JP5634025B2 - Cross-linking composition, cross-linked body and cross-linked foam, and footwear and laminate using the same - Google Patents

Description

  The present invention relates to a cross-linking composition, a cross-linked body and a cross-linked foam, and footwear and a laminate using the same.

  Cross-linked foams are light and flexible, and are widely used as footwear materials, various daily necessities, packaging materials, and the like as materials having high mechanical strength. In recent years, as base polymers for impact absorbers, resins such as polystyrene, polyethylene, and ethylene-vinyl acetate copolymers, and elastomers such as natural rubber, styrene-butadiene copolymers, and acrylonitrile-butadiene copolymers have been used. ing.

  For example, Patent Document 1 discloses a combination of a copolymer containing an aromatic vinyl monomer and a tackifier (non-hydrogenated aliphatic hydrocarbon) as a polymer for impact absorbing foam.

JP 2004-107519 A

  However, the performance of a crosslinked foam used as an impact absorber or the like is not always sufficient. There is a need for a crosslinked foam that is not only lightweight and flexible, but also has an excellent balance of various physical properties. For example, when used as an impact absorber for footwear, etc., it should be a crosslinked foam that is not only lightweight and flexible, but also has low rebound resilience and excellent tear strength.

  Accordingly, an object of the present invention is to provide a crosslinking composition, a crosslinked body and a crosslinked foaming composition excellent in low rebound resilience (impact absorbability) and tear strength, and footwear and a laminate using the same. To do.

  As a result of intensive studies to solve the above problems, the present inventor has (A) a copolymer mainly composed of an alkylene unit and a vinyl aromatic unit, or a conjugated diene unit and a vinyl aromatic monomer unit. A hydrogenated copolymer obtained by hydrogenating a part or all of the copolymer, (B) a hydrogenated hydrocarbon plasticizer, (C) an inorganic filler, and (D) a crosslinking agent. The present inventors have found that a cross-linking composition and a cross-linked foam having low rebound resilience and excellent tear strength can be obtained by using the cross-linking composition contained therein, and the present invention has been completed.

That is, the present invention provides the following.
[1] A part of (A) a copolymer mainly composed of an alkylene unit and a vinyl aromatic monomer unit, or a copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit, A crosslinking composition comprising a hydrogenated copolymer that is entirely hydrogenated, (B) a hydrogenated hydrocarbon plasticizer, (C) an inorganic filler, and (D) a crosslinking agent.
[2] The composition for crosslinking according to [1], wherein the softening point of the component (B) is 60 to 150 ° C.
[3] The crosslinking component according to [1] or [2], wherein the component (B) is hydrogenated of 10 mol% or more of unsaturated groups contained in the hydrocarbon-based plasticizer before hydrogenation. Composition.
[4] The component (A) is a hydrogenated copolymer in which a part or all of a copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit is hydrogenated. The composition for crosslinking according to any one of [3].
[5] The component (A) is a hydrogenated copolymer obtained by hydrogenating a part or all of a block copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit. [4] The composition for crosslinking according to 1.
[6] The crosslinking composition according to [5], wherein 10 to 90 mol% of the unsaturated groups contained before hydrogenation of the conjugated diene unit of the component (A) is hydrogenated.
[7] The crosslinking composition according to any one of [1] to [6], further comprising (E) an ethylene copolymer.
[8] The composition for crosslinking according to any one of [1] to [7], further comprising (F) a foaming agent.
[9] The crosslinking composition according to any one of [1] to [8], wherein the tan δ peak temperature of the component (A) is −10 to 40 ° C.
[10] The crosslinking composition according to [9], wherein the component (A) contains a hydrogenated copolymer block mainly composed of a vinyl aromatic monomer and a conjugated diene monomer.
[11] In the composition for crosslinking, the component (A) is 30 to 90% by mass, the component (B) is 0.5 to 20 mass, and the component (C) is 0.5 to 20 mass. The component (D) is 0.05 to 3% by mass, the component (E) is 0.2 to 10% by mass, and the component (F) is 5 to 60% by mass. [8] The composition for crosslinking according to any one of [10] to [10].
[12] A crosslinked product comprising the composition according to any one of [1] to [11].
[13] A cross-linked foam comprising the composition according to any one of [1] to [11].
[14] Footwear comprising the crosslinked foam according to [13].
[15] Footwear comprising the crosslinked foam according to [13] as a midsole or an insole.
[16] A laminate comprising the crosslinked foam according to [13] and a member on which the crosslinked foam is laminated.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for crosslinked foaming which can give the footwear and laminated body using the crosslinked body and crosslinked body excellent in tear strength while being low rebound resilience (impact absorbability) can be provided. .

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The crosslinking composition of the present embodiment includes (A) a copolymer mainly composed of alkylene units and vinyl aromatic monomer units, or a copolymer mainly composed of conjugated diene units and vinyl aromatic monomer units. A hydrogenated copolymer in which a part or all of is hydrogenated, (B) a hydrogenated hydrocarbon plasticizer, (C) an inorganic filler, and (D) a crosslinking agent. Contains the composition.

<(A) component>
Component (A) is hydrogenated by hydrogenating a copolymer mainly composed of alkylene units and vinyl aromatic monomer units, or a copolymer mainly composed of conjugated diene units and vinyl aromatic monomer units. It is a copolymer.

In this embodiment, the naming of each monomer unit constituting the copolymer is in accordance with the name of the monomer from which the monomer unit is derived.
For example, “vinyl aromatic monomer unit” means a structural unit of a polymer produced as a result of polymerizing a vinyl aromatic compound as a monomer. The structure is a molecular structure in which two carbons of a substituted ethylene group derived from a substituted vinyl group are binding sites.
The term “conjugated diene monomer unit” means a structural unit of a polymer produced as a result of polymerizing a monomer, conjugated diene, and its structure is the same as that of an olefin derived from a conjugated diene monomer. It is a molecular structure in which two carbons are binding sites.

In the present embodiment, “mainly” means that the copolymer contains 60% by mass or more of monomer units. From the viewpoint of lightness, flexibility, low rebound resilience, and high tear strength, it is preferable to contain 80% by mass or more of monomer units, more preferably 90% by mass or more, and 95% by mass or more. Is more preferable.
For example, in this embodiment, the copolymer mainly composed of an alkylene unit and a vinyl aromatic unit may be such that the total amount of the alkylene unit and the vinyl aromatic unit is 60% by mass or more based on the copolymer. Similarly, for a copolymer mainly composed of a conjugated diene unit and a vinyl aromatic unit, the total amount of the conjugated diene unit and the vinyl aromatic unit may be 60% by mass or more based on the copolymer.

  In the present embodiment, the vinyl aromatic monomer unit is not particularly limited, and a known one can be used. For example, vinyl such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene An aromatic compound is mentioned, These may use 1 type (s) or 2 or more types. Among these, styrene is preferable from the viewpoint of economy.

  In this embodiment, the conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl- Examples include 1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like. Preferably, 1,3-butadiene and isoprene are used. These may use 1 type (s) or 2 or more types. Among 1,3-butadiene and isoprene, it is more preferable that 1,3-butadiene is mainly used from the viewpoint of mechanical strength.

In this embodiment, an alkylene unit represents monoolefin units, such as an ethylene unit, a methylene unit, a propylene unit, a butylene unit, a hexylene unit, and an octylene unit. Among these, an ethylene unit, a propylene unit, and a butylene unit are preferable from the viewpoint of economy.
Alkylene represents monoolefins, such as ethylene, propylene, butene, hexene, and octene, and these may use 1 type, or 2 or more types.

  In this embodiment, the polymerization method of the component (A) is not particularly limited, and may be a known method. Examples thereof include polymerization methods such as coordination polymerization, anionic polymerization, and cationic polymerization. In the present embodiment, the component (A) is preferably anion polymerization from the viewpoint of easy structure control.

  For example, the method for producing an anionic polymerization block copolymer is not particularly limited, and a known method may be used. For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Examples thereof include the methods described in JP-B-56-28925, JP-A-59-166518, JP-A-60-186777, and the like.

  The component (A) preferably contains one or more blocks mainly composed of vinyl aromatic monomer units from the viewpoint of mechanical strength. From the viewpoint of tear strength, a structure having a block mainly composed of a vinyl aromatic monomer unit at both ends of the molecule is more preferable.

  The content of the block mainly composed of the vinyl aromatic monomer unit in the component (A) is not particularly limited, and is preferably 5% by mass or more and 65% by mass or less from the viewpoint of flexibility. . 10 mass% or more and 35 mass% or less are more preferable, and 13 mass% or more and 30 mass% or less are still more preferable.

The content of the block mainly composed of vinyl aromatic monomer in the hydrogenated copolymer is determined by a method in which the copolymer before hydrogenation is oxidatively decomposed with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (I M. KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946), hereinafter also referred to as “the osmium tetroxide method”)) It is defined by the following formula using mass (wherein the vinyl aromatic compound polymer having an average degree of polymerization of 30 or less is excluded).

Content (mass%) of vinyl aromatic compound polymer block = (mass of vinyl aromatic compound block in copolymer before hydrogenation / mass of copolymer before hydrogenation) × 100

  In the present embodiment, the component (A) is preferably a hydrogenated copolymer obtained by hydrogenating a copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit. Since (A) component is this hydrogenated copolymer, since high economical efficiency can be achieved, it is suitable.

  The binding mode of the copolymer of component (A) is not particularly limited, and may be, for example, a block copolymer, a graft copolymer, a random copolymer, an alternating copolymer, or a combination thereof. Among these, a block copolymer is preferable from the viewpoint of mechanical strength. From this point of view, the component (A) is more preferably a hydrogenated copolymer obtained by hydrogenating a part or all of a block copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit. .

The component (A) preferably has at least one tan δ peak temperature in the range of −10 to 40 ° C. from the viewpoint of low rebound resilience. More preferably, it is -5-30 degreeC, More preferably, it is the range of -3-25 degreeC.
In the present embodiment, the tan δ peak temperature can be measured by dynamic viscoelasticity measurement (1 Hz). More specifically, the dynamic viscoelasticity data is obtained by using a torsion type geometry of a rheometer device (for example, “ARES” (manufactured by TI Instruments Co., Ltd.)). It can be determined at 0.5%, frequency 1 Hz, from -50 ° C to 50 ° C, at a heating rate of 3 ° C / min. The peak temperature can be determined by, for example, “RSI Orchestrator” (manufactured by TI Instruments Inc.).

The control of the tan δ value peak temperature and the peak tan δ curve shape is, for example,
(1) controlling the amount of vinyl bonds in the conjugated diene;
(2) including a copolymer block of a conjugated diene and a vinyl aromatic compound,
(3) Inclining the concentration of the vinyl aromatic compound in the copolymer into a taper shape, a step shape, a concave shape or a convex shape,
(4) increasing the molecular weight distribution;
(5) controlling the size of the block mainly composed of vinyl aromatic compounds;
(6) making a copolymer block of two or more kinds of conjugated dienes,
(7) It can be performed by at least one of changing the hydrogenation rate of the double bond in the copolymer.

  The component (A) preferably contains a hydrogenated copolymer block mainly composed of a vinyl aromatic monomer and a conjugated diene unit from the viewpoint of the tear strength and the compatibility of the crosslinking composition. By containing such a copolymer block, it is also preferable from the viewpoint that the tan δ value peak temperature and the peak tan δ curve shape can be performed with high control.

  In the component (A), the ratio of the vinyl aromatic monomer contained in the hydrogenated copolymer block mainly composed of the vinyl aromatic monomer unit and the conjugated diene unit is not particularly limited. From a viewpoint, 25 mass% or more and 75 mass% or less are preferable from a viewpoint of a softness | flexibility and low repulsion elasticity. More preferably, it is 35 mass% or more and 70 mass% or less, More preferably, it is 45 mass% or more and 65 mass% or less.

  The distribution of the vinyl aromatic monomer contained in the hydrogenated copolymer block mainly composed of the vinyl aromatic monomer and the conjugated diene unit in the component (A) is not particularly limited and is uniformly distributed. Alternatively, the distribution may be tapered, tapered, stepped, concave or convex.

  In this embodiment, two or more hydrogenated copolymer blocks of vinyl aromatic monomer and conjugated diene having different vinyl aromatic monomer contents from the viewpoint of low-temperature curability and low rebound resilience (A ) It is preferable to contain in a component.

  The hydrogenation rate of the conjugated diene monomer contained in the component (A) is not particularly limited, and is preferably 10 to 90 mol% with respect to the total unsaturated bonds of the conjugated diene monomer before hydrogenation. More preferably, it is 15-75 mol%, More preferably, it is 20-50 mol.

  The microstructure (cis, trans, vinyl ratio) of the conjugated diene moiety in the copolymer before hydrogenation of the component (A) can be arbitrarily changed by using a polar compound described later. The amount of vinyl bonds in the conjugated diene moiety before hydrogenation is not particularly limited, but is preferably 5% or more from the viewpoint of manufacturability, and is preferably 75% or less from the viewpoint of mechanical strength. More preferably, it is 10-50%, More preferably, it is 15-40%, More preferably, it is 15% or more and less than 30%.

In this embodiment, the distribution of the vinyl bond amount in each molecule is not particularly limited, and the vinyl bond amount may vary.
“Vinyl bond amount” means 1,2-bond and 3 of 1,2-bond, 3,4-bond and 1,4-bond linkages of conjugated diene before hydrogenation. , 4-means the proportion of those incorporated by a bond.
The vinyl bond amount can be measured by a nuclear magnetic resonance apparatus (NMR).

The weight average molecular weight of the component (A) is preferably 60000 or more from the viewpoint of mechanical strength such as tensile strength, tear strength, and compression set resistance in the crosslinked foam, and is preferably 500000 or less from the viewpoint of molding processability. The range of 70000-450,000 is more preferable, and the range of 90000-400000 is still more preferable.
The molecular weight distribution of the hydrogenated copolymer of the present embodiment is not particularly limited and is preferably 1.01 to 6.00, more preferably 1.03 to 5.00 from the viewpoint of molding processability, The range of 1.03-2.00 is more preferable.

  In this embodiment, the amount of vinyl bonds based on the conjugated diene in the copolymer and the hydrogenation rate of the hydrogenated copolymer can be measured by a nuclear magnetic resonance apparatus (NMR).

  In this embodiment, the weight average molecular weight and molecular weight distribution of the copolymer are measured by gel permeation chromatography (apparatus: “LC-10” (manufactured by Shimadzu Corporation), column: TSKgelGMHXL (4.6 mmID × 30 cm), The molecular weight can be determined from the polystyrene-equivalent molecular weight of the solvent (tetrahydrofuran).

  When a plurality of polymer blocks are present in the component (A), the structures such as the molecular weight and composition may be the same or different. The boundaries and the extreme ends of each block need not be clearly distinguished.

The distribution of the vinyl aromatic monomer in each polymer block is not particularly limited, and may be uniformly distributed, or may be distributed in a taper shape, a step shape, a convex shape, or a concave shape. In addition, a crystal part may be present in the polymer block.
In each copolymer block, a plurality of segments having different vinyl aromatic compound contents may coexist.

In the present embodiment, the distribution of vinyl units of conjugated diene units in each block is not particularly limited, but may vary. The method for controlling the distribution of vinyl units is not particularly limited, and can be performed by a known method. For example, a vinylating agent is added during the polymerization reaction, or the temperature during the polymerization is changed.
The distribution of the hydrogenation rate of the conjugated diene unit is not particularly limited, but may vary. The method for controlling the distribution of the hydrogenation rate is not particularly limited, and can be performed by a known method. For example, changing the distribution of vinyl units or changing the hydrogenation rate of the monomer may be mentioned. For example, it can be controlled by a method in which isoprene and butadiene are copolymerized and then hydrogenated using a catalyst, and the difference between the hydrogenation rates of isoprene units and butadiene units is utilized.

The method for producing these copolymers is not particularly limited, and any known method may be used. For example, the copolymer can be obtained by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent.
It does not specifically limit as a hydrocarbon solvent, A well-known thing can be used. For example, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; benzene, Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene are listed.

The initiator is not particularly limited, and is generally an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound known to have anionic polymerization activity for a conjugated diene compound and a vinyl aromatic compound, An organic amino alkali metal compound or the like can be used.
Examples of the alkali metal include lithium, sodium, and potassium.

  The organic alkali metal compound is not particularly limited, and is preferably an aliphatic or aromatic hydrocarbon lithium compound having 1 to 20 carbon atoms, a compound containing one lithium in one molecule, and a plurality of compounds in one molecule. Dilithium compounds, trilithium compounds and tetralithium compounds containing lithium are preferred. Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec -Reaction product of butyllithium, reaction product of divinylbenzene, sec-butyllithium and 1,3-butadiene.

The hydrogenated product can be obtained, for example, by hydrogenating the copolymer obtained above. It does not specifically limit as a hydrogenation catalyst, A well-known thing can be used, For example, the following are mentioned.
(1) A supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like,
(2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum;
(3) A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr is used.

  Specific examples of the hydrogenation catalyst include, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-35381. The hydrogenation catalyst described in JP-B-2-9041 can be used.

Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.
As the titanocene compound, for example, compounds described in JP-A-8-109219 can be used. Specifically, it has at least one or more ligands having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  In this embodiment, an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group may be bonded to the component (A) as necessary.

  The content of the component (A) in the crosslinking composition of the present embodiment is not particularly limited, and is preferably 30% by mass or more from the viewpoint of low rebound resilience, tear strength, and permanent strain, and has workability and low cost. From the viewpoint, 90% by mass or less is preferable. 35 mass% or more and 85 mass% or less are more preferable, and 45 mass% or more and 80 mass% or less are still more preferable.

<(B) component>
The (B) hydrogenated hydrocarbon plasticizer used in this embodiment is a plasticizer obtained by hydrogenating a hydrocarbon resin.
The hydrocarbon plasticizer in the present embodiment is not particularly limited as long as it is a resin mainly composed of carbon and hydrogen. Specific examples include rosin or terpene resin based on natural resin, aliphatic resin or aromatic resin contained in synthetic resin based petroleum resin, copolymer of aliphatic monomer and aromatic monomer, alicyclic group Examples thereof include resins, coumarone / indene resins, styrene resins, and hydrogenated resins thereof.

The natural resin rosin is not particularly limited, and examples thereof include gum rosin, polymerized rosin, modified rosin glycerin and pentaerythritol ester.
The natural resin terpene is not particularly limited, and examples thereof include terpene resins (α-pinene, β-pinene, dipentene), aromatic modified terpene resins, and terpene phenol resins.
The synthetic resin-based aliphatic resin is not particularly limited, and examples thereof include polymers such as isoprene and piperylene.
The synthetic resin-based aromatic resin is not particularly limited, and examples thereof include polymers such as styrene, vinyl toluene, and indene.
It does not specifically limit as alicyclic resin, Polymers, such as dicyclopentadiene, are mentioned.
In this embodiment, these hydrogenated hydrocarbon plasticizers may be used alone or in combination of two or more.

Commercially available hydrogenated hydrocarbon plasticizers include “ALCON P” (produced by Arakawa Chemical Co., fully hydrogenated product), “ALCON M” (produced by Arakawa Chemical Industries, partially hydrogenated product), “Clearon P” (Yasuhara Chemical). And a completely hydrogenated product), “Picotac 8095” (manufactured by Eastman), and the like.
By including the component (B) in the crosslinking composition, the compatibility of the crosslinking composition is increased, unevenness in crosslinking speed can be reduced, and in the case of a crosslinked body or a crosslinked foamed body, bubbles are reduced. In addition, since the variation in shape can be reduced, a homogeneous crosslinked body or crosslinked foamed body can be obtained. As a result, a molded body having not only excellent mechanical strength but also excellent surface smoothness can be obtained.

From the viewpoint of mechanical strength, the component (B) is preferably one in which 10 mol% or more of unsaturated groups contained in the hydrocarbon plasticizer before hydrogenation are hydrogenated. From the viewpoint of reducing unevenness in the crosslinking rate, a partial hydrogenation type in which 90 mol% or less of unsaturated groups before hydrogenation is hydrogenated is preferable.
According to this embodiment, the component (B) is preferably a partially hydrogenated hydrocarbon plasticizer. More preferred is a partial hydrogenation type with a hydrogenation rate of 15 mol% or more and 85 mol% or less, and further preferred is a partial hydrogenation type with a hydrogenation rate of 20 mol% or more and 80 mol% or less.

  In the present embodiment, the hydrogenation rate of the component (B) can be obtained from the iodine value before and after hydrogenation. The iodine value of (B) component is not specifically limited, 200 g or less is preferable. The iodine value is mainly used for comparing the number of C═C bonds contained in a complex mixture derived from nature, and can be determined by a method according to ASTM-D1959 in this embodiment.

  The weight average molecular weight of (B) component is not specifically limited, 100 or more are preferable from a viewpoint of mechanical strength, and 3000 or less is preferable from a compatible viewpoint of a composition. The weight average molecular weight of the component (B) can be measured by gel permeation chromatography (GPC). The weight average molecular weight of the component (B) is determined from the polystyrene-equivalent molecular weight by GPC measurement (apparatus: “LC-10” (manufactured by Shimadzu Corporation), column: TSKgel GMHXL (4.6 mm ID × 30 cm), solvent: tetrahydrofuran). Can do.

The component (B) is preferably a hydrogenated hydrocarbon plasticizer obtained by hydrogenating a hydrocarbon resin having an alicyclic structure from the viewpoint of compatibility of the composition.
The method for hydrogenation is not particularly limited, and a known method can be used. For example, there is a method in which a noble metal such as palladium, ruthenium, rhodium or the like supported on a carrier such as activated carbon, activated alumina, diatomaceous earth, or the like is used as a catalyst.

  There is no particular limitation on the reaction mode when performing hydrogenation, and a known method can be used. For example, a batch system in which the reaction is performed while suspending and stirring the powdered catalyst may be used, or a continuous system using a reaction tower filled with the molded catalyst may be used.

  The reaction solvent for hydrogenation may or may not be used. When using a reaction solvent, the kind of reaction solvent is not specifically limited, The solvent used normally can be used. For example, alcohols, ethers, esters, and saturated hydrocarbons are used.

  Although the reaction temperature in the case of hydrogenation is not specifically limited, Preferably it is 20-250 degreeC, More preferably, it is 50-200 degreeC. By setting the reaction temperature to 20 ° C. or higher, the hydrogenation rate can be increased, and by setting the reaction temperature to 250 ° C. or lower, the decomposition reaction of the hydrogenated product can be suppressed.

The softening point of the component (B) is not particularly limited, and is preferably in the range of 50 ° C. or higher and 150 ° C. or lower, more preferably in the range of 75 ° C. or higher and 135 ° C., more preferably in the range of 85 ° C. or higher and 125 ° C. A range of ° C is more preferred.
In the present embodiment, the softening point can be measured according to ASTM-E28.
In general, the glass transition temperature of a hydrocarbon resin tends to correlate with the softening point, and the glass transition temperature of the hydrocarbon resin tends to be about 50 ° C. lower than the softening point of the hydrocarbon resin. Accordingly, since the low resilience can be achieved, it is preferable that the component (B) has such a softening point.

  The content of the component (B) in the crosslinking composition of the present embodiment is not particularly limited, and is preferably 0.5% by mass or more from the viewpoint of low rebound resilience, and 20% by mass or less from the viewpoint of mechanical strength. preferable. More preferably, they are 2 mass% or more and 15 mass% or less, More preferably, they are 3 mass% or more and 10 mass% or less.

<(C) component>
The (C) inorganic filler used in the present embodiment is not particularly limited, and known ones can be used. For example, those generally used for blending thermoplastic resins and rubber-like polymers can be used.
Specifically, inorganic fillers such as silica, talc, mica, calcium silicate, hadrotalcite, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, etc. And carbon black.

  The content of the component (C) in the crosslinking composition of the present embodiment is not particularly limited, and is preferably 0.5% by mass or more from the viewpoint of foamability and shape stability, and from the viewpoint of weight reduction and tear strength. 20 mass% or less is preferable. More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

<(D) component>
The component (D) is not particularly limited as long as it is a crosslinkable compound. Examples thereof include organic peroxides and sulfur compounds. Among these, organic peroxides are preferable from the viewpoint of economy.
Specifically, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t -Butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4 -Bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperbenzoate, t-butylperoxyisopropylcarbonate, diacetyl peroxide, lauroyl Peroxide, t-butylcumyl peroxy De, and the like.

  The content of the component (D) in the crosslinking composition of the present embodiment is not particularly limited, and is preferably 0.05% by mass or more from the viewpoints of mechanical strength, compression set resistance and foamability, and flexibility and machine From the viewpoint of strength, 3% by mass or less is preferable. 0.2 mass% or more and 1.5 mass% or less are more preferable, and 0.3 mass% or more and 1.0 mass% or less are still more preferable.

<(E) component>
The crosslinked foaming composition of the present embodiment preferably further contains (E) a foaming agent. Thereby, not only efficient foaming but also lightening can be achieved.

  (E) It does not specifically limit as a component, A well-known thing can be used. Specific examples include azodicarbonamide (ADCA), N, N′-dinitrosopentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3′-disulfonylhydrazide, p-toluene. Organic pyrolytic foaming agents such as sulfonyl semicarbazide and trihydrazinotriazine, and inorganic pyrolytic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate and ammonium carbonate are preferred. Among these, azodicarbonamide (ADCA) and sodium hydrogen carbonate are more preferable from the viewpoint of tear strength.

  The content of the component (E) in the crosslinked foaming composition of the present embodiment is not particularly limited, and is 0.2% by mass or more from the viewpoint of weight reduction, and 10% by mass or less from the viewpoint of tear strength and compression set. Is preferred. More preferably, they are 0.5 mass% or more and 5 mass% or less, More preferably, they are 0.8 mass% or more and 2.0 mass% or less.

<(F) component>
In the present embodiment, it is preferable to contain (F) an ethylene-based copolymer.
The ethylene copolymer that can be used in the present embodiment is not particularly limited as long as it is a copolymer containing ethylene as a structural unit, and a known one can be used. For example, polyethylene (PE) which is an ethylene polymer, ethylene / vinyl acetate copolymer (EVA) obtained by copolymerizing ethylene and vinyl acetate, ethylene and an α-olefin having 3 to 10 carbon atoms, An ethylene / α-olefin copolymer, which is a low-crystalline random copolymer comprising a block copolymer containing ethylene and α-olefin (for example, a hard segment is crystalline polyethylene and a soft segment is ethylene-octene) Multiblock copolymer comprising random blocks). As the ethylene / α-olefin, one containing a soft segment portion and a hard segment portion is preferable. By having both the soft segment portion and the hard segment portion in the molecular chain, the compression set can be further reduced.
These ethylene copolymers may be used alone or in combination of two or more.

In order to adhere the crosslinking composition of the present embodiment to other materials, it is preferable to use an ethylene / vinyl acetate copolymer (EVA) together when an adhesive is used.
In order to increase the mechanical strength of the crosslinking composition, it is particularly preferable to use an ethylene / α-olefin copolymer in combination. An ethylene / vinyl acetate copolymer (EVA) and an ethylene / α-olefin copolymer may be used in combination.
The ethylene / vinyl acetate copolymer (EVA) that can be used in the present embodiment is not particularly limited, and a commercially available one can be used.
The ethylene / α-olefin copolymer that can be used in the present embodiment is not particularly limited, and a commercially available one can be used. For example, “Tuffmer (made by Mitsui Chemicals)”, “Engage (made by Dow)”, “Infuse (made by Dow)” and the like can be mentioned.

  The kind of polyethylene is not limited, A well-known thing can be used. Examples include high density polyethylene, ultra high molecular weight high density polyethylene, low density polyethylene, linear low density polyethylene, and ultra low density polyethylene.

  The component (F) preferably contains an ethylene copolymer having a Shore A hardness of 70 degrees or more from the viewpoint of tear strength and low rebound resilience. From the viewpoint of tear strength and weight reduction, it is preferable to contain an ethylene copolymer having a Shore A hardness of 75 degrees or more, more preferably 80 degrees or more, and still more preferably 83 degrees or more.

  The Shore A hardness in the present embodiment is performed according to ASTM-D2240, and can be measured using, for example, an Asker C type durometer hardness meter.

In the present embodiment, butyl rubber may be used in combination from the viewpoint of low rebound resilience.
The butyl rubber that can be used in the present embodiment is not particularly limited, and known ones can be used.

In the present embodiment, a halogen-containing polymer may be used in combination for the purpose of improving processability and physical properties during production.
The polymer having halogen that can be used in the present embodiment is not particularly limited, and a known polymer can be used. Brominated butyl rubber and chlorinated polyethylene are preferred.

  In the crosslinking composition in the present embodiment, if necessary, other polymers, crosslinking aids, heat stabilizers, weathering stabilizers, flame retardants, hydrochloric acid absorbents, antistatic agents, glass fibers, carbon fibers, Various additives such as reinforcing agents such as metal whiskers, titanium oxide, iron oxide, carbon black, pigments, and dyes can be blended within a range that does not impair the purpose of the present embodiment.

In the present embodiment, in order to obtain a composition having more excellent low resilience (impact absorbability) and mechanical strength, in the resin composition for crosslinking, the component (A) is 30% by mass or more and 90% by mass or less. , (B) component is 0.5 mass% or more and 20 mass% or less, (C) component is 0.5 mass% or more and 20 mass% or less, and (D) component is 0.05 mass% or more and 3 mass% or less. It is preferable that (E) component is 0.2 mass% or more and 10 mass% or less, and (F) component is 5 mass% or more and 60 mass% or less.
More preferably, the component (A) is 45% by mass to 85% by mass, the component (B) is 2% by mass to 15% by mass, and the component (C) is 0.5% by mass to 15% by mass. (D) component is 0.2 mass% or more and 1.5 mass% or less, (E) component is 0.5 mass% or less, 5 mass% or less, and (F) component is 20 mass% or less. It is not less than 50% by mass.

  The cross-linking composition and the cross-linking foaming composition according to the present embodiment include the components (A) to (D), and if necessary, the components (E) and (F) using a kneader at a predetermined ratio. Can be melt mixed and prepared. In particular, when (D) a crosslinking agent or (E) a foaming agent is used, it is preferable to prepare by melt mixing at a temperature lower than the decomposition temperature.

  The kind of kneader that can be used in the present embodiment is not particularly limited, and for example, a Henschel mixer, a Banbury mixer, a roll, an extruder, or the like can be used.

  In this embodiment, the mixing method is not particularly limited. For example, after mixing components (D) and (E) in advance, the components (D) and (E) are added and mixed. May be.

Moreover, the shape of the composition for crosslinking which concerns on this embodiment is not specifically limited, A mixture can be shape | molded in a desired shape as needed. For example, it can be prepared in a pellet form, a sheet form (sometimes referred to as a film form), a strand form, a chip form or the like by a granulator or the like.
The sheet | seat of the composition for bridge | crosslinking which concerns on this embodiment can be prepared by using the extruder obtained by making it above, or a calendar molding machine, for example.
Alternatively, after the components of the crosslinking composition of the present embodiment are kneaded with a Brabender or the like, a method of forming into a sheet shape with a calender roll, a method of forming a sheet with a press molding machine, a kneading with an extruder, and a T die Alternatively, an uncrosslinked and unfoamed foamable sheet can be prepared by a method of forming a sheet through an annular die.

  A crosslinked foam can be obtained by crosslinking and foaming the crosslinking composition of the present embodiment. The crosslinked foam of this embodiment is excellent in low rebound resilience and tear strength. In the present embodiment, the crosslinking composition can be crosslinked and foamed by press molding or injection molding. For example, the crosslinking composition of the present embodiment is also suitable for the case of injection-crosslinking (foaming) molding into a predetermined mold using the pelletized composition.

Here, an example in which the crosslinking composition of this embodiment is formed into a sheet will be described.
The composition for crosslinking according to the present embodiment formed into a sheet by the above method or the like is cut into a size in the range of 1.0 to 1.2 times the volume of the mold, and held at 120 to 200 ° C. Insert into the mold. The mold clamping pressure is 30 to 300 kgf / cm ² , and the composition is obtained by pressurizing and melting under the conditions of a holding time of 10 to 90 minutes, performing a crosslinking reaction and decomposing the foaming agent, and then opening the mold. A primary cross-linked foam can be produced by foaming.

  The shape of the cross-linking foam mold for producing the primary cross-linked foam is not particularly limited, but a mold having such a shape that a sheet can be obtained is used. The cross-linking foaming mold preferably has a completely sealed structure so that gas generated when the resin is melted or when the foaming agent is decomposed is not released. As the mold, a mold having a taper on the inner surface is preferable from the viewpoint of resin releasability.

In this embodiment, you may provide a predetermined shape by compression-molding a primary crosslinked foam as needed. The compression molding conditions at this time are not particularly limited. For example, the mold temperature is 120 to 200 ° C., the clamping pressure is 30 to 300 kgf / cm ² , the compression time is 5 to 60 minutes, and the compression ratio is 1.1 to The range is 3.0.

  In the present embodiment, the foamed foamed product can be formed by molding the crosslinked foaming composition into various shapes and sizes in addition to the sheet shape. In this embodiment, the shape and magnitude | size of the foaming molding obtained and the composition for bridge | crosslinking which comprises it are not specifically limited, It can shape | mold into various shapes other than a sheet form.

  The crosslinked foam of the present embodiment can be used as a sheet (sometimes referred to as a film), injection molded products of various shapes, hollow molded products, compressed air molded products, vacuum molded products, extrusion molded products, and the like.

  Specifically, the crosslinked body or crosslinked foamed body of the present embodiment can be used as a sheet or a molded article having various shapes. For example, building materials such as flooring for condominiums, wall materials, ceilings, window frames, shutters, doors, soundproof walls, roofing materials, vibration control devices, new vibration isolation surfaces, dampers, pipes for water supply and drainage pipes, etc .; Anti-tumbling sheets, mats and films such as vibration-damping films, vibration-isolating sheets, anti-vibration mats, etc .: Audio equipment such as record support turntables, CD players, microphone holders, speaker cone edges, radio cassettes, mini-discs, photocopiers, It can be used as a member capable of reducing unpleasant noise and resonance noise of office automation equipment such as FAX and printer; information transmission device such as mobile phone and mobile PC.

  It can also be used as a member to reduce uncomfortable and resonant noise caused by motor driving in household appliances such as TV, refrigerator, air conditioner outdoor units and sound in ducts, noise in automobile engine rooms and automobiles, etc. it can. Among them, because of its high shock absorption, it is suitable for shock-absorbing foams such as shoes, fall prevention sheets, mats and films, and also suitable as a soundproof sheet for piping such as water supply pipes and drain pipes. is there.

  Among these, the crosslinked foam of this embodiment can be suitably used as a footwear material, and can be suitably used as a midsole or insole for shoes among footwear materials.

  Midsole, insole, etc. are not only lightweight as soles used for shoe soles, but also need to have low rebound resilience to mitigate impact when landing and have sufficient mechanical strength . From such a viewpoint, in order to obtain a desired shape, it is not only easy to mold, but also excellent in low rebound resilience (impact absorbability) and tear strength.

  The midsole for shoes of this embodiment is used by bonding an outsole or an upper after molding, for example. The insole (insole) for shoes of this embodiment is used, for example, by inserting the shoe into the shoe after manufacturing the shoe.

In this embodiment, a crosslinked foam can be used as a laminated body with various materials. Thereby, it can be used according to various uses.
For example, it can be set as the laminated body etc. which contain the crosslinked foam of this embodiment, and the plywood laminated | stacked with this crosslinked foam. In the present embodiment, the method for stacking is not particularly limited, and a known method can be used. For example, bonding with an adhesive, molding and adhesion at the same time in a mold, superheating after lamination, cross-linking and adhesion can be mentioned.

  Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to these examples.

(I) Measurement of properties and physical properties of polymer The properties and physical properties of the polymer were measured as follows.
(1) Styrene content, vinyl bond amount of conjugated diene, hydrogenation rate of double bond based on conjugated diene compound vinyl aromatic monomer unit, 1,4-bond unit and 1,2-bond unit of butadiene, The amount of ethylene units or butylene units was measured by nuclear magnetic resonance spectrum analysis (NMR). Detailed measurement conditions are as follows.
Measuring equipment: “JNM-LA400” (manufactured by JEOL)
Solvent: Deuterated chloroform Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift criteria: Tetramethylsilane (TMS)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

(2) Polystyrene block content Using a copolymer before hydrogenation, M.M. Kolthoff, et al. , J .; Polym. Sci. 1, 429 (1946). For the decomposition of the copolymer, a 0.1 g / 125 mL tertiary butanol solution of an osmic acid solution was used.

(3) Weight average molecular weight and molecular weight distribution In this embodiment, the weight average molecular weight and molecular weight distribution of the copolymer are measured by gel permeation chromatography (GPC) (measuring device: “LC-10” (manufactured by Shimadzu Corporation), It calculated | required from the polystyrene conversion molecular weight by the commercially available standard polystyrene by column: TSKgelGMHXL (4.6mmID * 30cm) 2 pieces, a solvent: Tetrahydrofuran).
The molecular weight distribution is a ratio (M _w / M _n ) of the obtained weight average molecular weight (M _w ) and number average molecular weight (M _n ).

(4) Coupling rate The molecular weight distribution of GPC measurement was determined using the peak area before coupling and the peak area after coupling.

(5) tan δ peak temperature The tan δ peak temperature was determined by dynamic viscoelasticity measurement (1 Hz). Specifically, the dynamic viscoelasticity data is obtained by cutting the sample into a size of 10 mm in width and 35 mm in length, and using the twisted geometry of the device “ARES” (manufactured by TI Instruments Co., Ltd.) The effective measurement length is 25 mm, the strain is 0.5%, the frequency is 1 Hz, and the value obtained from −50 ° C. to 50 ° C. at a temperature increase rate of 3 ° C./min. The peak temperature was determined by automatic measurement of “RSI Orchestrator” (manufactured by TA Instruments Inc.).
(II) Production method of copolymer (A) containing vinyl aromatic (1) Preparation of hydrogenation catalyst Hydrogenation catalyst I used for the hydrogenation reaction was prepared by the following method.
Charge 1 L of dried and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride, add an n-hexane solution containing 200 mmol of trimethylaluminum with sufficient stirring, The reaction was performed at room temperature for 3 days.

(2) Production method of copolymer (A) A block copolymer was prepared by the following method using an agitator having an internal volume of 10 L and a jacketed tank reactor.
A predetermined amount of cyclohexane was charged into the reactor and the temperature was adjusted to 70 ° C., and then the amount of n-butyllithium was set to 0. 0 relative to the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). N is added from the bottom of the reactor so as to be 09 parts by mass, and further, the amount of N, N, N ′, N′-tetramethylethylenediamine is 0.7 mol with respect to 1 mol of n-butyllithium. , N, N ′, N′-tetramethylethylenediamine in cyclohexane solution is added, and then a cyclohexane solution containing 20 parts by mass of styrene as a monomer (monomer concentration: 24% by mass) is supplied over 10 minutes. Adjusted to 70 ° C. After stopping the supply, the reaction was carried out for 15 minutes while adjusting the temperature in the reactor to 70 ° C.
Next, a cyclohexane solution (monomer concentration: 24% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene is continuously supplied to the reactor at a constant rate over 60 minutes, and the temperature in the reactor during that period is 70. It adjusted so that it might become -80 degreeC, and it was made to react, adjusting temperature in a reactor to 70 degreeC for 10 minutes after supply stop.
After completion of the polymerization, a cyclohexane solution of ethyl benzoate was added so that the amount of the bifunctional coupling agent ethyl benzoate was 0.5 equivalent to 1 mol of n-butyllithium, and the temperature in the reactor was adjusted to 70 ° C. The reaction was carried out for 10 minutes while adjusting.
When the copolymer obtained by batch coupling polymerization was analyzed, the styrene content was 67% by mass, the polystyrene block content was 20% by mass, and the vinyl bond content of the butadiene part was 25% by mass, The coupling rate was 50%, the weight average molecular weight (M _w ) was 1900000, and the molecular weight distribution (M _w / M _n ) was 1.7.
Next, to the copolymer obtained by batch coupling polymerization, 100 ppm of the above hydrogenation catalyst is added in terms of titanium per 100 parts by mass of the non-hydrogenated copolymer, and hydrogenation reaction is performed at a hydrogen pressure of 0.7 MPa and 65 ° C. Went. After completion of the reaction, methanol was added, and then octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the polymer. As a result, a hydrogenated copolymer (Polymer 1) was obtained.
Polymer 1 had a hydrogenation rate of 30%, a melt flow rate (MFR, 190 ° C., 2.16 kg) of 4 g / 10 min, and a tan δ peak temperature of 18 ° C.

(III) Other formulation composition (B-1): “Arcon M-100” (trade name, manufactured by Arakawa Chemical Industries, softening point: 100 ° C., partially hydrogenated type)
-(B-2): "Arcon P-100" (trade name, manufactured by Arakawa Chemical Industries, softening point: 100 ° C, complete hydrogenation type, iodine value of 30 g or less)
-Non-hydrogenated hydrocarbon plasticizer (1): "HIKOREZ A-1100" (trade name, manufactured by KOLON, non-hydrogenated type)
Ethylene copolymer (1): “ENGAGE 8480” (trade name, manufactured by Dow, specific gravity 0.902, Shore A hardness: 89 degrees, glass transition temperature: −31 ° C.)
Brominated butyl rubber (1): “BROMOBUTYL2244” (trade name, manufactured by JSR, halogen content 2%, specific gravity 0.93)
-Foaming agent: "Exceller AK-2" (trade name, manufactured by Eiwa Kasei Kogyo, DPT / ADCA)
* DPT: N, N'-dinitrosopentamethylenetetramine * ADCA: Azodicarboxylic acid amide

(IV) Production of Cross-Linked Foam Using a kneader as a melt kneader, the components of the first step shown in Table 1 were kneaded and kneaded at a temperature of 110 to 120 ° C. and a kneading time of 15 minutes. Next, using a two-roll open mill as a melt kneader, the kneaded product of the first step and each compounding component of the second step shown in Table 1 are kneaded at a temperature of 90 to 100 ° C. and a kneading time of 10 minutes. Kneaded.
Next, the kneaded product obtained using the compression molding machine is compressed at a temperature of 170 ° C. and a pressure of 150 kgf / cm ² for 15 minutes, and the mold is opened to foam the composition, thereby producing a primary crosslinked foamed body. did. After storage at room temperature for 24 hours, the primary foam is held at 170 ° C. for 15 minutes at a pressure of 150 kgf / cm ² (compression ratio: 140 to 150%), held for 10 minutes, cooled to room temperature with water cooling, the pressure is released, A cross-linked foamed molded article having a thickness of 1 cm was obtained.

(V) Measurement of characteristics of crosslinked foamed molded article (1) Surface smoothness The smoothness of the surface of the primary crosslinked foam obtained in (IV) was visually evaluated. A bubble having a fine and uniform shape was evaluated as “◯” because it was evaluated as smooth. The case where the bubble shape was non-uniform or coarse and the roughness was large was evaluated as “bad” and evaluated as “x”.

(2) 22 ° C hardness (Asker C)
It measured based on ASTM-D2240 using the crosslinked foaming molding obtained by (IV).

(3) Peel strength After the cross-linked foam molded product obtained in (IV) was cut into a width of 2 cm, a cut was made in the central portion of the thickness and peeled at a rate of 100 mm / min.
Peel strength = measured maximum peel strength / 2 (N / cm)

(4) Rebound resilience Using the cross-linked foam molded product obtained in (IV), a steel ball (16.3 g) was dropped on the test piece, and the rebound resilience was measured from the following formula. The measurement temperature was 22 ° C. A smaller value of rebound resilience indicates better shock absorption.
14% or less was regarded as acceptable “◯”, and 16% or more was regarded as unacceptable “x”. 15% was set as “Δ”.

Rebound resilience (%) = [H _R / H ₀ ] × 100
H ₀ = sphere fall height
H _R = The height at which the sphere repels

  The results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1 below.

In each of Examples 1 to 5, the specific gravity is 0.21 g / cc or less, the 22 ° C. hardness is 16 degrees or more, the peel strength is 19 N / cm or more, and the rebound resilience is “◯” (14 % Or less).
On the other hand, Comparative Example 1 had a surface smoothness of “x” and a peel strength of 15 N / cm. In Comparative Example 2, the rebound resilience was “x” (16% or more). In Comparative Example 3, the surface smoothness was “x” and the peel strength was 15 N / cm.
As described above, according to this example, at least (A) a copolymer mainly composed of an alkylene unit and a vinyl aromatic monomer unit, or a copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit. By using a hydrogenated copolymer obtained by hydrogenating a polymer, (B) a hydrogenated hydrocarbon plasticizer, (C) an inorganic filler, and (D) a crosslinking composition containing a crosslinking agent, low rebound resilience It was shown that a crosslinked body and a crosslinked foam excellent in (impact absorbability) and tear strength can be obtained.

  The crosslinking composition, crosslinked body, and crosslinked foamed body of the present invention can be used in a wide range of fields as molded articles having various shapes. For example, it can be used in a wide range of fields as building materials for condominiums, various films, equipment devices such as acoustic equipment, OA equipment and mobile phones, and various members for home appliances. In particular, the cross-linked foam of the present invention is suitable as a footwear material, and can be suitably used as a midsole or insole for shoes, especially among footwear.

Claims (15)

(A) a hydrogenated copolymer in which a part of a copolymer mainly composed of a conjugated diene unit and a vinyl aromatic monomer unit is hydrogenated;
(B) a hydrogenated hydrocarbon plasticizer;
(C) an inorganic filler;
(D) a crosslinking agent;
Containing
The composition for crosslinking in which the hydrogenation rate of the conjugated diene monomer contained in the component (A) is 10 to 50 mol% with respect to the total unsaturated bonds of the conjugated diene monomer before hydrogenation.   The composition for crosslinking according to claim 1, wherein the softening point of the component (B) is 60 to 150 ° C.   The crosslinking composition according to claim 1 or 2, wherein the component (B) is obtained by hydrogenating 10 mol% or more of unsaturated groups contained in the hydrocarbon-based plasticizer before hydrogenation. The component (A) is a hydrogenated copolymer in which a part of a block copolymer mainly composed of the conjugated diene unit and the vinyl aromatic monomer unit is hydrogenated. The composition for crosslinking according to any one of the above. The crosslinking composition according to any one of claims 1 to 4, wherein a tan δ peak temperature of the component (A) is -10 to 40 ° C. The composition for crosslinking according to claim 5, wherein the component (A) contains a hydrogenated copolymer block mainly composed of the vinyl aromatic monomer and the conjugated diene monomer. (E) The composition for crosslinking according to any one of claims 1 to 6 , further comprising a foaming agent. (F) The composition for crosslinking according to any one of claims 1 to 6 , further comprising an ethylene-based copolymer. The composition for crosslinking according to any one of claims 1 to 6 , further comprising (E) a foaming agent and (F) an ethylene-based copolymer. In the crosslinking composition,
The component (A) is 30 to 90% by mass,
Said (B) component is 0.5-20 mass,
The component (C) is 0.5 to 20% by mass,
The component (D) is 0.05 to 3% by mass,
The component (E) is 0.2 to 10% by mass,
The composition for crosslinking according to claim 9, wherein the component (F) is 5 to 60% by mass.   The crosslinked body which consists of a composition as described in any one of Claims 1-10.   The crosslinked foamed body which consists of a composition as described in any one of Claims 1-10.   Footwear comprising the crosslinked foam according to claim 12.   Footwear comprising the cross-linked foam according to claim 12 as a midsole or an insole.   A laminate comprising the crosslinked foam according to claim 12 and a member on which the crosslinked foam is laminated.