JP2011110105A - Sheet for shoe sole, and shoe sole using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shoe sole forming sheet that is useful for efficiently joining a crosslinked rubber layer as a stud and a thermoplastic elastomer layer as a sole. <P>SOLUTION: The sheet is made of a resin component (A) that contains polyamide resin (a) and having an amino group concentration of not less than 10 mmol/kg and a flexural modulus of not less than 300 MPa according to ISO178. The polyamide resin (a) may contain a polyamide resin having a melting point of not less than 165°C with a prescribed concentration (e.g., 30 wt% or more) with respect to the entire polyamide resin (a). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sheet suitable for forming a shoe sole, a shoe sole using the sheet (or a composite molded product for a shoe sole), and a method for producing the shoe sole.

  As a member for a shoe sole, a soft material obtained by crosslinking natural rubber or synthetic rubber is frequently used from the viewpoint of grip performance and wear resistance. The components of the shoe are broadly divided into the upper (the part that wraps the foot), the midsole (the part that exhibits cushioning properties), and the shoe sole (the part that contacts the ground). And a sole (a part other than a stud on the shoe sole). Rubber is generally useful for the stud from the viewpoint of grip performance and wear resistance, and thermoplastic elastomer is generally useful for the sole from the viewpoint of spring performance.

  Conventionally, with respect to the adhesion between the stud and the sole, since the adhesion area thereof is small and it is difficult to obtain sufficient adhesion strength by a normal adhesion method, the stud and the sole are usually both rubber or thermoplastic. Often it was an elastomer. However, when both are rubber, since the specific gravity of rubber is large, there has been a problem that the weight of shoes becomes heavy and it is difficult to obtain spring performance. On the other hand, when both are thermoplastic elastomers, there have been problems such as fusing by frictional heat on artificial grass grounds and gymnasiums, and slipping easily on wet road surfaces.

  Therefore, various methods have been tried to perform composite molding so that both members have sufficient adhesive strength even if the stud and the sole are made of different materials. Composite molding by direct bonding without using an adhesive is one of the effective methods, so that even if the stud is made of rubber and the sole is made of a thermoplastic elastomer, a shoe sole having sufficient adhesive strength for both members can be obtained. Became possible.

  For example, JP-A-8-294933 (Patent Document 1) discloses a polyurethane block (for example, polyether urethane, polyester urethane) and a polyamide-based polymer (for example, a polyamide block such as polyether ester amide) and a polyether block. In the method of multi-color molding of the thermoplastic resin (I) selected from among the polymers having rubber) on the rubber (II), after the rubber surface is halogenated, the thermoplastic resin is subjected to compression molding or injection molding. A method for color molding is disclosed. And in this document, the composite material obtained by this method is used for manufacturing athletic shoes having a sole made of polyamide elastomer to which a rubber stud or a rubber heel for preventing the wear of the sole is fixed. It is described.

  JP-A-8-51741 (Patent Document 2) discloses a thermoplastic polymer in which a vulcanized elastomer containing a carboxylic acid group contains a block (for example, polyether ester, polyurethane ether, polyurethane ester, polyurethane ether ester). Etc.) are disclosed. And this literature describes that this composite structure is useful as a shoe sole of an athletic shoe.

  However, since composite molding of rubber and thermoplastic elastomer generally uses methods involving heating and pressurization, such as injection molding and compression molding, manufacturing defects due to deformation on the thermoplastic elastomer side are particularly problematic. When the conditions of heating and pressurization are relaxed, there are problems that the vulcanization time of the rubber is extended and that the adhesion between the rubber and the thermoplastic elastomer is poor. There is no description on how to solve the problem. In addition, the method of Patent Document 1 requires a pretreatment step of preliminarily halogenating the rubber surface, which is problematic when it is desired to shorten the process time.

  On the other hand, Japanese Patent Laid-Open No. 2000-41702 (Patent Document 3) discloses that an outsole member composed of a synthetic rubber outsole design portion and a thermoplastic elastomer sheet joined and integrated is used for molding a shoe sole body. A shoe sole in which a three-layer structure is formed by simultaneously integrally molding the outsole member and the sole body by injection molding of a thermoplastic elastomer is disclosed. In this document, such a sole is added by placing an outsole design member obtained by die-cutting a kneaded sheet of uncrosslinked synthetic rubber in an outsole design recess of a preformed shoe sole mold. After the pressure heating, the outsole design member opens the mold at the initial stage of cross-linking and installs a thermoplastic elastomer sheet having a shape substantially matching the outer shape of the outsole design recess, and then added again. An outsole member in which the synthetic rubber design portion and the thermoplastic elastomer sheet are integrally formed by pressure heating is formed, and the outsole member is trimmed into a design concave shape of an injection mold for outsole, and then used for outsole It is described that a thermoplastic elastomer for forming a shoe sole body can be manufactured by injection molding after being placed so as to match a design concave portion of an injection mold and clamped.

  However, this document does not describe any method for solving the problems in the composite molding as described above. In this document, when the outsole design portion and the outsole member are joined and integrated, the synthetic rubber crosslinking process is interrupted to open the mold, and after the thermoplastic elastomer sheet is installed, the mold is closed again. A process of complex integration is required, which is a problem when work efficiency is required. In addition, when the thermoplastic elastomer for forming the sole body is injection-molded on the outsole member, it is substantially fused as a resin for the outsole member and a thermoplastic elastomer so as to be thermally fused (melted and integrated). It is necessary to use the same kind of resin, and the combination of resin materials is limited.

JP-A-8-294933 (Claims, paragraph [0001]) JP-T 8-51741 (Claims, page 12, lines 2-5) Japanese Unexamined Patent Publication No. 2000-41702 (Claims, paragraphs [0025] to [0029])

  Accordingly, an object of the present invention is to use a sheet useful for efficiently joining a crosslinked rubber layer as a stud and a thermoplastic elastomer layer as a sole (sole (formation) sheet), and using this sheet. Another object of the present invention is to provide a composite molded article for a shoe sole (or a shoe sole) and a method for producing the composite molded article for a shoe sole.

  Another object of the present invention is a sheet useful for joining a stud and a sole without deformation with high workability, and a composite product for a shoe sole (or a shoe sole) obtained using the sheet. And a method of manufacturing the composite molded article for a shoe sole.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a specific amino group concentration and flexural elasticity are present between a crosslinked rubber layer as a stud (member) and a thermoplastic elastomer layer as a sole (member). When a sheet formed of a specific resin component having a ratio is interposed, unexpectedly, the cross-linked rubber layer does not have to be subjected to surface treatment (for example, halogenation treatment), and is complicated as in Patent Document 3. Without requiring a method, it is possible to achieve both prevention or suppression of deformation in the sheet or thermoplastic elastomer layer and joining of both layers, and by using such a sheet, a wide range of rubbers and thermoplastics can be obtained. The present inventors have found that a crosslinked rubber layer and a thermoplastic elastomer layer can be bonded in combination with an elastomer, thereby completing the present invention.

  That is, the sheet of the present invention (shoe sole sheet) is interposed between a crosslinked rubber layer as a stud and a thermoplastic elastomer layer as a sole in direct contact with these layers, and is a composite molding for a shoe sole. A sheet for forming a body (or one surface on which a crosslinked rubber layer as a stud is directly formed and another surface on which a thermoplastic elastomer layer as a sole is directly formed, and a composite molding for a shoe sole Sheet for forming a body). And this sheet | seat is comprised with the resin component (A) containing a polyamide resin (a), and the said resin component (A) has a bending elastic modulus of 300 MPa or more by the amino group concentration of 10 mmol / kg or more and ISO178.

  The polyamide resin (a) may be composed of at least one selected from polyamide (aliphatic polyamide, alicyclic polyamide, etc.) and polyamide elastomer. The polyamide resin (a) may contain a polyamide resin having a relatively high melting point (for example, a melting point of 165 ° C. or higher), and the ratio of the polyamide resin having the high melting point is the entire polyamide resin (a). It may be about 30% by weight or more.

  The resin component (A) (or polyamide resin (a)) may typically be any of the following (1) to (3).

(1) Polyamide resin alone having an amino group concentration of 10 mmol / kg or more, a melting point of 165 ° C. or more, and a flexural modulus of elasticity of 300 MPa or more according to ISO 178 (2) A resin composition composed of a plurality of polyamides having a melting point of 165 ° C. or more Polyamide resin composition containing 30% by weight or more of the polyamide and satisfying an amino group concentration of 10 mmol / kg or more as a whole and a bending elastic modulus of 300 MPa or more according to ISO 178. (3) Resin composition comprising polyamide and polyamide elastomer And 30% by weight or more of the polyamide and / or the polyamide elastomer has a melting point of 165 ° C. or more, and satisfies an amino group concentration of 10 mmol / kg or more as a whole and a bending elastic modulus of 300 MPa or more according to ISO 178. , The resin component (A) (or polyamide resin (a)) may be a polyamide resin composition (3), and among these polyamide resin compositions (3), the amino group concentration of the polyamide elastomer is 10 mmol. / Kg may be included.

  The sheet may further contain a filler. The thickness of the sheet may be about 0.1 to 0.7 mm.

  The present invention comprises the sheet, a crosslinked rubber layer as a stud directly formed on one surface of the sheet, and a thermoplastic elastomer layer as a sole directly formed on the other surface of the sheet. Also included are composite molded articles for shoe soles (or shoe soles).

  In such a composite molded article for shoe sole, the crosslinked rubber layer may be formed by crosslinking of an uncrosslinked rubber composition containing uncrosslinked rubber and peroxide (or unvulcanized rubber composition). May be a crosslinked product. The uncrosslinked rubber composition may further contain a crosslinking aid.

  The thermoplastic elastomer layer may be composed of, for example, at least one selected from a polyurethane elastomer and a polyamide elastomer, and may be composed of a polyurethane elastomer.

  Further, the present invention includes a method for producing a composite molded article for a shoe sole by directly forming a crosslinked rubber layer on one surface of the sheet and a thermoplastic elastomer layer on the other surface. In such a method, typically, the melted uncrosslinked rubber composition is brought into contact with one surface of the sheet placed in a mold, and the uncrosslinked rubber composition is crosslinked under heating to form the above-mentioned You may manufacture a composite molded object by forming a crosslinked rubber layer. In such a method, in particular, the crosslinked rubber layer may be formed without opening the mold.

  In the method, the sheet (or polyamide resin (a) or resin component (A)) may be crosslinked without melting. Typically, in the method, the sheet contains a polyamide resin having a melting point of 165 ° C. or higher of 30% by weight or more of the polyamide resin (a), and a temperature lower than the melting point of the polyamide resin having a melting point of 165 ° C. or higher [for example, Crosslinking may be performed at 150 ° C. or higher (for example, 150 to 190 ° C. and lower than the melting point of polyamide resin having a melting point of 165 ° C. or higher by 5 ° C. or higher). In the present invention, since a sheet composed of the specific resin component as described above is used, the rubber layer (and further the thermoplastic elastomer layer) can be firmly adhered without necessarily melting the sheet. It is possible to efficiently prevent or suppress the deformation.

  The sheet of the present invention (shoe sole sheet) is useful for efficiently joining a crosslinked rubber layer as a stud and a thermoplastic elastomer layer as a sole. Specifically, by using such a sheet, the stud and the sole can be joined efficiently without being deformed. In particular, when the sheet of the present invention is used, integral molding with the crosslinked rubber layer is possible without using a complicated method as in Patent Document 3, and the crosslinked rubber layer is surface-treated (for example, halogenated). Therefore, it is possible to join the stud and the sole without deforming them with high workability.

FIG. 1 is a photograph of the rubber mold used in the examples.

[Sheet]
The sheet | seat of this invention is comprised by the resin component (it may be called a resin component (A) etc.) containing a polyamide resin (it may be called a polyamide resin (a)). And the resin component which comprises such a sheet | seat has specific amino group density | concentration and a bending elastic modulus, and the sheet | seat of this invention is especially useful as a sheet | seat for shoe soles so that it may mention later.

  Examples of the polyamide resin include polyamide and polyamide elastomer.

  Examples of the polyamide include aliphatic polyamide resins, alicyclic polyamide resins, and aromatic polyamide resins. The polyamide may be a homopolyamide or a copolyamide.

Among the aliphatic polyamide resins, homopolyamides include aliphatic diamine components (for example, C _4-16 alkylene diamines such as tetramethylene diamine, hexamethylene diamine, and dodecane diamine, preferably C _6-14 alkylene diamine, more preferably C _6-12 alkylene diamine) and an aliphatic dicarboxylic acid component (for example, C _4-20 alkane dicarboxylic acid such as adipic acid, sebacic acid, dodecanedioic acid, preferably C _5-16 alkane dicarboxylic acid, more preferably C _{6 -14} alkanedicarboxylic acid) etc.], or lactam [lactams such as ε-caprolactam, ω-laurolactam and the like having about 4 to 20 carbon atoms (preferably 4 to 16 carbon atoms)] or aminocarboxylic acid (For example, ω-aminoundecanoic acid Which _{C 4-20} aminocarboxylic acids, preferably a homo- or copolyamide, and an aliphatic diamine component, aliphatic dicarboxylic acid component of the _{C 4-16} aminocarboxylic acids, more preferably such _{C 6-14} aminocarboxylic acids), Copolyamides with lactams or aminocarboxylic acids are included.

  Specific examples of the aliphatic polyamide include polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 613, polyamide 1010, polyamide 6, polyamide 11, polyamide 12, polyamide 611, polyamide 612, polyamide 66/11, and polyamide. 66/12, polyamide 6/12/612, and the like.

  Preferred aliphatic polyamides include polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 613, polyamide 1012, polyamide 1010, polyamide 1212 and the like.

  Examples of the alicyclic polyamide resin include a homopolyamide or a copolyamide having at least one selected from an alicyclic diamine component and an alicyclic dicarboxylic acid component as constituents, such as a diamine component and a dicarboxylic acid component. Among them, an alicyclic polyamide obtained by using an alicyclic diamine and / or an alicyclic dicarboxylic acid as at least a part of the components can be used. In particular, as the diamine component and dicarboxylic acid component, it is preferable to use the aliphatic diamine component and / or aliphatic dicarboxylic acid component exemplified above together with the alicyclic diamine component and / or alicyclic dicarboxylic acid component. Such an alicyclic polyamide resin has high transparency and is known as a so-called transparent polyamide.

Examples of the alicyclic diamine component include diaminocycloalkanes such as diaminocyclohexane (diamino C _5-10 cycloalkanes); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, Bis (aminocycloalkyl) alkanes such as 2-bis (4′-aminocyclohexyl) propane [bis (aminoC _5-8 cycloalkyl) C _1-3 alkane etc.]; hydrogenated xylylenediamine and the like. The alicyclic diamine component has a substituent such as an alkyl group (C _1-6 alkyl group such as methyl group or ethyl group, preferably C _1-4 alkyl group, more preferably C _1-2 alkyl group). It may be. Examples of the alicyclic dicarboxylic acid include cycloalkane dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylic acid (C _5-10 cycloalkane-dicarboxylic acid and the like).

  Of the alicyclic polyamide resins, a condensate (homo or copolyamide) of an aliphatic dicarboxylic acid component and an alicyclic diamine component is preferable. Typical alicyclic polyamide resins (alicyclic polyamide resins having alicyclic diamine and aliphatic dicarboxylic acid as constituent components) include alicyclic polyamides represented by the following formula (1). .

(In the formula, X represents a direct bond, an alkylene group or an alkenylene group, R ¹ and R ² represent the same or different substituents, m and n are 0 or an integer of 1 to 4, and p and q are 1) Indicates an integer greater than or equal to
In the formula (1), examples of the alkylene group (or alkylidene group) represented by the group X include C _1-6 such as methylene, ethylene, ethylidene, propylene, propane-1,3-diyl, 2-propylidene, and butylene. An alkylene group (or alkylidene group), preferably a C _1-4 alkylene group (or alkylidene group), more preferably a C _1-3 alkylene group (or alkylidene group). Further, examples of the alkenylene group represented by the group X include C _2-6 alkenylene groups such as vinylene and propenylene, preferably C _2-4 alkenylene groups.

Examples of the substituents R ¹ and R ² include hydrocarbon groups such as alkyl groups. Examples of the alkyl group include C _1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups, preferably C _1-4 alkyl groups, and more preferably C _1-2 alkyl groups.

The numbers m and n of R ¹ and R ² can be selected from 0 or an integer of 1 to 4, but are usually 0 or an integer of 1 to 3, preferably 0 or an integer of 1 to 2, and more preferably 0 or 1 It may be. Further, the substitution positions of the substituents R ¹ and R ² can usually be selected from the 2-position, the 3-position, the 5-position, and the 6-position with respect to the amide group, and preferably the 2-position and the 6-position.

  In the formula (1), p is, for example, 4 or more (for example, about 4 to 30), preferably 6 or more (for example, about 6 to 20), and more preferably 8 or more (for example, about 8 to 15). There may be. In the formula (1), q (degree of polymerization) is, for example, 5 or more (for example, about 10 to 1000), preferably 10 or more (for example, about 30 to 800), more preferably 50 or more (for example, About 100 to 500).

  The aromatic polyamide resin includes a polyamide in which at least one of the aliphatic diamine component and the aliphatic dicarboxylic acid component is an aromatic component, for example, a polyamide [MXD] in which the diamine component is an aromatic component. -6 and other aromatic diamines (metaxylylenediamine etc.) and aliphatic dicarboxylic acid condensates], polyamides whose dicarboxylic acid component is an aromatic component [aliphatic diamine (trimethylhexamethylenediamine etc.) and aromatic Condensates with dicarboxylic acids (terephthalic acid, isophthalic acid, etc.)] and the like.

  The aromatic polyamide resin may be a wholly aromatic polyamide (aramid) of polyamide [poly (m-phenyleneisophthalamide) or the like] in which the diamine component and the dicarboxylic acid component are aromatic components.

  The polyamide resin may further be a modified polyamide such as a polyamide having dimer acid as a dicarboxylic acid component or a polyamide having a branched chain structure introduced therein.

  Preferred polyamides include aliphatic polyamides (particularly polyamide 12), alicyclic polyamides, and the like.

  Polyamides may be used alone or in combination of two or more.

  In many cases, the flexural modulus of polyamide according to ISO 178 is relatively large compared to polyamide elastomer and the like, for example, 300 MPa or more (for example, 500 MPa or more), preferably 600 MPa or more (for example, about 700 to 5000 MPa), and more preferably. May be 700 MPa or more (for example, about 800 to 3500 MPa), particularly 900 MPa or more (for example, about 1000 to 3000 MPa). Therefore, when the resin component (A) is composed of at least polyamide, it is easy to adjust the flexural modulus to a range that satisfies the scope of the present invention.

  As described above, the polyamide resin includes a polyamide elastomer. As such a polyamide elastomer (polyamide block copolymer), a polyamide block copolymer comprising a polyamide as a hard segment (or hard block) and a soft segment (or soft block), for example, a polyamide-polyether block copolymer. Examples thereof include a polymer, a polyamide-polyester block copolymer, and a polyamide-polycarbonate block copolymer.

A typical polyamide elastomer is a polyamide-polyether block copolymer. In the polyamide-polyether block copolymer, as the polyether (polyether block), for example, polyalkylene glycol (for example, poly C _2-6 alkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, preferably Poly _C2-4 alkylene glycol) and the like.

  Examples of such a polyamide-polyether block copolymer include a block copolymer obtained by copolycondensation of a polyamide block having a reactive end group and a polyether block having a reactive end group. Ether amide [for example, a block copolymer of a polyamide block having a diamine end and a polyalkylene glycol block having a dicarboxyl end (or a polyoxyalkylene block), a polyamide block having a dicarboxyl end and a polyalkylene glycol having a diamine end Block (or block copolymer with polyoxyalkylene block, etc.)], polyether ester amide [polyamide block having dicarboxyl terminal and polyalkylene glycol having dihydroxy terminal] Block (or polyoxyalkylene block) block copolymers], and others. Note that commercially available polyamide elastomers usually have few amino groups.

  Polyamide elastomers may be used alone or in combination of two or more.

  In the polyamide elastomer (polyamide block copolymer), the number average molecular weight of the soft segment (polyether block, polyester block, polycarbonate block, etc.) can be selected from a range of about 100 to 10000, preferably 300 to 6000 (for example, 300 to 5000), more preferably 500 to 4000 (for example, 500 to 3000), particularly about 1000 to 2000.

  In the polyamide block copolymer, the ratio (weight ratio) between the polyamide block (polyamide segment) and the soft segment block is, for example, the former / the latter = 95 / 5-20 / 80, preferably 90 / 10-30. / 70, more preferably 80/20 to 40/60, particularly about 75/25 to 50/50 (for example, 73/27 to 55/45).

  The Shore D hardness of the polyamide elastomer may be, for example, 40 to 80, preferably 45 to 75, and more preferably about 50 to 65. The Shore D hardness can be measured according to ASTM D2240.

  The number average molecular weight of the polyamide resin may be, for example, about 8000 to 200000, preferably about 9000 to 150,000, and more preferably about 10,000 to 100,000.

  The melting point of the polyamide resin may be, for example, about 80 ° C to 300 ° C, preferably about 90 ° C to 280 ° C, and more preferably about 100 ° C to 260 ° C. In particular, in the present invention, as described later, a relatively high melting point [for example, a melting point of 165 ° C. or higher (for example, 165 to 280 ° C., preferably 170 to 260 ° C., more preferably about 175 to 250 ° C.), particularly a melting point 170 It is preferable to use a resin component containing at least a polyamide resin (for example, aliphatic polyamide, etc.) at or above (for example, 175 to 260 ° C.). Examples of such a high melting point polyamide resin include polyamides (aliphatic polyamides such as polyamide 612, polyamide 12, and polyamide 1012, alicyclic polyamides, etc.) and polyamides having a relatively small proportion of soft segments. An elastomer etc. are mentioned. High melting point polyamides may be used alone or in combination of two or more. Although depending on the ratio and type of hard segment, the melting point of polyamide elastomer (for example, polyamide elastomer having polyamide 12 as a hard segment) may be relatively low (for example, melting point less than 165 ° C.). Many.

  The ratio of the polyamide resin having such a high melting point (for example, a melting point of 165 ° C. or more) is, for example, 20% by weight or more (for example, about 25 to 100% by weight), preferably 30%, based on the entire polyamide resin (a). % By weight or more (for example, about 35 to 100% by weight), more preferably 40% by weight or more (for example, about 45 to 100% by weight), and usually 50% by weight or more (for example, about 55 to 100% by weight), In particular, it may be 60% by weight or more (preferably 70% by weight or more).

  In addition, when the polyamide resin (a) includes a plurality of polyamide resins having a melting point of 165 ° C. or higher, the above ratio is the total amount thereof. Further, when a polyamide resin having a melting point of 165 ° C. or higher and a polyamide resin (polyamide elastomer or the like) having a melting point of less than 165 ° C. are combined, these ratios are, for example, the former / the latter (weight ratio) = 99/1 to 20/80. (For example, 98/2 to 25/75), preferably 97/3 to 30/70 (for example, 95/5 to 35/65), more preferably 93/7 to 40/60 (for example, 90/10 to 10/10) 45/55), especially 85/15 to 50/50 (for example, 80/20 to 55/45), and usually 95/5 to 60/40 (for example, 93/7 to 65/35, Preferably, it may be about 90/10 to 70/30).

  Polyamide resins may be used alone or in combination of two or more. When two or more types of polyamide resins are combined (for example, a combination of two or more types of polyamides, one or two or more types of polyamides and one or two or more types of polyamide elastomers), the amino group concentration and the flexural modulus (as a result, It is easy to control the adhesiveness and deformability with rubber and / or thermoplastic elastomer. In particular, polyamide elastomers generally have a low flexural modulus and melting point, and are easy to improve adhesion while being easily deformed. Therefore, it is easy to achieve both good adhesion and deformability in combination with polyamide.

  The resin component which comprises a sheet | seat may be comprised only with a polyamide resin (a), and may contain other resin in addition to the polyamide resin (a). Examples of other resins include, but are not limited to, thermoplastic elastomers other than polyamide resins, such as polyurethane elastomers, polyester elastomers, polyolefin elastomers, polystyrene elastomers, fluorine elastomers, and ethylene-vinyl acetate copolymers. . Other resins may be used alone or in combination of two or more.

  When other resin is included, the ratio of the other resin is, for example, 100 parts by weight or less (for example, about 1 to 80 parts by weight), preferably 70 parts by weight or less (100 parts by weight with respect to 100 parts by weight of the polyamide resin (a). For example, it may be about 2 to 60 parts by weight), more preferably 50 parts by weight or less (for example, about 2 to 40 parts by weight), particularly 30 parts by weight or less (for example, about 3 to 20 parts by weight).

  The sheet of the present invention is characterized in that a resin component having a specific amino group concentration and a flexural modulus is used as the resin component (A). By comprising such a specific resin component, it is possible to obtain a sheet having excellent adhesion to both the rubber layer and the thermoplastic elastomer layer, although the resistance to deformation is relatively strong.

  The amino group concentration of such a resin component (A) may be 10 mmol / kg or more (for example, about 10 to 300 mmol / kg), for example, 15 mmol / kg or more (for example, about 25 to 200 mmol / kg), Preferably 30 mmol / kg or more (for example, about 35 to 150 mmol / kg), more preferably 40 mmol / kg or more (for example, about 45 to 120 mmol / kg), particularly 50 mmol / kg or more (for example, about 55 to 100 mmol / kg). In particular, it may be 60 mmol / kg or more (for example, about 62 to 100 mmol / kg), usually 10 to 100 mmol / kg (for example, 12 to 90 mmol / kg, preferably 15 to 80 mmol / kg, more preferably 20-70 mmol / kg) It may be.

  The amino group concentration is the concentration relative to the entire resin component (A). For example, when the resin component (A) is composed of a plurality of polyamide resins, the amino group concentration of the entire polyamide resin composition is as follows. It is a group concentration, and all polyamide resins may have the amino group concentration, and some polyamide resins may have the amino group concentration. The amino group is usually contained in the polyamide resin itself, but the amino group concentration can also be adjusted by adding a compound having an amino group (a compound not a polyamide resin) to the resin component (A).

  Examples of compounds having amino groups (amino group-containing compounds having a high amino group concentration and a relatively low molecular weight) include monoamines (aliphatic, alicyclic, aromatic monoamines having 2 to 24 carbon atoms), polyamines (for example, diamines). (Such as aliphatic diamines, alicyclic diamines and aromatic diamines exemplified above), polyalkylene polyamines such as diethylenetriamine and triethylenetetramine, etc.], polyamide oligomers (specifically, free at molecular terminals and / or branched chains, etc.) And polyamide oligomers having amino groups). These compounds having an amino group may be used alone or in combination of two or more.

  The proportion of the compound having an amino group is, for example, 0.01 to 30 parts by weight, preferably 0.02 to 20 parts by weight, based on 100 parts by weight of the polyamide resin (specifically, the base polyamide resin). Preferably, it may be about 0.03 to 15 parts by weight, usually 10 parts by weight or less [eg, 0.05 to 8 parts by weight, preferably about 5 parts by weight or less (eg, 0.1 to 3 parts by weight). ].

  Of these compounds having an amino group, a polyamide oligomer is particularly preferable. The polyamide oligomer means a low molecular weight polyamide, and as the polyamide oligomer, a conventional method, for example, using the above-exemplified polyamide components (diamine component, dicarboxylic acid component, lactam, aminocarboxylic acid, etc.), Polyamide having a relatively low molecular weight obtained by adjusting the monomer formulation, polycondensation conditions, etc. can be used.

  The number average molecular weight of the polyamide oligomer is, for example, less than 8000 (for example, 200 to 7500), preferably 500 to 7000, more preferably about 1000 to 5000, and usually about 2000 to 6500 (for example, 2500 to 6000). There may be. The amino group of the polyamide oligomer may be at least at one end of the main chain, may be at both ends of the main chain, or may be at a branched chain.

  The amino group concentration of the polyamide oligomer is, for example, 100 to 4000 mmol / kg, preferably 120 to 3000 mmol / kg, more preferably 200 to 2000 mmol / kg, and may usually be about 150 to 1500 mmol / kg.

  In particular, the ratio (use ratio) of the polyamide oligomer is 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably about 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin. It may be.

  As described above, the resin component (A) has an amino group. Among these amino groups, the amino group contained in the polyamide resin (and further the polyamide oligomer) may be located at any of the molecular chain terminal, the side chain, etc., but from the viewpoint of adhesiveness, It is preferably an amino group contained at the chain end. In addition, as described above, the polyamide resin itself often has an amino group. Among them, when a polyamide elastomer having an amino group at a predetermined concentration (10 mmol / kg or more) is used, the adhesiveness is increased. And further advantageous in terms of prevention or suppression of deformation.

  The flexural modulus of the resin component (A) according to ISO 178 may be 300 MPa or more (for example, about 300 to 5000 MPa), preferably 400 MPa or more (for example, about 450 to 3500 MPa), and more preferably 500 MPa or more (for example, , About 550 to 3000 MPa), particularly 600 MPa or more (for example, about 600 to 2800 MPa), and usually about 500 to 3000 MPa (for example, 600 to 2500 MPa). The flexural modulus is the concentration relative to the entire resin component (A), similar to the amino group concentration. For example, when the resin component (A) is composed of a plurality of polyamide resins, It is a bending elastic modulus of the whole resin composition containing this polyamide resin.

  The typical resin component (A) (or polyamide resin (a)) includes the following (1) to (3).

(1) A polyamide resin alone having an amino group concentration of 10 mmol / kg or more, a melting point of 165 ° C. or more, and a flexural modulus according to ISO 178 of 300 MPa or more (for example, polyamide alone, polyamide elastomer alone, etc.)
When the polyamide resin is polyamide alone, the flexural modulus according to ISO 178 is relatively high as described above [for example, 600 MPa or more (for example, 700 to 5000 MPa, preferably 800 to 3500 MPa, more preferably 1000 It is about ˜3000 MPa).

  On the other hand, when the polyamide resin is a polyamide elastomer alone, the flexural modulus according to ISO 178 is relatively small within a range satisfying the range of the present invention [for example, less than 600 MPa (for example, about 300 to 580 MPa), preferably 550 MPa or less (for example, about 310 to 530 MPa), more preferably 500 MPa or less (for example, about 320 to 480 MPa), particularly 450 MPa or less (for example, about 330 to 420 MPa). When such a flexural modulus is relatively small, it has a very high melting point [for example, a melting point of 180 ° C. or higher (for example, 180 to 280 ° C., preferably 185 to 250 ° C., more preferably about 190 to 220 ° C.) A polyamide resin (especially a polyamide elastomer) having a melting point of 190 ° C. or higher, more preferably 200 ° C. or higher may be suitably used.

(2) A resin composition composed of a plurality of polyamides, comprising a polyamide having a melting point of 165 ° C. or higher in a proportion of 30% by weight or more, and an amino group concentration of 10 mmol / kg or more as a whole and a flexural modulus of 300 MPa or more according to ISO178 Note that, in the plurality of polyamides, all the polyamides may have an amino group of 10 mmol / kg or more, and may contain a polyamide having an amino group concentration of less than 10 mmol / kg. .

  Representative resin composition (2) includes (2a) a resin composition comprising a plurality of polyamides having a melting point of 165 ° C. or higher and a flexural modulus of 300 MPa or higher (particularly 600 MPa or higher) according to ISO 178, and the amino group as a whole A polyamide resin composition having a concentration of 10 mmol / kg or more is included.

(3) A resin composition comprising a polyamide (one or more polyamides) and a polyamide elastomer (one or more polyamide elastomers), wherein 30% by weight or more of the polyamide and / or the polyamide elastomer has a melting point. Polyamide resin composition satisfying an amino group concentration of 10 mmol / kg or more as a whole and a flexural modulus of 300 MPa or more according to ISO 178 in the above polyamide resin composition, the polyamide and the polyamide elastomer all have 10 mmol of amino groups. / Kg or more, and may contain a polyamide or polyamide elastomer having an amino group concentration of less than 10 mmol / kg. In particular, it is preferable to use a polyamide elastomer having an amino group concentration of 10 mmol / kg or more as the polyamide elastomer.

  The typical resin composition (3) includes the following resin compositions (3a) to (3d).

(3a) one or two or more polyamides (a1) having a melting point of 165 ° C. or higher and a bending elastic modulus of 300 MPa or higher (particularly 600 MPa or higher) according to ISO 178, and a melting point of less than 165 ° C. and a bending elastic modulus of ISO 178 of less than 300 MPa 1 or A polyamide resin composition composed of two or more polyamide elastomers (a2), comprising the polyamide (a1) in a proportion of 30% by weight or more, as a whole, having an amino group concentration of 10 mmol / kg or more and flexural elasticity according to ISO178 Polyamide resin composition satisfying a rate of 300 MPa or more (3b) One or more polyamides (b1) having a melting point of 165 ° C. or higher and a flexural modulus of 300 MPa or higher (particularly 600 MPa or higher) according to ISO 178, a melting point of 165 ° C. or higher and ISO 178 by A polyamide resin composition composed of one or more polyamide elastomers (b2) having a flexural modulus of less than 300 MPa, and as a whole satisfies an amino group concentration of 10 mmol / kg or more and a flexural modulus of 300 MPa or more according to ISO178. Polyamide resin composition (3c) One or more polyamides (c1) having a melting point of 165 ° C. or higher and a bending elastic modulus of 300 MPa or higher (particularly 600 MPa or higher) according to ISO 178, a melting point of less than 165 ° C. and a bending elastic modulus of 300 MPa or higher according to ISO 178 A polyamide resin composition comprising 1 or 2 or more polyamide elastomers (c2), wherein the polyamide (c1) is contained in a proportion of 30% by weight or more, and the amino group concentration as a whole is 10 mmol / kg or more. Polyamia to satisfy (3d) One or more polyamides (d1) having a melting point of 165 ° C. or higher and a bending elastic modulus of 300 MPa or higher (particularly 600 MPa or higher) according to ISO 178, a melting point of 165 ° C. or higher and a bending elastic modulus of 300 MPa or higher according to ISO 178 A polyamide resin composition composed of one or two or more polyamide elastomers (d2) having an amino acid concentration of 10 mmol / kg or more as a whole.

  Among the above (3) (or (3a) to (3d)), it is particularly preferable that the amino group concentration of the polyamide elastomer (or polyamide elastomer (a2) to (d2)) is 10 mmol / kg or more.

  The sheet of the present invention is a component other than the resin component (A), for example, filler (or reinforcing agent), stabilizer (ultraviolet absorber, antioxidant, heat stabilizer, etc.), as long as the effects of the present invention are not impaired. In addition, additives such as a colorant, a plasticizer, a lubricant, a flame retardant, and an antistatic agent may be included. The additives may be used alone or in combination of two or more. Among these, in particular, when a filler is added to the sheet, the bending elastic modulus of the sheet itself can be further improved.

  Examples of the filler (filler) include fibrous fillers and non-fibrous fillers (powder or plate-like fillers). Examples of fibrous fillers include organic fibers (natural fibers, etc.), inorganic fibers (glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, wollastonite, zirconia fibers, potassium titanate fibers, etc.). , Including metal fibers.

  Examples of non-fibrous fillers include mineral particles (talc, mica, calcined siliceous clay, kaolin, sericite, bentonite, smectite, clay, silica, quartz powder, glass beads, glass powder, glass flakes, Milled fiber, wollastonite (or wollastonite, etc.), boron-containing compounds (boron nitride, boron carbide, titanium boride, etc.), metal carbonates (magnesium carbonate, heavy calcium carbonate, light calcium carbonate, etc.), metals Silicate (calcium silicate, aluminum silicate, magnesium silicate, alumino magnesium silicate, etc.), metal oxide (magnesium oxide, etc.), metal hydroxide (aluminum hydroxide, calcium hydroxide, magnesium hydroxide, etc.), metal sulfate ( Calcium sulfate, barium sulfate, etc.), metal carbide ( Of silicon, aluminum carbide, and titanium carbide), metal nitride (aluminum nitride, silicon nitride, titanium nitride, etc.), white carbon, and various metal foils. These non-fibrous fillers can be used alone or in combination of two or more.

  The average fiber length of the fibrous filler may be, for example, about 0.1 to 10 mm, preferably about 0.3 to 7 mm, and more preferably about 0.5 to 5 mm. The average fiber diameter of the fibrous filler may be, for example, about 0.1 to 50 μm, preferably about 0.5 to 30 μm, and more preferably about 1 to 10 μm. The average particle diameter of the non-fibrous filler (powdered filler) is, for example, 0.1 to 10 μm, preferably 0.3 to 5 μm, and more preferably about 0.5 to 5 μm.

  When an additive (non-resin component) is used, the proportion of the additive is 50 parts by weight or less (for example, 0.01 to 40 parts by weight), preferably 30 parts by weight with respect to 100 parts by weight of the resin component (A). Part or less (for example, 0.1 to 25 parts by weight), more preferably 20 parts by weight or less (for example, 1 to 18 parts by weight).

  In particular, when a filler is used, the ratio of the resin component (A) to the filler is, for example, the former / the latter (volume ratio) = 99/1 to 70/30 (for example, 99/1 to 75/25), preferably May be about 98/2 to 80/20 (for example, 97/3 to 85/15), more preferably about 96/4 to 90/10. The ratio of the resin component (A) to the filler is, for example, the former / the latter (weight ratio) = 99/1 to 40/60 (for example, 98/2 to 50/50), preferably 97/3 to 60. / 40 (for example, 96/4 to 70/30), more preferably about 95/5 to 75/25, and usually 99/1 to 80/20 (for example, 97/3 to 85/15). It may be a degree.

  The thickness of the sheet is not particularly limited, but may be, for example, 2 mm or less (for example, 0.05 to 1.5 mm), preferably 0.07 to 1 mm, and more preferably about 0.1 to 0.7 mm. Usually, it may be about 0.15 to 0.8 mm (for example, 0.2 to 0.75 mm). Since the sheet having a small thickness as described above can be sufficiently adhered according to the shape of the sole while maintaining its strength, the effect of direct bonding can be further enhanced. In addition, even if the resin component is relatively low in transparency, it is often possible to obtain a certain degree of light transmission, so that, for example, the design and color of the sole can be seen through the sheet. The variation in terms can be expanded.

  The sheet | seat of this invention can be obtained by sheet-molding the said resin component (Moreover, the composition containing an additive as needed) by a conventional method. The method for forming the sheet is not particularly limited, and for example, extrusion molding, injection molding, solution casting method, or the like can be used.

  Such a sheet of the present invention is effective as a sheet for forming a shoe sole (a composite molded article for a shoe sole). That is, the sheet of the present invention is interposed between a crosslinked rubber layer as a stud (member) and a thermoplastic elastomer layer as a sole (member), and a sheet (or one of them) for directly laminating these layers. A cross-linked rubber layer as a stud (member) is directly formed on the surface, and a thermoplastic elastomer layer is directly formed as a sole (member) on the other surface to form a shoe sole (composite molded product for shoe sole). Sheet).

  If the crosslinked rubber layer as the stud and the thermoplastic elastomer layer as the sole are directly bonded, the surface treatment of the crosslinked rubber layer as described above is necessary or the deformation of the thermoplastic elastomer layer is prevented. Difficult to do. And in order to prevent such a deformation | transformation, when the material of high heat resistance and high rigidity is used for a sole, the softness | flexibility which is a required performance as a sole (shoe sole) will be impaired. Moreover, in the said patent document 3, by setting it as the three-layer structure of the outsole design part of synthetic rubber, the thermoplastic elastomer sheet joined and integrated with this design part, and also the thermoplastic elastomer of a shoe sole main body. The production efficiency of the shoe sole can be improved to some extent, but in order to suppress or prevent deformation of the thermoplastic elastomer sheet, it is necessary to open the mold at the initial stage of crosslinking of the rubber, and the outsole design portion of the synthetic rubber Adhesion failure with a thermoplastic elastomer sheet may occur.

  On the other hand, the sheet of the present invention is composed of a specific component and has a relatively large rigidity. Therefore, even if the crosslinked rubber layer is not surface-treated, it can be firmly bonded to the crosslinked rubber layer without being deformed. Moreover, by interposing the sheet of the present invention between the crosslinked rubber layer and the thermoplastic elastomer layer, the sheet and the sole can be firmly bonded without deforming the sole composed of the thermoplastic elastomer. In addition, the flexibility as a sole (or a shoe sole) is not impaired.

  Therefore, by using the sheet of the present invention, the stud and the sole can be firmly bonded with high workability without using a solvent or chemicals and without opening the mold in the middle of crosslinking of rubber. In addition, a shoe sole that satisfies the required performance as a sole can be obtained.

  Below, the shoe sole (composite molding for shoe soles) using the sheet | seat of this invention is explained in full detail.

[Shoe sole (composite molded product for shoe sole)]
The shoe sole (composite molded product for shoe sole) of the present invention, as described above, has a cross-linked rubber layer (as a stud) directly formed (directly joined) on one surface of the sheet. And a thermoplastic elastomer layer (as a sole) formed directly on the other surface of the sheet.

(Crosslinked rubber layer)
The crosslinked rubber layer is formed of a layer obtained by crosslinking rubber, and such a layer is formed by crosslinking uncrosslinked rubber (composition) (that is, uncrosslinked rubber (composition) is crosslinked). Layer).

  The rubber (or uncrosslinked rubber) is not particularly limited, and is a diene rubber, olefin rubber, acrylic rubber, fluorine rubber, silicone rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, propylene oxide rubber, ethylene-vinyl acetate. Examples thereof include a copolymer (EAM), polynorbornene rubber, and modified rubbers thereof (such as acid-modified rubber). These rubbers can be used alone or in combination of two or more.

  Examples of the diene rubber include the weight of diene monomers such as natural rubber (NR), isoprene rubber (IR), isobutylene isoprene rubber (butyl rubber) (IIR), butadiene rubber (BR), and chloroprene rubber (CR). Copolymer; for example, acrylonitrile-diene copolymer rubber such as acrylonitrile butadiene rubber (nitrile rubber) (NBR), nitrile chloroprene rubber (NCR), nitrile isoprene rubber (NIR); styrene butadiene rubber (SBR, for example, styrene and butadiene Random copolymers, SB block copolymers composed of styrene blocks and butadiene blocks, etc.), styrene-diene copolymer rubbers such as styrene chloroprene rubber (SCR) and styrene isoprene rubber (SIR) are included. The diene rubber includes hydrogenated rubber such as hydrogenated nitrile rubber (HNBR).

  Examples of the olefin rubber include ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM and the like), polyoctenylene rubber and the like.

  Examples of the acrylic rubber include rubbers mainly composed of alkyl acrylate, such as a copolymer ACM of an alkyl acrylate and a chlorine-containing crosslinkable monomer, and a copolymer ANM of an alkyl acrylate and acrylonitrile. Examples thereof include a copolymer of an acrylic acid alkyl ester and a carboxyl group and / or an epoxy group-containing monomer, and ethylene acrylic rubber.

  As the fluororubber, a rubber using a fluorine-containing monomer, for example, a copolymer FKM of vinylidene fluoride and perfluoropropene and, if necessary, tetrafluoroethylene, a copolymer of tetrafluoroethylene and propylene, A copolymer FFKM of tetrafluoroethylene and perfluoromethyl vinyl ether can be exemplified.

  Examples of the silicone rubber include methyl silicone rubber (MQ), vinyl silicone rubber (VMQ), phenyl silicone rubber (PMQ), phenyl vinyl silicone rubber (PVMQ), and fluorinated silicone rubber (FVMQ).

  Examples of the modified rubber include acid-modified rubbers of the above rubbers, such as carboxylated styrene butadiene rubber (X-SBR), acid-modified nitrile rubber (carboxylated nitrile rubber, X-NBR), and carboxylated ethylene propylene rubber (X-EPM). And rubber having a carboxyl group or an acid anhydride group.

  The crosslinked rubber layer may be usually formed of a composition (uncrosslinked rubber composition or unvulcanized rubber composition) containing uncrosslinked rubber (or unvulcanized rubber). The uncrosslinked rubber composition may be composed of at least uncrosslinked rubber and a crosslinking agent.

  Examples of crosslinking agents (vulcanizing agents) include radical generators (organic peroxides, azo compounds, sulfur-containing organic compounds, etc.), sulfur-based vulcanizing agents (powder sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, high Sulfur such as dispersible sulfur, sulfur chloride such as sulfur monochloride and sulfur dichloride, surface-treated sulfur, alkylphenol disulfide, morpholine disulfide, etc.), oxime-based cross-linking agents (for example, p-quinone dioxime, p, p ′) -Dibenzoylquinone dioxime, etc.), resin-based crosslinking agents (eg, alkylphenol / formaldehyde resins, sulfurized p-tertiary butylphenol resins, hexamethoxymethyl / melamine resins), fatty acid salts (potassium laurate, palm fatty acid soda, etc.) ), Metal salts (such as zinc oxide and zinc peroxide). The crosslinking agents may be used alone or in combination of two or more.

Examples of the organic peroxide (or peroxide) include hydroperoxide [eg, alkyl hydroperoxide (eg, t-butyl hydroperoxide), alkane dihydroperoxide (eg, cumene hydroperoxide), etc.], Dialkyl peroxides (eg, di-C _1-10 alkyl peroxides such as di-t-butyl peroxide; diaralkyl peroxides such as dicumyl peroxide; alkyl-aralkyl peroxides such as t-butyl-cumyl peroxide) , diacyl peroxides [e.g., diacetyl peroxide, (such as di-C _1-18 alkanoyl peroxide) dialkanoyl peroxides such as lauroyl peroxide; benzoyl peroxide, 4-chlorobenzo Peroxide, 2,4-dichlorobenzoyl peroxide, benzoyl toluyl peroxide, di-alloy peroxide such as toluyl peroxide (such as di-C _7-12 alloy peroxide), etc.], di (alkyl peroxy) alkane [e.g., Di (C _1-10 alkylperoxy) C _1-10 alkanes such as 2,2-di (t-butylperoxy) butane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane ], Di (alkylperoxy) cycloalkane [for example, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, etc. di _{(C 1-10} alkyl _{peroxy) C 5-10} cycloalkane, di (Arukirupao Shiarukiru) arene [e.g., 1,3-bis (t-butylperoxy isopropyl) di benzene _{(C 1-10} alkyl peroxy _{C 1-4 alkyl) C 6-10} arene], di (alkyl peroxy) Alkynes [for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, etc.], di (acylperoxy) alkanes (for example, 2,5-dimethyl-2,5-dibenzoyl) Peroxyhexane etc.), peracid esters [e.g., peracid alkyl esters (e.g., peracetic acid alkyl esters (e.g., t-butyl peracetate, t-butyl peroxyoctoate, t-butyl peroxydecanoate) (C _1-18 such as peracetic acids _{C 1-6} alkyl ester); t-butyl peroxybenzoate, di -t- Buchirupao Shi (iso) (such as C _1-6 alkyl esters) over arene-carboxylic acid alkyl esters such as phthalates, etc.], ketone peroxide, and the like peroxycarbonate.

  Examples of the azo compound include an azonitrile compound [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyryl). Nitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)], azoamide compounds {2,2′-azobis {2-methyl-N- [1,1-bis (hydroxy) Methyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyanopenta) Acid), etc.] and the like.

Examples of sulfur-containing organic compounds include thiurams (tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD), dipentamethylenethiuram tetrasulfide (DPTT). ), etc.), dithiocarbamates (dimethyldithiocarbamate, and di C _1-4 alkyl dithiocarbamic acid, such as diethyldithiocarbamate, sodium, potassium, iron, copper, zinc, and salts with selenium or tellurium), thiazole - Le acids (2-mercaptobenzothiazol, 2- (4′-morpholinodithio) benzothiazole, etc.) and the like are included. In addition, a sulfur-containing organic compound such as TMTD may be combined with sulfur, or may be used as a sulfur-free crosslinking agent without being combined with sulfur.

  Of these crosslinking agents, radical generators are preferred, and organic peroxides are particularly preferred from the viewpoint of adhesiveness to the sheet member.

  The ratio of the crosslinking agent is, for example, 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, particularly 1 to 100 parts by weight of the uncrosslinked rubber. It may be about 8 parts by weight.

  The uncrosslinked rubber composition may contain a crosslinking aid (or vulcanization activator or vulcanization aid). The crosslinking aid can be appropriately selected according to the type of the crosslinking agent, for example, vinyl monomers (divinylbenzene, etc.), allyl monomers (diallyl phthalate, triallyl phosphate, triallyl (iso) cyanurate, Triallyl trimellitate, etc.), (meth) acrylic monomers, maleimide compounds, di (meth) acrylic acid metal salts (zinc salts, magnesium salts, etc.), ammonia derivatives, carbon disulfide derivatives and the like. These crosslinking aids can be used alone or in combination of two or more.

Examples of (meth) acrylic monomers include bifunctional (meth) acrylates [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, etc. C _2-10 alkylene glycol di (meth) acrylate; poly C such as diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate _2-4 alkylene glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylates, _{C 2-4} a bisphenol a Di (meth) acrylates of xylene oxide adducts], trifunctional or polyfunctional (meth) acrylates [glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like].

  Examples of maleimide compounds include aromatic bismaleimides (N, N′-1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimaleimide, N, N′-3-methyl-1, 4-phenylenedimaleimide, 4,4′-bis (N, N′-maleimide) diphenylmethane, 4,4′-bis (N, N′-maleimido) diphenylsulfone, 4,4′-bis (N, N ′) -Maleimide) diphenyl ether), aliphatic bismaleimide (N, N'-1,2-ethylenebismaleimide, N, N'-1,3-propylene bismaleimide, N, N'-1,4-tetramethylenebis) And maleimide).

  Ammonia derivatives include aldehyde-ammonia (hexamethylenetetramine, acetaldehyde-ammonia, ethyl chloride-formaldehyde-ammonia reactant, etc.), aldehyde-amines (n-butyraldehyde-aniline reactant, butyraldehyde-acetaldehyde-butylidene). Aniline reactants) and guanidines (N, N-diphenylguanidine, diortolylguanidine, orthotolylbiguanide, etc.).

The carbon disulfide derivatives, thioureas (thiocarbonate anilides, di- ortho tri thiourea, ethylene thiourea, dimethyl thiourea, etc. trimethyl thiourea), dithiocarbamates (dimethyldithiocarbamate, di C _1-4 alkyl dithiocarbamic such as diethyl dithiocarbamate Salt of acid and sodium, potassium, iron, copper, zinc, selenium or tellurium, etc.), thiazole [2-mercaptobenzothiazol (MBT), salt of 2-mercaptobenzothiazol ( Metal salts such as zinc and sodium, amine salts such as cyclohexylamine), dibenzothiazyl disulfide, 2- (4′-morpholinodithio) benzothiazole, etc.], sulfenamides (N-cyclohexyl-2-benzothiazole sulf Fenamide, -T-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N, N'-diisopropyl-2-benzothiazole sulfenamide, N-cyclohexyl-1,2-benzo And thiazoylsulfenamide) and xanthates (salts of alkylxanthogenic acid such as isopropylxanthogenic acid and butylxanthogenic acid with sodium and zinc).

  Preferred crosslinking aids can be selected according to the type of crosslinking agent. When a radical generator such as an organic peroxide is used as a crosslinking agent, a vinyl monomer, an allyl monomer, a (meth) acrylic monomer Preference is given to monomers, maleimide compounds and the like.

  The amount of the crosslinking aid (vulcanization activator) can be selected according to the type of vulcanization activator used, but is usually an amount that can promote the adhesion between the polyamide resin and the rubber, for example, rubber (not yet used). It may be about 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, and more preferably about 0.3 to 5 parts by weight with respect to 100 parts by weight of the crosslinked rubber). The proportion of the crosslinking aid is about 0.01 to 10 parts by weight, preferably about 0.05 to 5 parts by weight, more preferably about 0.1 to 4 parts by weight with respect to 1 part by weight of the crosslinking agent. Also good.

  The uncrosslinked rubber composition may further contain various additives such as fillers [granular filler or reinforcing agent (mica, clay, talc, silica, calcium carbonate, magnesium carbonate, carbon black, white carbon, ferrite Etc.), fibrous fillers or reinforcing agents (organic fibers such as rayon, nylon, vinylon, aramid, etc.), softeners (linoleic acid, oleic acid, castor oil, palm oil, etc.) Vegetable oil; paraffin, process oil, extender and other mineral oil), plasticizer (phthalate ester, aliphatic dicarboxylic acid ester, sulfur-containing plasticizer, polyester polymer plasticizer, etc.), co-crosslinking agent (zinc oxide) , Metal oxides such as titanium oxide), anti-aging agent (thermal anti-aging agent, ozone deterioration) Stopper, antioxidant, UV absorber, etc.), tackifier, processing aid, lubricant (stearic acid, metal stearate, wax, etc.), flame retardant, antistatic agent, coloring agent, etc. Good. These additives may be used alone or in combination of two or more.

  The thickness of the crosslinked rubber layer may be, for example, 1 to 30 mm, preferably 2 to 20 mm, more preferably about 3 to 15 mm, and usually about 2 to 20 mm. The thickness of the crosslinked rubber layer may be selected according to the use of the shoe, and may be, for example, about 2 to 3.5 mm for running shoes and about 10 to 20 mm for soccer shoes.

  Further, the thickness ratio between the crosslinked rubber layer and the sheet may be the former / the latter = 100/1 to 1/1, preferably 90/1 to 2/1, more preferably about 80/1 to 3/1. It may be about 75/1 to 4/1 (for example, 70/1 to 5/1).

From the viewpoint of forming studs, the amount of Akron wear of the crosslinked rubber (layer) can be selected from a range of about 200 mm ³ or less (for example, 0 to 150 mm ³ ), for example, 100 mm ³ or less (for example, 0.1 to 90 mm). ^3), preferably 80 mm ³ or less (e.g., 0.5～75Mm ^3), may be more preferably 70 mm ³ or less (e.g., 1～60Mm about ^3), typically 1 to 50 mm ³ (for example, 2 It may be about 40 mm ³ ). The Akron wear can be measured, for example, by the Akron wear B method as a wear volume per 1000 rotations at a load of 27 N, an inclination angle of 10 degrees, and a rotation speed of 75 rpm.

  The Shore A hardness of the crosslinked rubber (layer) may be, for example, 30 to 80, preferably 35 to 70, and more preferably about 40 to 60. The Shore A hardness can be measured according to ASTM D2240.

  In addition, the crosslinked rubber layer forms a stud (stud portion) of a shoe sole (a composite molded article for a shoe sole). Therefore, the shape of the crosslinked rubber layer can be selected in accordance with a desired stud shape, and the crosslinked rubber layer may be formed on one whole surface or a part of the surface of the sheet.

  The crosslinked rubber layer is directly bonded (joined) to one surface of the sheet without using an adhesive layer or the like. Such adhesion between the crosslinked rubber layer and the sheet is strong. For example, in the composite molded article for shoe sole of the present invention, the crosslinked rubber layer and the sheet are bonded for 4 days under conditions of a temperature of 23 ° C. and a humidity of 50%. When peeled after holding, the crosslinked rubber layer and the sheet are bonded to such an extent that at least a part of the interface is broken (cohesive failure).

(Thermoplastic elastomer layer)
The thermoplastic elastomer layer is composed of a thermoplastic elastomer. It does not specifically limit as a thermoplastic elastomer, For example, a polyurethane elastomer (thermoplastic polyurethane elastomer), a polyamide elastomer, a polyester elastomer, a polyolefin elastomer, a polystyrene elastomer, a fluorine-type elastomer, an ethylene-vinyl acetate copolymer etc. are mentioned. These thermoplastic elastomers may be used alone or in combination of two or more.

  The polyurethane elastomer is generally a polyurethane block having a polyurethane (block) as a hard segment (hard block) and a soft segment [or soft block, such as a polyether block, a polyester block (such as an aliphatic polyester block)). It may be a polymer.

  Typical polyurethane elastomers include, for example, polyester urethane elastomers, polyester ether urethane elastomers, polyether urethane elastomers, polycarbonate urethane elastomers, etc., depending on the type of soft segment.

  Of the polyurethane elastomers, polyester urethane elastomers, polyester ether urethane elastomers, polyether urethane elastomers and the like are preferable.

  In the polyurethane elastomer, the number average molecular weight of the soft segment (for example, a polyether block) can be selected from a range of about 100 to 10,000, for example, preferably 300 to 6000 (for example, 300 to 5000), more preferably. About 500-4000 (for example, 500-3000) may be sufficient and about 1000-4000 may be sufficient normally.

  Moreover, as a polyamide elastomer, the polyamide elastomer illustrated by the term of the said sheet | seat etc. are mentioned. The polyamide elastomer constituting the thermoplastic elastomer layer may satisfy the melting point, the amino group concentration, and the bending elastic modulus as described above, but it does not need to be satisfied.

  Preferred thermoplastic elastomers include polyurethane elastomers and polyamide elastomers from the viewpoint of adhesion, and polyurethane elastomers are particularly preferred. These polyurethane elastomers and / or polyamide elastomers may be combined with other thermoplastic elastomers.

  When the thermoplastic elastomer is composed of such polyurethane elastomer and / or polyamide elastomer, the ratio of the polyurethane elastomer and / or polyamide elastomer to the entire thermoplastic elastomer is, for example, 30% by weight or more (for example, 40 to 100% by weight). 50% or more (for example, 60 to 100% by weight), more preferably 70% by weight or more (for example, 80 to 100% by weight).

  The flexural modulus of thermoplastic elastomer according to ISO 178 can be selected from the range of, for example, less than 600 MPa (for example, about 20 to 550 MPa), preferably less than 500 MPa (for example, about 30 to 480 MPa), and more preferably 450 MPa or less (for example, About 50 to 420 MPa), particularly 400 MPa or less (for example, about 80 to 400 MPa), and usually about 100 to 500 MPa (for example, 120 to 450 MPa, preferably about 130 to 400 MPa).

  The Shore D hardness of the thermoplastic elastomer may be, for example, 40 to 100, preferably 45 to 90, more preferably about 50 to 80, and usually about 50 to 70. The Shore D hardness can be measured according to ASTM D2240.

  The thermoplastic elastomer layer is a component other than the thermoplastic elastomer, for example, a stabilizer (thermal stabilizer, ultraviolet absorber, antioxidant, etc.), plasticizer, lubricant, filler, as long as the effects of the present invention are not impaired. Additives such as a colorant, a flame retardant, and an antistatic agent may be included. These additives may be used alone or in combination of two or more.

  The thickness of the thermoplastic elastomer layer may be, for example, 1 to 30 mm, preferably 2 to 20 mm, and more preferably about 3 to 15 mm.

  The thickness ratio between the thermoplastic elastomer layer and the sheet is, for example, the former / the latter = 100/1 to 1/1, preferably 80/1 to 1.5 / 1, and more preferably 50/1 to 2/1. About 30/1 to 2/1 (for example, about 20/1 to 2.5 / 1).

  Further, the thickness ratio between the thermoplastic elastomer layer and the crosslinked rubber layer is the former / the latter = 10/1 to 0.01 / 1, preferably 5/1 to 0.03 / 1, more preferably 4/1 to 0. .05 / 1 may be sufficient, usually 3/1 to 0.05 / 1 (for example, 2/1 to 0.07 / 1).

  The thermoplastic elastomer layer forms a sole (sole portion) of a shoe sole (a composite molded product for a shoe sole). Therefore, the shape of the thermoplastic elastomer layer can be selected in accordance with a desired sole shape.

  The thermoplastic elastomer layer is directly bonded (joined) to the other surface of the sheet (that is, a surface different from the surface on which the crosslinked rubber layer is formed) without using an adhesive layer or the like. Such adhesion between the thermoplastic elastomer layer and the sheet is strong. For example, in the composite molded article for a shoe sole of the present invention, the thermoplastic elastomer layer and the sheet are bonded under the conditions of a temperature of 23 ° C. and a humidity of 50%. When peeled after being held for 4 days, the thermoplastic elastomer layer and the sheet are bonded to such an extent that at least a portion breaks (cohesive failure) at the interface.

(Manufacturing method of shoe sole (composite molded product for shoe sole))
A shoe sole (a composite molded article for a shoe sole) can be produced by directly forming a crosslinked rubber layer on one surface of the sheet and a thermoplastic elastomer layer on the other surface. The order of forming the crosslinked rubber layer and the thermoplastic elastomer layer is not particularly limited, but usually, after forming the crosslinked rubber layer on one side of the sheet, the thermoplastic elastomer layer is often formed on the other side of the sheet. . That is, in the present invention, after obtaining a composite of a sheet and a crosslinked rubber layer formed on one surface of the sheet (sheet / crosslinked rubber layer composite), the other sheet of the composite is usually obtained. A thermoplastic elastomer layer is formed on the surface.

  The sheet / crosslinked rubber layer composite (sheet / crosslinked rubber integral molded body) can be obtained by bringing a sheet and the uncrosslinked rubber (or uncrosslinked rubber composition) into contact with each other for crosslinking. In this contact and crosslinking, in particular, the sheet (or the resin component constituting the sheet) may be crosslinked without melting. When it is made to crosslink without melting (or almost without melting), deformation of the composite (or sheet) can be efficiently prevented. In the present invention, since the sheet composed of the specific resin component is used, not only the crosslinking reaction between the uncrosslinked rubber and the crosslinking agent occurs but also the sheet and the uncrosslinked rubber are brought into contact with the crosslinking. At the interface with the (composition), a reaction between the polyamide resin constituting the sheet and a crosslinking agent (and a crosslinking aid) contained in the uncrosslinked rubber composition or a reaction between the polyamide resin and the uncrosslinked rubber occurs. For this reason, a composite in which the sheet and the crosslinked rubber layer are firmly bonded can be obtained without using the melting of the sheet.

  A method for obtaining a composite by bringing a sheet and uncrosslinked rubber (composition) into contact with each other is not particularly limited, and general-purpose molding methods such as extrusion molding, injection molding, press molding, and transfer molding can be used. In particular, in the present invention, a cross-linked rubber layer is formed by contacting (or injecting) a molten non-cross-linked rubber composition with one surface of a sheet disposed in a mold and cross-linking the non-cross-linked rubber composition. It may be formed. For example, by storing a sheet in a mold (or cavity) corresponding to the shape of the composite, injecting or extruding an uncrosslinked rubber composition to the sheet, and crosslinking the unvulcanized rubber composition, You may adhere | attach a crosslinked rubber layer. The sheet and the uncrosslinked rubber composition may be brought into contact under pressure. For pressurization, hot press molding, injection molding, or the like may be used, or press molding may be performed in a reduced pressure atmosphere.

  In such a method, since a crosslinked rubber layer can be formed without requiring mold opening (demolding) as in Patent Document 3, the working efficiency can be greatly improved. That is, in Patent Document 3, in order to prevent the deformation of the outsole member (stud), it is necessary to open the mold once in the initial stage of rubber cross-linking, but in the present invention, it is composed of the specific resin component. By using such a sheet, a crosslinked rubber stud firmly bonded to the sheet can be formed without causing deformation even if the crosslinking is completed without requiring such mold opening.

  Crosslinking may be performed under heating. The crosslinking temperature (or the contact temperature between the uncrosslinked rubber composition and the sheet) can be selected from the range of, for example, about 80 to 230 ° C, preferably 100 to 210 ° C, and more preferably about 150 to 190 ° C. In particular, if the crosslinking temperature is low (for example, less than 140 ° C.), the time required for crosslinking may become long or the adhesion may be insufficient. Therefore, the crosslinking temperature is 140 ° C. or more from the viewpoint of work efficiency. (For example, 145-200 degreeC), Preferably it is 150 degreeC or more (for example, 150-190 degreeC), More preferably, about 155-185 degreeC (for example, 160-180 degreeC) may be sufficient. As described above, from the viewpoint of deformation, the temperature is preferably lower than the melting point of the polyamide resin constituting the sheet. For example, the sheet includes a polyamide resin having a melting point of 165 ° C. or higher (for example, a polyamide resin). In the case of 30% by weight or more of the total), the crosslinking temperature is lower than the melting point of the polyamide resin [for example, 3 ° C. or more (for example, 3 to 100 ° C.), preferably 5 ° C. or more (for example, 5 to 5 ° C. 50 ° C.) low temperature, more preferably 10 ° C. or higher (for example, 10-30 ° C. low temperature)]. In particular, when a mold used for integral molding is large, a temperature distribution is generated depending on the mold portion. Therefore, it is preferable that the melting point of the polyamide resin be higher with a margin as described above than the temperature used for molding. .

  In the present invention, as described above, since the sheet is composed of a polyamide resin having a specific bending elastic modulus and a relatively high melting point, the sheet is not deformed even if it is crosslinked at such a temperature. And the crosslinked rubber layer can be firmly bonded.

  As described above, the crosslinking is preferably performed without melting the sheet (or the polyamide resin constituting the sheet).

  A sheet / crosslinked rubber layer composite is obtained as described above.

  A composite (or a composite molded article for a shoe sole) in which a sheet (or a sheet / crosslinked rubber layer composite) and a thermoplastic elastomer layer formed on the other surface of the sheet are directly bonded is, for example, a sheet (or a composite molded article for a shoe sole). It can be obtained by forming a thermoplastic elastomer layer on the other surface of the sheet / crosslinked rubber layer composite. Typically, it can be produced by bringing a sheet and the thermoplastic elastomer layer into contact with each other under heating.

  The method for forming the thermoplastic elastomer layer is not particularly limited, and general-purpose methods such as extrusion molding, injection molding, compression molding, transfer molding, laser welding, and high-frequency welding can be used. In particular, in the present invention, the thermoplastic elastomer layer may be formed by contacting (or injecting) a molten thermoplastic elastomer (or a composition thereof) with the other surface of the sheet.

  The contact temperature (or the melting temperature or thermal fusion temperature of the thermoplastic elastomer) may be, for example, about 120 to 280 ° C, preferably about 150 to 260 ° C, and more preferably about 180 to 250 ° C. In particular, when the thermoplastic elastomer is a polyamide elastomer, the contact temperature is about 180 to 270 ° C. (eg, 200 to 250 ° C.), and when the thermoplastic elastomer is a polyurethane elastomer, 180 to 240 ° C. (eg, 200 to 220). Degree). The contact temperature may be a temperature in the kneader (for example, a cylinder temperature of an injection molding machine).

  In addition, due to the contact between the sheet and the thermoplastic elastomer layer under heating, at these interfaces, direct bonding based on the affinity (compatibility) between the polyamide resin constituting the sheet and the thermoplastic elastomer, or from the polyamide resin The two layers are firmly bonded to each other because of direct bonding due to the effect of the amino group. In particular, direct bonding by compatibility is more advantageous when the thermoplastic elastomer includes a polyamide elastomer, and the effect of direct bonding by amino groups is more advantageous when the thermoplastic elastomer includes a polyurethane elastomer. It seems.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In addition, the used component is shown below.

[Sheet]
Polyamide resin (a): Alicyclic polyamide (manufactured by Daicel-Evonik Co., Ltd., “CX7233”, amino group concentration 23 mmol / kg, melting point 247 ° C., flexural modulus 1700 MPa)
Polyamide resin (b): Polyamide 613 (amino group concentration 57 mmol / kg, melting point 207 ° C., flexural modulus 2500 MPa)
Polyamide resin (c): polyamide elastomer (a block copolymer having polyamide 612 as a hard segment and polyether as a soft segment, amino group concentration 19 mmol / kg, melting point 196 ° C., flexural modulus 340 MPa)
Polyamide resin (d): Polyamide 1012 (amino group concentration 35 mmol / kg, melting point 185 ° C., flexural modulus 1500 MPa)
Polyamide resin (e): Polyamide 12 (manufactured by Daicel-Evonik Co., Ltd., “ZL9500”, amino group concentration 65 mmol / kg, melting point 178 ° C., flexural modulus 1200 MPa)
Polyamide resin (f): Polyamide 12 (manufactured by Daicel-Evonik Co., Ltd., “L7321”, amino group concentration 5 mmol / kg, melting point 178 ° C., flexural modulus 1200 MPa)
Polyamide resin (g): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “X4442”, amino group concentration 5 mmol / kg, melting point 175 ° C., Flexural modulus 490MPa)
Polyamide resin (h): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “E62-S4”, amino group concentration 5 mmol / kg, melting point 172 ° C, flexural modulus 340 MPa)
Polyamide resin (i): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “E62-K1”, amino group concentration 17 mmol / kg, melting point 164 ℃, flexural modulus 240MPa)
Polyamide resin (j): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “E55-S4”, amino group concentration 5 mmol / kg, melting point 164 ℃, flexural modulus 210MPa)
Polyamide resin (k): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “ZE0900”, amino group concentration 42 mmol / kg, melting point 164 ° C., Bending elastic modulus 230MPa)
Polyamide resin (l): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “E55-K1”, amino group concentration 17 mmol / kg, melting point 160 ℃, flexural modulus 170MPa)
Polyamide resin (m): Polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “E30-S4”, amino group concentration 30 mmol / kg, melting point 152 ℃, flexural modulus 45MPa)
Polyamide resin (n): polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Daicel Evonik Co., Ltd., “E58-S4”, amino group concentration 38 mmol / kg, melting point 144 ℃, flexural modulus 190MPa)
Polyamide resin (o): Polyamide elastomer (Block copolymer with polyamide 12 as hard segment and polyether as soft segment, manufactured by Arkema Co., Ltd., “PEBAX 6333”, amino group concentration 9 mmol / kg, melting point 169 ° C., flexural elasticity Rate 290 MPa)
Polyamide resin (p): polyamide elastomer (a block copolymer having polyamide 12 as a hard segment and polyether as a soft segment, manufactured by Arkema Co., Ltd., “PEBAX5533”, amino group concentration 9 mmol / kg, melting point 159 ° C., flexural elasticity Rate 160 MPa).

  Using the above polyamide resin, a sheet (thickness 0.5 mm, 10 cm square) composed of the following polyamide resins (or compositions) (1) to (26) was obtained.

Polyamide resin (1): Polyamide resin (a) alone (amino resin concentration 23 mmol / kg, flexural modulus 1700 MPa, melting point 247 ° C., melting point 165 ° C. or higher (247 ° C.) ratio of polyamide resin = 100 wt%)
Polyamide resin (2): Polyamide resin (b) alone (ratio of polyamide resin having amino group concentration 57 mmol / kg, flexural modulus 2500 MPa, melting point 207 ° C., melting point 165 ° C. or higher (207 ° C.) = 100% by weight)
Polyamide resin (3): Polyamide resin (c) alone (ratio of polyamide resin having amino group concentration 19 mmol / kg, flexural modulus 340 MPa, melting point 196 ° C., melting point 165 ° C. or higher (196 ° C.) = 100% by weight)
Polyamide resin (4): Polyamide resin (d) alone (ratio of polyamide resin having an amino group concentration of 35 mmol / kg, a flexural modulus of 1500 MPa, a melting point of 185 ° C., and a melting point of 165 ° C. or higher (185 ° C.) = 100% by weight)
Polyamide resin (5): Polyamide resin (e) alone (amino group concentration 65 mmol / kg, flexural modulus 1200 MPa, melting point 178 ° C., melting point 165 ° C. or higher (178 ° C.) ratio of polyamide resin = 100 wt%)
Polyamide resin (6): a molten mixture of 30 parts by weight of polyamide resin (d) and 70 parts by weight of polyamide resin (e) (as a whole, polyamide having an amino group concentration of 56 mmol / kg, a flexural modulus of 1250 MPa, a melting point of 165 ° C. or higher (Ratio of resin = 100% by weight)
Polyamide resin (7): Melted mixture of polyamide resin (e) 50 parts by weight and polyamide resin (k) 50 parts by weight (as a whole, amino group concentration 53.5 mmol / kg, flexural modulus 600 MPa, melting point 165 ° C. or higher) Of polyamide resin = 50% by weight)
Polyamide resin (8): Melted mixture of 70 parts by weight of polyamide resin (e) and 30 parts by weight of polyamide resin (k) (as a whole, amino group concentration 58.1 mmol / kg, flexural modulus 870 MPa, melting point 165 ° C. or higher Of polyamide resin = 70% by weight)
Polyamide resin (9): A molten mixture of 70 parts by weight of polyamide resin (e) and 30 parts by weight of polyamide resin (j) (as a whole, polyamide having an amino group concentration of 47 mmol / kg, a flexural modulus of 850 MPa, a melting point of 165 ° C. or higher (Ratio of resin = 70% by weight)
Polyamide resin (10): a molten mixture of 60 parts by weight of polyamide resin (e) and 40 parts by weight of polyamide resin (h) (as a whole, polyamide having an amino group concentration of 41 mmol / kg, a flexural modulus of 750 MPa, a melting point of 165 ° C. or higher (Ratio of resin = 100% by weight)
Polyamide resin (11): A molten mixture of 10 parts by weight of polyamide resin (d), 40 parts by weight of polyamide resin (e), and 50 parts by weight of polyamide resin (j) (as a whole, the amino group concentration is 30.4 mmol / kg. , Ratio of polyamide resin having a flexural modulus of 730 MPa and a melting point of 165 ° C. or higher = 50% by weight)
Polyamide resin (12): a melt mixture of 50 parts by weight of polyamide resin (c) and 50 parts by weight of polyamide resin (f) (as a whole, polyamide having an amino group concentration of 12 mmol / kg, a flexural modulus of 1400 MPa, a melting point of 165 ° C. or higher (Ratio of resin = 100% by weight)
Polyamide resin (13): A molten mixture of 50 parts by weight of polyamide resin (a) and 50 parts by weight of polyamide resin (f) (as a whole, polyamide having an amino group concentration of 14 mmol / kg, a flexural modulus of 1500 MPa, and a melting point of 165 ° C. or higher. (Ratio of resin = 100% by weight)
Polyamide resin (14): A molten mixture of 50 parts by weight of polyamide resin (e), 35 parts by weight of polyamide resin (p), and 15 parts by weight of glass fiber (amino group concentration 42 mmol / kg as a whole resin component, flexural elasticity Ratio of polyamide resin having a rate of 800 MPa, a melting point of 247 ° C., and a melting point of 165 ° C. or more = 100% by weight, as a whole composition, an amino group concentration of 37 mmol / kg, a flexural modulus of 2100 MPa)
Polyamide resin (15): Polyamide resin (f) alone (amino group concentration 5 mmol / kg, flexural modulus 1200 MPa, melting point 178 ° C., melting point 165 ° C. or higher (178 ° C.) ratio of polyamide resin = 100 wt%)
Polyamide resin (16): Polyamide resin (g) alone (amino group concentration 5 mmol / kg, flexural modulus 490 MPa, melting point 175 ° C., melting point 165 ° C. or higher (175 ° C.) ratio of polyamide resin = 100 wt%)
Polyamide resin (17): Polyamide resin (h) alone (Amino group concentration 5 mmol / kg, flexural modulus 340 MPa, melting point 172 ° C., melting point 165 ° C. or higher (172 ° C.) ratio of polyamide resin = 100 wt%)
Polyamide resin (18): Polyamide resin (i) alone (amino group concentration 17 mmol / kg, flexural modulus 240 MPa, melting point 164 ° C., proportion of polyamide resin with melting point 165 ° C. or higher = 0 wt%)
Polyamide resin (19): Polyamide resin (j) alone (amino group concentration 5 mmol / kg, flexural modulus 210 MPa, melting point 164 ° C., proportion of polyamide resin with melting point 165 ° C. or higher is 0% by weight)
Polyamide resin (20): Polyamide resin (k) alone (amino group concentration 42 mmol / kg, flexural modulus 230 MPa, melting point 164 ° C., proportion of polyamide resin with melting point 165 ° C. or higher = 0 wt%)
Polyamide resin (21): Polyamide resin (l) alone (amino group concentration 17 mmol / kg, flexural modulus 170 MPa, melting point 160 ° C., proportion of polyamide resin with melting point 165 ° C. or higher = 0 wt%)
Polyamide resin (22): Polyamide resin (m) alone (amino group concentration 30 mmol / kg, flexural modulus 45 MPa, melting point 152 ° C., proportion of polyamide resin with melting point 165 ° C. or higher of 0% by weight)
Polyamide resin (23): Polyamide resin (n) alone (amino group concentration 38 mmol / kg, flexural modulus 190 MPa, melting point 144 ° C., proportion of polyamide resin with melting point 165 ° C. or higher = 0 wt%)
Polyamide resin (24): Polyamide resin (o) alone (amino group concentration 9 mmol / kg, flexural modulus 290 MPa, melting point 169 ° C., ratio of polyamide resin with melting point 165 ° C. or higher = 100 wt%)
Polyamide resin (25): Polyamide resin (p) alone (amino group concentration 9 mmol / kg, flexural modulus 160 MPa, melting point 159 ° C., proportion of polyamide resin with melting point 165 ° C. or higher 0% by weight)
Polyamide resin (26): A molten mixture of polyamide resin (f) 40 parts by weight and polyamide resin (p) 60 parts by weight (as a whole, amino group concentration 7.4 mmol / kg, flexural modulus 550 MPa, melting point 159 ° C., (The ratio of polyamide resin having a melting point of 165 ° C. or higher = 40% by weight)
The amino group concentration, melting point and flexural modulus of the polyamide resin (or resin composition) were measured as follows.

(Amino group concentration)
About 0.5 g of a polyamide-based material used as a sample is taken and dissolved in 40 ml of a phenol / methanol mixed solution. After confirming the dissolution, 10 ml of methanol is further added. This was used as a sample and measured by titration with an aqueous hydrochloric acid solution. In addition, Hiranuma Sangyo Co., Ltd. product and Hiranuma automatic titration apparatus COM-200 were used as an apparatus.

(Melting point)
By thermal analysis (DSC), 10 ° C./min. After melting to 250 ° C. at a temperature rising rate of 10 ° C./min. At −30 ° C. and further at 10 ° C./min. The melting peak top at the time of melting at a temperature rising rate of was defined as the melting point.

(Flexural modulus)
Measurement was performed in accordance with ISO178.

[Uncrosslinked rubber composition]
Using a rubber composition (uncrosslinked rubber composition) containing the following components, an uncrosslinked rubber sheet (thickness 0.5 mm, 10 cm square) was prepared.

(Rubber composition 1)
50 parts by weight of natural rubber, 50 parts by weight of butadiene rubber (manufactured by Dow Chemical Co., Ltd., “Buna EM 1500”), 5 parts by weight of polyoctenylene (manufactured by Evonik GmbH, “Vestenemer 8012”), clay (manufactured by Hoffmann Mineral, “Silitin Z86” ) 25 parts by weight, 45 parts by weight of carbon black (N335), 10 parts by weight of plasticizer (manufactured by Bayer Co., Ltd., “Vulcanol 88”), 1 part by weight of stearic acid, vulcanization activator (manufactured by Seiko Chemical Co., Ltd.) “Hicross M”, compound name: trimethylolpropane trimethacrylate 2 parts by weight, cross-linking agent (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”, compound name: 1,3-bis (t-butylperoxyisopropyl) ) Benzene) 6 parts by weight (Rubber composition 2)
50 parts by weight of styrene butadiene rubber (manufactured by JSR Corporation, “JSR # 1502”), 50 parts by weight of butadiene rubber (manufactured by Dow Chemical Co., Ltd., “Buna EM 1500”), polyoctenylene (manufactured by Evonik GmbH, “Vestenemer 8012”) 10 parts by weight, clay (manufactured by Hoffmann Mineral, “Silitin Z86”) 25 parts by weight, carbon black (N335) 45 parts by weight, plasticizer (manufactured by Bayer, “Vulcanol 88”) 10 parts by weight, stearic acid 1 part by weight Parts, vulcanization activator (manufactured by Seiko Chemical Co., Ltd., “Hicross M”, compound name: trimethylolpropane trimethacrylate), cross-linking agent (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”, Compound name: 1,3-bis (t-butylperoxyisopropyl Pill) benzene) 6 parts by weight (rubber composition 3)
97 parts by weight of ethylene propylene diene rubber (manufactured by DSM Corporation, “DSM 509 × 100”), 3 parts by weight of polyoctenylene (manufactured by Evonik GmbH, “Vestenemer 8012”), 0.3 part by weight of carbon black (N335), white 25 parts by weight of carbon (manufactured by Nippon Mystron Co., Ltd., “Mistron vapor”), 1 part by weight of plasticizer (PEG 4000), 3 parts by weight of zinc oxide, 0.5 part by weight of stearic acid, vulcanizing activator (Seiko Chemical Co., Ltd.) ), “Hicross M”, compound name: trimethylolpropane trimethacrylate 0.5 parts by weight, cross-linking agent (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”, compound name: 1,3-bis ( t-butylperoxyisopropyl) benzene) 2.5 parts by weight (rubber composition 4)
Carboxylated ethylene propylene rubber ("Excel VA 1803") 100 parts by weight, carbon black (N774) 60 parts by weight, plasticizer (naphthenic oil) 40 parts by weight, zinc oxide 5 parts by weight, anti-aging agent (TMQ) 2 parts by weight Parts, vulcanization activator (triallyl cyanurate) 3 parts by weight, cross-linking agent (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”, compound name: 1,3-bis (t-butylperoxyisopropyl) benzene ) 7.5 parts by weight (Rubber composition 5)
50 parts by weight of nitrile rubber (manufactured by JSR Corporation, “JSR N240S”), 50 parts by weight of carboxylated nitrile rubber (manufactured by Nippon Zeon Co., Ltd., “Nipol 1027J”), 60 parts by weight of silica (“Vulkasil C”), 10 parts by weight of plasticizer (manufactured by Bayer Co., Ltd., “Vulkanol 88”), 3 parts by weight of titanium oxide, 2 parts by weight of coloring material (“Opasin blue 690”), 1 part by weight of stearic acid, vulcanizing activator (triallyl) 1.5 parts by weight of isocyanurate), 6 parts by weight of crosslinking agent (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”, compound name: 1,3-bis (t-butylperoxyisopropyl) benzene) Item 6)
Hydrogenated nitrile rubber (manufactured by Nippon Zeon Co., Ltd., “Zetpol 3110”) 100 parts by weight, carbon black (Asahi Carbon Co., Ltd., “Asahi 60”, N550) 50 parts by weight, plasticizer (Bayer Co., Ltd.) , "Vulkanol 88") 10 parts by weight, zinc oxide 2 parts by weight, vulcanization activator (manufactured by DuPont, "HVA-2", compound name: N, N'-m-phenylene dimaleimide) 4 parts by weight , 7 parts by weight of a cross-linking agent (manufactured by Kayaku Akzo Co., Ltd., “Perkadox 14/40”, compound name: 1,3-bis (t-butylperoxyisopropyl) benzene) (rubber composition 7)
100 parts by weight of acrylic rubber (manufactured by DuPont, “VAMAC-G”), 100 parts by weight of carbon black (manufactured by Asahi Carbon Co., Ltd., “Asahi 60”, N550), plasticizer (“Armin 18D”) 5 parts by weight, plasticizer (manufactured by Toho Chemical Co., Ltd., “Phosphanol RL 210”), 2 parts by weight of stearic acid, anti-aging agent (manufactured by Ouchi Shinsei Co., Ltd., “NOCRACK CD”) 2 Parts by weight, vulcanization activator (manufactured by Kawaguchi Chemical Co., Ltd., DPG, compound name: N, N-diphenylguanidine), 4 parts by weight, crosslinking agent (MDA) 1.25 parts by weight (rubber composition 8)
Fluororubber (Daikin Co., Ltd., “Dai-EL G902”) 100 parts by weight, carbon black (N990) 10 parts by weight, cross-linking agent (Atchem Yoshiaki Co., Ltd., “Luperox 101 XL45”) 3 parts by weight, cross-linking 4 parts by weight of an agent (manufactured by DuPont, “Diak No. 7”, compound name: triallyl isocyanurate).

[Sole (thermoplastic elastomer)]
Polyurethane elastomer (TPU1): ester polyurethane elastomer, “T470A”,
Polyurethane elastomer (TPU2): ester polyurethane elastomer, “Desmopan 8785”,
Polyamide elastomer (PAE1): Polyamide elastomer, manufactured by Daicel Evonik Co., Ltd., “E62-S4”, flexural modulus 340 MPa,
Polyamide elastomer (PAE2): Polyamide elastomer, manufactured by Arkema Co., Ltd., “PEBAX6333”, flexural modulus 290 MPa.

[Preparation of specimen and its evaluation]
Using the above materials, a test piece of a composite molded article for shoe soles was obtained as follows.

  On the metal flat plate (40 cm square), aluminum foil (adhesion-preventing silicone surface baked) is placed, and on that, the polyamide resin sheet (10 cm square, thickness 0.5 mm) is placed. The rubber mold (thickness 3 mm) shown in the photograph was placed. On top of that, the uncrosslinked rubber sheet (9 cm square, thickness 2.5 mm) was placed, and then an aluminum foil (silicone surface baked for adhesion prevention) and a metal flat plate (40 cm square) were placed thereon, It was installed in a hot press machine adjusted to a predetermined crosslinking temperature (150 ° C., 160 ° C. or 170 ° C.) shown in the table below. After holding for 400 hours under a pressure of 400 N for a predetermined time (20 minutes when the crosslinking temperature is 150 ° C., 10 minutes when the temperature is 160 ° C., 7 minutes when the temperature is 170 ° C.), the pressure condition is released, and the sheet member and the stud member The integrally molded member was obtained. It is further inserted into a resin mold (mold temperature 40 ° C), and a thermoplastic elastomer is overmolded thereon with a thickness of 2 mm (cylinder temperature: 210 ° C for TPU1 and TPU2, 250 ° C for PAE1 and PAE2). Thus, a test piece of a composite molded article for shoe soles was obtained.

  In addition, similar test pieces were obtained by changing the thickness of the polyamide resin sheet from 0.5 mm to 0.3 mm and 0.7 mm.

  And in the obtained test piece (3 types of 10 cm square, thickness 0.3 mm, 0.5 mm, and 0.7 mm), adhesiveness and deformation | transformation were evaluated on the following references | standards.

(Adhesiveness)
Evaluation of adhesiveness was performed by holding the obtained test piece for 4 days under the conditions of a temperature of 23 ° C. and a humidity of 50%, and then peeling between the sheet and the stud or between the sheet and the sole with radio pliers. It was. The obtained results were evaluated as follows.

A: Very strong (the interface between members does not peel off and the test piece breaks)
B: Strong (partially peeled off the interface between the members, and the test piece was partially broken)
C: Adhesion (the interface between members is peeled)
When the evaluation between the sheet and the stud was “C”, the adhesion between the sheet and the sole was evaluated with a composite molded body having only the sheet and the sole.

(Deformability)
Deformability was evaluated by visually observing a 10 cm square region from the end of the obtained test piece.

+: Not deformed ±: Partially deformed (there is deformation at the end or part of the adhesive part)
-: Large deformation (the area of the deformed part is larger than the area of the non-deformed part)
The results are shown in the table. The table numbers correspond to the polyamide resin numbers used. For example, in Table 1, polyamide resin (1) was used, and in Table 10, polyamide resin (10) was used. In the stud column of the table, the parentheses indicate the crosslinking temperature (° C.) of the rubber composition.

  As is apparent from the results of the table, it is recognized that the amino group content of the polyamide resin has a large difference in adhesiveness before and after 10 mmol / kg, and when the flexural modulus of the polyamide resin is 300 MPa or more, deformation is caused. It was found that can be prevented or suppressed. Further, it has been found that such adhesion and prevention of deformation can be seen preferentially when a resin having a melting point of 165 ° C. or higher is contained in the polyamide resin.

  The composite molded article for shoe sole of the present invention can be used for various shoe soles. In particular, it is useful as a shoe sole of shoes that require functions such as friction resistance and cushioning properties [for example, shoes used in the field of sports (shoes for gymnasiums, shoes for artificial turf, etc.)].

Claims (16)

  A sheet for forming a composite molded article for a shoe sole, which is interposed between a crosslinked rubber layer as a stud and a thermoplastic elastomer layer as a sole in direct contact with these layers, A sheet comprising a resin component (A) containing a), wherein the resin component (A) has an amino group concentration of 10 mmol / kg or more and a flexural modulus of 300 MPa or more according to ISO178.   The sheet according to claim 1, wherein the polyamide resin (a) is composed of at least one selected from polyamide and polyamide elastomer.   The sheet according to claim 1 or 2, wherein the polyamide resin (a) contains a polyamide resin having a melting point of 165 ° C or higher in an amount of 30% by weight or more based on the entire polyamide resin (a). The sheet according to any one of claims 1 to 3, wherein the resin component (A) is any one of the following (1) to (3).
(1) Polyamide resin alone having an amino group concentration of 10 mmol / kg or more, a melting point of 165 ° C. or more, and a flexural modulus of elasticity of 300 MPa or more according to ISO 178 (2) A resin composition composed of a plurality of polyamides having a melting point of 165 ° C. or more Polyamide resin composition containing 30% by weight or more of the polyamide and satisfying an amino group concentration of 10 mmol / kg or more as a whole and a bending elastic modulus of 300 MPa or more according to ISO 178. (3) Resin composition comprising polyamide and polyamide elastomer And 30% by weight or more of the polyamide and / or the polyamide elastomer has a melting point of 165 ° C. or more, and satisfies an amino group concentration of 10 mmol / kg or more and a flexural modulus of 300 MPa or more according to ISO 178 as a whole.   The sheet according to claim 4, wherein the resin component (A) is a polyamide resin composition (3), and the amino group concentration of the polyamide elastomer is 10 mmol / kg.   Furthermore, the sheet | seat in any one of Claims 1-5 containing a filler.   The sheet according to any one of claims 1 to 6, which has a thickness of 0.1 to 0.7 mm.   The sheet according to any one of claims 1 to 7, a crosslinked rubber layer as a stud directly formed on one surface of the sheet, and a thermoplastic elastomer as a sole directly formed on the other surface of the sheet A composite molded article for a shoe sole composed of layers.   The composite molded body according to claim 8, wherein the crosslinked rubber layer is formed by crosslinking an uncrosslinked rubber composition containing uncrosslinked rubber and a peroxide.   The composite molded body according to claim 9, wherein the uncrosslinked rubber composition further contains a crosslinking aid.   The composite molded body according to any one of claims 8 to 10, wherein the thermoplastic elastomer layer is composed of at least one selected from a polyurethane elastomer and a polyamide elastomer.   A method for producing a composite molded article for a shoe sole by directly forming a crosslinked rubber layer on one surface of the sheet according to claim 1 and a thermoplastic elastomer layer on the other surface, respectively. Production of a composite molded body in which a melted uncrosslinked rubber composition is brought into contact with one surface of the sheet placed in a mold and the uncrosslinked rubber composition is crosslinked under heating to form the crosslinked rubber layer. Method.   The manufacturing method of Claim 12 which forms a crosslinked rubber layer, without opening a metal mold | die.   The production method according to claim 12 or 13, wherein the sheet is crosslinked without melting.   The sheet according to any one of claims 12 to 14, wherein the sheet contains a polyamide resin having a melting point of 165 ° C or higher of 30% by weight or more of the polyamide resin (a) and is crosslinked at a temperature lower than the melting point of the polyamide resin having a melting point of 165 ° C or higher. Manufacturing method.   The process according to claim 15, wherein the crosslinking is performed at a temperature of 150 ° C or higher and 5 ° C or lower than the melting point of a polyamide resin having a melting point of 165 ° C or higher.