0.5 mm, width 15.0 mm, length 250 mm) Aluminum plate) was laminated, and then the loss coefficient was measured by a central vibration method at 0 ° C. using a measuring device manufactured by Rion Co., Ltd. under the trade name “SA-01”.

(2) Content of 1,2-bond and 3,4-bond units (vinyl bond content)
The block copolymer was dissolved in CDCl3 and the ¹ H-NMR spectrum was measured [apparatus: JNM-Lambda 500 (manufactured by JEOL Ltd., measurement temperature: 50 ° C.]] to obtain isoprene, butadiene, or isoprene and butadiene. Total peak areas of structural units derived from the mixture, 1,2-bond units and 3,4-bond units in isoprene structural units, 1,2-bond units and 3,4-bond units in butadiene structural units, or isoprene In the case of a mixture of butadiene, the vinyl bond content (total content of 1,2-bond units and 3,4-bond units) was calculated from the ratio of peak areas corresponding to the respective bond units.

(3) Bending resistance A prosthesis fitted with cotton socks is inserted into a composite body molded into shoes by insert injection molding, and attached to a shoe product bending tester (STM184-2) manufactured by SATRA, at an angle of 50 degrees, A bending test of 400,000 times was performed three times at a bending speed of 140 times / min, and the appearance was evaluated for ranking. An average value of rank 2 or less was used as a guide for good bending resistance.
1. There are wrinkles 2. Many wrinkles, but almost no wrinkles 3. There are wrinkles 4. Large wrinkles and no pinholes 5. Large wrinkles, pinholes, and tears

(4) Adhesiveness The insert injection joint part of the composite is cut out with a width of 5 mm, and the shear adhesive strength between the sheet material (D) and the resin layer (B) is controlled by Shimadzu Corporation under an atmosphere of 23 ° C and 50% RH. Graph Using the model number AG-1 and 500N, the shear adhesive force was measured at a pulling speed of 100 mm / min, and 1 kg or more was used as a standard for good adhesiveness.

(5) Flexibility Using the resin layers (B) and (C) prepared in the examples and comparative examples, athletic shoes were prepared and mounted on the monitors of 10 people, and flexibility (flexibility, stiff feeling) was obtained by walking for 5 km. ) Was listened to in a four-level evaluation, and an average value of rank 2 or less was used as an index of good flexibility.
Rank 1: Good flexibility Rank 2: Slightly lacking Rank 3: Rugged feeling Rank 4: Rigid feeling Remarkable At the same time, ankle fatigue (vibration absorption, shock absorption) was heard on a four-point scale and averaged. However, a rank of 2 or lower was used as an index for good ankle fatigue.
Rank 1: Ankle fatigue Only Rank 2: Ankle fatigue Somewhat Rank 3: Ankle fatigue Yes Rank 4: Ankle fatigue Large (6) Molding processability Resin layers (B) and () prepared in Examples and Comparative Examples C) is used in the final production stage of the athletic shoe, the resin layer (C) is injection-molded 10 times, and the formability is evaluated in 4 stages. An average value of rank 2 or less is a good formability index. did.
Rank 1: Good mold releasability, non-stickiness (stickiness) Good Rank 2: Mold releasability, non-stickiness A little lacking Rank 3: Mold releasability, non-stickiness Poor Rank 4: Go mold release Type, non-stickiness Very bad

<Examples 1 to 10 and Comparative Examples 1 to 5>
Using a twin-screw extruder (bore diameter 46 mm, L / D = 46), the following components were mixed according to the formulation shown in Table 1, and then melt-kneaded at 220 ° C. to obtain a pelletized resin composition (B ) And (C) were obtained.

As a method for laminating the resin layer (B) on the base fabric (A), a T-type die single-screw extruder (caliber 40 mm, L / D = 24, 230 ° C.) is used, and the resin composition (B) is used as the base fabric. Extrusion lamination of (A) gave a sheet material (D).
After that, using the obtained sheet-shaped material (D), a 24-cm shoe-sized cover is created, inserted into a mold and attached, and then the resin composition (C) is put into an injection molding machine, and the melting temperature is 250 ° C. Insert injection was carried out to obtain a composite shoe by integrally molding the bottom material and the cover.

<Base cloth (A)>
A plain weave fabric having a basis weight of 82 g / m ² and a density of 0.4 g / cm ³ was used as a base fabric (A), using a 30-count yarn containing 60% cotton and 40% polyester.

<Thermoplastic elastomer (a)>
・ Component (a1)
Type: styrene-isoprene-styrene type triblock copolymer, content of vinyl bond 55 mol%, content of structural unit derived from vinyl aromatic compound 32% by mass
・ Component (a2)
Type: hydrogenated block copolymer of styrene-isoprene / butadiene-styrene type triblock copolymer, vinyl bond content 8 mol%, content of structural unit derived from vinyl aromatic compound 30% by mass

<Olefin resin (b)>
・ Component (b-1)
Type: Admer QF551 (trade name), manufactured by Mitsui Chemicals, maleic anhydride modified polyolefin / component (b-2)
Type: PH943B (trade name), Sun Allomer, random polypropylene, MFR = 21

<Softening agent (c)>
・ Component (d-1)
Type: Diana Process Oil PW-90 (trade name), Idemitsu Petrochemical Co., Ltd., paraffin oil, kinematic viscosity (40 ° C.): 95.5 mm ² / s, ring analysis paraffin: 71%, ring analysis naphthene: 29 %, Weight average molecular weight: 790
・ Component (d-2)
Type: YUBASE8J (trade name), SK (Korea), oil, kinematic viscosity (40 ° C.): 47 mm ² / s, molecular weight = about 500

<Non-olefin resin>
・ Component (d)
Type: Pandex T8180 (trade name), DIC Covestro Polymer, polyurethane, hardness 80A

  As shown in Tables 1 and 2, the resin composition comprises the styrene thermoplastic elastomer (a) of the present invention (a), the olefin resin (b), and the softening agent (c), and the vinyl bond in the component (a). The composites of Examples 1 to 9 each containing at least a resin layer (B) and a resin layer (C) whose content, softener (b) content and polyolefin resin (c) content are within specific ranges. Has excellent vibration damping property, bending resistance, adhesiveness and flexibility.

  As shown in Tables 1 and 2, in Comparative Example 1, the addition amount of the olefin resin (b), which is a component of the resin layer (C), was less than 10% by mass, and a composite was obtained in the same manner as in Example 1. However, the resulting composite had poor moldability.

  In Comparative Example 2, the addition amount of the olefin resin (c), which is a component of the resin layer (C), was set to exceed 30% by mass, and a composite was obtained in the same manner as in Example 1, but the obtained composite was As a result, the adhesiveness and molding processability deteriorated.

  In Comparative Example 3, the softening agent (c), which is a component of the resin layer (C), was added in an amount of less than 30% by mass, and a composite was obtained in the same manner as in Example 1, but the obtained laminate was bent. As a result, the flexibility and flexibility deteriorated.

  In Comparative Example 4, the loss coefficient (η) of the resin layer (C) was set to less than 0.1 and a composite body was obtained in the same manner as in Example 1. However, the obtained composite body had a result of worsening ankle fatigue. became.

  In Comparative Example 5, the vinyl bond content of the resin layer (C) was less than 35 mol%, and a composite was obtained in the same manner as in Example 1, but the obtained composite resulted in worse ankle fatigue. .

  In Comparative Example 6, the addition amount of the olefin resin (b), which is a component of the resin layer (B), was more than 10% by mass, and a composite was obtained in the same manner as in Example 1, but the obtained composite was As a result, bending resistance and flexibility deteriorated.

  In Comparative Example 7, the addition amount of the non-olefin resin (d), which is a component of the resin layer (B), was set to exceed 30% by mass, and a composite was obtained in the same manner as in Example 1, but the obtained composite was obtained. Resulted in poor adhesiveness and moldability.

  In Comparative Example 8, the softener (c), which is a component of the resin layer (B), was added in an amount of more than 30% by mass to obtain a composite in the same manner as in Example 1, but the obtained composite was bonded. As a result, the sex deteriorates.

  In Comparative Example 9, the loss coefficient (η) of the resin layer (B) was set to less than 0.1, and a composite was obtained in the same manner as in Example 1. However, the obtained composite showed that the fatigue of the ankle deteriorates. became.

  In Comparative Example 10, the vinyl bond content of the resin layer (B) was less than 35 mol% and a composite was obtained in the same manner as in Example 1. However, the obtained composite resulted in deterioration of ankle fatigue. .

Claims (5)

A composite comprising a sheet material (D) and a resin layer (C), wherein the sheet material (D) comprises a base cloth (A) and a resin layer (B),
The resin layer (B) and the resin layer (C) are respectively
(A) a polymer block (X) composed of structural units derived from at least one vinyl aromatic compound and a polymer block (Y) composed of structural units derived from at least one conjugated diene compound A block copolymer comprising and / or a thermoplastic elastomer which is a hydrogenated product of the block copolymer,
(B) containing at least an olefin resin and (c) a softening agent,
The resin layer (B) has a content of the olefin resin (b) in the resin layer (B) of 10% by mass or less, a content of the softening agent (c) of 30% by mass or less, and a loss factor. (Η) is 0.1 or more, and the resin layer (C) has a content of the olefin resin (b) in the resin layer (C) of more than 10% by mass and a content of the softening agent (c). Is more than 30% by mass, and the loss factor (η) is 0.1 or more.   The thermoplastic elastomer (a) has a content of 3,4-bond units and 1,2-bond units in the structural unit derived from isoprene and / or butadiene in the thermoplastic elastomer (a) (hereinafter, vinyl bond content). A thermoplastic elastomer (a1) whose content is 45 mol% or more, or a mixture of the thermoplastic elastomer (a1) and a thermoplastic elastomer (a2) having a vinyl bond content of less than 45 mol%. And the vinyl bond content in the mixture is 35 mol% or more.   The composite according to claim 1 or 2, wherein the base fabric (A) is at least one selected from the group consisting of woven fabric, non-woven fabric, and composite fabric.   The composite according to claim 1, wherein the composite is an insert injection molded product. A method for producing the composite according to any one of claims 1 to 4, comprising:
1) a step of impregnating or laminating the resin composition (B) constituting the resin layer (B) on the base fabric (A) to obtain a sheet material (D), and 2) at least one of the sheet material (D) A method, which comprises a step of insert-injecting a resin composition (C) constituting the resin layer (C) into the part.