TW201213426A - Foam and foaming composition - Google Patents

Abstract

To obtain a foam having excellent hardness, dimensional stability, thermal moldability, and mechanical strength; the foam being suitable for the midsole, inner sole, or outer sole of a shoe. Provided is a foam that has a specific gravity of 0.1-0.98 g/cc and is obtained by crosslinking a foaming composition containing: (a) a block copolymer containing 65-95 mass% of a vinyl aromatic hydrocarbon and 5-35 mass% of a conjugated diene, the block ratio of the vinyl aromatic hydrocarbon polymer being 40-98 mass%, the storage modulus (E') at 30 DEG C in dynamic viscoelastic measurement being 3 108 to 2.35 109 Pa, and one or more peak temperatures existing in the range of 85 to 125 DEG C for the tand function of a dynamic viscoelastic measurement; (b) isoprene rubber and/or diene rubber; (c) a filler; and (d) a blowing agent; the mass ratio of component (a)/component (b) being 1-30/70-99, and the content of components (c) and (d) being 1-100 mass parts and 0.1-30 mass parts, respectively, relative to a total of 100 mass parts of components (a) and (b).

Description

201213426 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition for a material for a shoe midsole, a (four) or an outsole, and a composition for a foam. [Prior Art] Foam materials used in sports shoes, etc. require materials such as cushioning, impact cushioning, and lightweight properties. Previously, the material used was: ethylene-vinyl acetate copolymer (EVA) A foam of a main component or a foamed base rubber having a polyaminocarbamic acid (PU) as a main component, and a rubber composition containing a filler such as a dioxide dream or a carbon black Foamed body. The above-mentioned air bubbles can be contained in the crosslinked foamed body for foaming by foaming of a foaming agent, blending of fine hollow spheres, etc., and further weight reduction is being studied. First, various foam materials as described later are proposed. For example, Patent Document 1 discloses a material containing syndiotactic 12-polybutylene dilute as a foamed rubber sole which is excellent in abrasion resistance, lightweight, and non-slip. Patent Document 2 discloses a block copolymer-based crosslinked foam which is intended to be lightweight, has a cushioning air permeability, and has sound insulating properties. In Lie 3, it is revealed that the content containing styrene is tender. The foam of the material of the styrene-butadiene block copolymer is a foam which is small in hardness change even in a high-temperature and low-temperature environment, and is excellent in cushioning property and impact cushioning property. In Patent Document 4, a thermoplastic elastomer and a composition containing a radiation-type thermoplastic elastomer and a linear [2-mertene-butadiene] are disclosed as excellent moldability, and excellent in flexibility and moldability. Molding composition. Patent Document 5 discloses a hydrogenated block copolymer useful for producing a foam having excellent tear strength, compression set resistance, low rebound resilience, and abrasion resistance. PRIOR ART DOCUMENT Patent Document Patent Document 1: Patent Japanese Laid-Open Patent Publication No. JP-A-63-225638 Patent Document 3: Japanese Patent Laid-Open Publication No. Hei No. Hei. Patent Document 5: International Publication No. 2007/094216 SUMMARY OF THE INVENTION Problems to be Solved by the Invention However, various foam materials previously disclosed as described above are in hardness, dimensional stability, thermoforming There is still room for improvement in terms of properties and mechanical strength, and as a foam for shoes (sole), it does not have sufficient characteristics. Therefore, the object of the present invention is to provide a foam which is particularly suitable for a shoe midsole, a shoe last and an outsole which is excellent in hardness, dimensional stability, thermoformability and mechanical strength. Means for Solving the Problems The inventors of the present invention have repeatedly studied in order to solve the problems of the prior art regarding foams as described above, and found that the inclusion of vinyl aromatic hydrocarbons having specific viscoelastic behavior at a specific ratio and A block copolymer of a conjugated diene, a specific rubber component, a filler, and a foam of a foaming agent, 157712.doc 201213426 or a block copolymer containing a blend of aromatic aromatic and co-diene The foam is formed into a foam having a specific hardness in the specific gravity of the specific (4), and the above purpose can be achieved by this, l·+., J, thereby completing the present invention. That is, the present invention is as follows. [1] A foam obtained by crosslinking a composition for a foam comprising the following components: (4) a block copolymer containing at least two vinyl aromatic tobacco polymer blocks, And at least one copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon, and the content of the ethylene-based aromatic tobacco is 65 to 95% by mass, and the content of the total two women is 5 to 35% by mass. The block ratio of the vinyl aromatic hydrocarbon polymer contained in the block copolymer is 40 to 98% by mass, and the storage elastic modulus (E,) at 30 ° C in the dynamic viscoelasticity measurement is 3χ1〇8 Pa or more and 2.35. Χ109 pa or less, and the dynamic viscoelasticity measurement function has a peak temperature of (10) of at least 85 ° C and above 125 ° C below! (b) isoprene-based rubber and/or diene-based rubber; (c) filler; (d) foaming agent; (a) block copolymer and (b) isoprene The mass ratio of the rubber and/or the dilute rubber is from 1 to 30/70 to 99; and is relative to the above (a) block copolymer and the above (b) isoprene rubber and/or diene rubber. 1 part by mass of the total amount, and containing the above (c) filling 157712.doc 201213426 agent 1 to 100 parts by weight, the above (sentence foaming agent 〇丨~3 〇 parts by mass and the specific gravity of the foam is 0.1 to 0.98 [2] The foam of the above [1] wherein the peak temperature of the function (4) of the above-mentioned (4) block copolymer dynamic viscous measurement ΐαηδ is at least one of 9 (rc or more and 125 cp or less). [3] The foam of the above [1] or [2], wherein the (4) segment copolymer contains at least one vinyl aromatic hydrocarbon content of 7 〇 mass% or more and less than 1 〇〇 mass. The random copolymer block of the vinyl aromatic hydrocarbon and the conjugated diene. [4] The foam of any one of the above [1] to [3], wherein the (4) block copolymer contains at least one of Vinyl aroma The random copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene having a hydrocarbon content of 75% by mass or more and more by mass%. [5] The foaming according to any one of the above [1] to [4] The body of the above-mentioned (c) filler is 2 to 90 parts by mass with respect to 100 parts by mass of the total of the block copolymer and the (b) isoprene-based rubber and/or the diene-based rubber. The foaming agent according to any one of the above [1] to [5], wherein the above (&) block copolymer, and the above (b) 100 parts by mass of the isoprene-based rubber and/or the diene rubber 157712.doc -6 - 201213426, and further contains: (e) a thermoplastic elastomer and/or a thermoplastic resin 1 to i 〇〇 [7] The foam according to any one of the above [1] to [6] wherein the specific gravity is 〇1 to 〇7 g/cc, or the specific gravity is 〇.8 to 〇98 g/cc. And a composition for foaming, comprising: (4) a block copolymer, wherein the foam is formed by the foam of any one of the above [丨] to [7]. It contains at least 2 vinyl aromatic hydrocarbons a block of the copolymer and at least one copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon, and the content of the vinyl aromatic smoke is 65 to 95% by volume, and the total of the total amount of the diene is 5 to 5 The mass fraction of the vinyl aromatic hydrocarbon polymer contained in the block copolymer is 40 to 98% by mass, and the storage elastic modulus (ε,) at 3 G ° C in the measurement is 3x1〇8

PaU on 235x10 PaW' and the peak temperature of the function of dynamic viscoelasticity measurement is above 8 5 °C and above 12 5 °Γ at least 1 below it f; (b) Isoprene rubber and/or diterpenoid (c) filler; (d) foaming agent; V () mass ratio 1 and the mass ratio of the above (b) isodecane rubber and/or diene rubber is 1~ 30/70~99;

S 157712.doc A 201213426 The above (4) block copolymer is contained in combination with the above (b) isoprene rubber and/or diene rubber in an amount of 1 part by mass, and the above (4) filler 1 to 100 is contained. The mass part and the above (d) foaming agent are 0.1 to 30 parts by mass. [10] A foam comprising: (a') a block copolymer comprising at least two vinyl aromatic hydrocarbon polymer blocks, and at least one of which comprises a conjugated diene and a vinyl aromatic hydrocarbon The copolymer block has a vinyl aromatic hydrocarbon content of 65 to 95% by mass and a conjugated diene content of 5 to 35 mass. /. The block ratio of the ethylene-based aromatic tobacco polymer contained in the block copolymer is 40 to 98% by mass; (b) the isoprene-based rubber and/or the diene-based rubber knee; Ο) filler; (d) a foaming agent; when the specific gravity is 0.1 to 0.7 g/cc, the hardness measured by the model c is 45-98; and when the specific gravity is 0.8 to 〇 98 g/", the hardness measured by the model a is 6 0 to 9 8. Effects of the Invention According to the present invention, a foam which is excellent in hardness, dimensional stability, thermoformability and mechanical strength and which is mainly suitable for a midsole, an insole or an outsole for shoes can be obtained. MODES OF THE INVENTION The following is a description of the form of the present invention (hereinafter referred to as "the present embodiment 157712.doc 201213426 state"). It is to be understood that the invention is not limited thereto, and various modifications may be made without departing from the scope of the invention. [Foam j] [Foam of the first embodiment] The foam of the first embodiment of the foam of the present embodiment contains the following components (a) to (d). a (:) block copolymer comprising at least two ethylenic aromatic hydrocarbon polymer inclusions, and at least one copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon, and a vinyl aromatic The content of the hydrocarbon is 65 to 95% by mass, the cerium content of the conjugated dilute is 5 to 35% by mass, and the block ratio of the ethylene-based aromatic hydrocarbon polymer contained in the monomer is 40. ~98% by mass, in the dynamic viscoelasticity measurement 3 (the storage elastic modulus (E,) under rc is 3χΐ〇8 Pa or more and 2.35xlG9pa or less' and the peak value of the dynamic viscoelasticity measurement (5) is above 85 °C There is at least one at 125 ° C. (b) Isoprene-based rubber and/or diene-based rubber. 0) Filler. (d) a blowing agent. Further, in the foam of the present embodiment, the mass ratio of the (a) block copolymer to the (b) isoprene-based rubber and/or the diene-based rubber is from 1 to 30/70 to 99. Further, the above (a) block copolymer and the above (^ isocene-based rubber and/or diene-based rubber are contained in a total amount of 1 part by mass, and the above (c) filler 1 to 1 is contained. 〇 mass part, the above (d) foaming agent 〇丨 〇 3 〇 mass 157712.doc 201213426 parts of the foam composition cross-linked to a specific gravity of 〇 H ^ / cc. The following components (a) ~ ingredients (d) (Component (a): Block copolymer) Component (4) contains a block copolymer of a vinyl aromatic hydrocarbon and a divalently dilute as described above. The ethylene group in the component (a) The content of the aromatic hydrocarbon is 65 to 95% by mass, preferably 68 to 93% by mass, more preferably 70 to 90% by mass. The concentric content in the fraction (4) is 5 to 35% by mass, preferably (4). The mass % 'better is 1 0 to 30 mass 〇 / 〇. Person: the content of the ethyl spheroidal aromatic smoke is 65 to 95% by mass, and the total amount of the second diluted glass is set to 5 to 35% by mass. Foaming The hardness of the disk is excellent in the balance between the elongation of the disk and the thermoformability, and is suitable for the foam of (4). The content of the ethylene-based aromatic hydrocarbon in the two-part (4) and the ultraviolet-based spectrophotometer are used in the mixture of the two-wheel mixture. The measurement is carried out for the light of a specific wavelength and the light-receiving degree. The block ratio of the aromatic (tetra) compound contained in 40% of 98%) is preferably 5% to 95% by mass. More preferably 6〇~90% by mass. : The block ratio of the aromatic hydrocarbon polymer is 4 〇, the mass % is 2 = the stability of the inch and the thermoformability are excellent, and the block ratio suitable as the shoe-based aromatic smog polymer can be obtained by the component (4) The content (% by mass) of the random copolymer chain-based aromatic hydrocarbon containing the hydrocarbon and the diene is adjusted. Ethylene and olefin constituents (4) The ethylene copolymer occupied by the random copolymer chain of the block copolymer 157712.doc 201213426 The more the aromatics * the amount of work, the lower the rate of the ethylene-based aromatic hydrocarbon polymer is less. Then the block rate becomes high. As for the money rate of the ethylene-based aromatic-smoke polymer, the method of oxidizing and pulverizing the component (10) copolymer by using peroxidized tert-butyl alcohol as a catalyst is used (oxidative decomposition method··j M k 〇lth〇ff, αL Polym. Sci. 1, 429 (1946), which comprises a vinyl chain aromatic component: a block chain component (having an average degree of polymerization of about 30 or less) The mixture of the hydrocarbon polymer components was separated, and the weight of the ethylene-based aromatic hydrocarbon polymer block chain was measured and found according to the following formula. Block ratio (% by mass) = (the weight of the vinyl group in the block copolymer, the weight of the polymer chain, the weight of the polymer chain, the total weight of the aromatic fluoride in the sequent copolymer in the sequent copolymer of 100) The total weight of the vinyl aromatic fumes in the product is obtained according to the input ratio at the time of polymerization or by analysis by NMR, etc. The component (a) contains at least two vinyl aromatic hydrocarbon polymer blocks, and at least A copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon. The polymer structure of the component (a) is not particularly limited, and for example, a linear block copolymer or radiation represented by the following formula may be used. a block copolymer, or a mixture of any polymer structure such as cough. Further, in the light-emitting block copolymer represented by the following formula, at least one enemy A and/or block is bonded to; X. (Α-Β)η+1 ' Α-(Β-Α)η ' Β-(Α-Β)η+ι, [(AB)k]m+iX, [(AB)k_A]m+1 -X, [(BA)ic]m+iX, [(BA)kB]m+1-X, § 157712.doc 201213426 In the above formulas, block A is composed of a vinyl aromatic hydrocarbon polymer, embedded Section B consists of a total of two dilute and B (a) hydrocarbons In the above formula, X represents, for example, a coupling agent such as antimony tetrachloride, tin tetrachloride, antimony or tris(N,N-glycidylaminomethyl)cyclohexane'epoxidized soybean oil. a residue of a starting agent such as a residue or a polyfunctional organolithium compound. n, k and m are each an integer of i or more, and are usually an integer of 5. Further, the structure of a plurality of bonded polymer chains may be The same component may be different. The above-mentioned component (4) constituting the foam: the ethylene-based aromatic hydrocarbon in the copolymer of the ethylene-based aromatic cigarette and the co-rolled diene in the block B of the block copolymer The distribution of the ground may also be in the form of a wedge-shaped (decreasing) shape. In the copolymer, the portion of the plurality of ethylene-based aromatic hydrocarbons and the distribution of the wedge-shaped distribution may be coexisted in the block towel. The knife (a) melon copolymer preferably contains at least one random copolymer block containing a vinyl aromatic hydrocarbon content of 7 〇 mass% and less than _ mass 乂 k is 75% by mass or more and 98% by mass. The following ethylene-based aromatic cigarettes and a total of two dilute, which can achieve good hardness and dimensional stability Froth. <Production method of component (a) block copolymer> The component (4) can be obtained by polymerizing an ethylene-based aromatic hydrocarbon and a co-diazole by using an organic compound as a starting negative in a hydrocarbon solvent. Obtained. For your cation-based aromatics, for example: styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 1,3-dimethyl phenyl ethene , Ethyl group, Ethyl onion, ^ diphenylethylene N, N--subunit _ p-aminoethyl benzene, n > n_ two n (four) | 157712.doc 5 •12· 201213426 Ethyl styrene, particularly as an ordinary one, may be styrene. These may be used alone or in combination of two or more. a / yoke-ene, a diene having a fluorene pair conjugated double bond, such as '3 butyl-ene, 2-methyl-1,3-butadiene (isoprene), 2,3- Dimethyl _ 1,3-butane coal, ruthenium sulphate, pentane-ene, fluorene, 3-hexadiene, etc., particularly as ordinary ones, may include dibutyl sulphate and isoprene. These may be used alone or in combination of two or more. As the solvent, for example, an aliphatic hydrocarbon such as n-butane, isobutane, n-pentane, an alkyl-n-heptane or n-octane, cyclopentane, methylcyclopentane, or a methyl ring can be used. Alicyclic, cycloheptane, methylcycloheptane and other alicyclic (four) '-benzene, toluene, xylene, ethylbenzene and other aromatic hydrocarbons. These may be used alone or in combination of two or more. As the polymerization initiator for carrying out the polymerization of the component (a), generally: ten; eight aliphatic and ethylenic aromatic compounds having an anionic polymerization activity, an aliphatic hydrocarbon metal compound, an aromatic hydrocarbon alkali metal compound, An organic amine based metal compound or the like. As the organic metal constituting the above-mentioned materials, examples include a solution of sodium, potassium, etc., and as an organic alkali metal compound of the formula: an aliphatic and aromatic lithium compound which is a carbon number and a samarium compound A compound having one lithium or a lithium compound having a plurality of lithium in one molecule, and a tetralithium compound 'tetralithium compound 0 can be specifically exemplified by n-propyl lithium, n-butyl lithium, second butyl lithium, and third butyl. Reaction product of lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium 'diisopropenylbenzene and second butyl lithium, and further diethylene 157712.doc 5 •13 · 201213426 Base benzene and second butyl core and a small amount of 1,3·Τ dimorphic reaction products. Further, it is also possible to use an organic metal test compound which is disclosed in U.S. Patent No. 5, (4), British Patent No. 2, No. 2,241,239, and U.S. Patent No. 5,527,753. These may be used alone or in combination of two or more. The polymerization temperature at the time of forming the knife (a) is usually 〇.匚~15〇 It is preferably 40°C~120. (:. Poly. The time required varies depending on the conditions, usually within ι〇 hours, particularly preferably 0.5 to 5 hours. Further, the ambient gas of the polymerization system is preferably replaced by an inert gas such as nitrogen. The range in which the monomer and the solvent are maintained in the liquid layer in the polymerization temperature range (4) is not particularly limited. Further, it is preferable to note impurities such as inerting the catalyst and the living polymer. Water, oxygen, carbon dioxide, etc. are not mixed into the polymerization system. Component (a): The block copolymer contains at least 2 vinyl aromatic hydrocarbon polymer blocks, and at least one of the conjugated diene and vinyl groups. a block copolymer of a copolymer block of an aromatic hydrocarbon. In order to obtain such a composition, in the polymerization step of the component (a" block copolymer, a vinyl aromatic compound which is a monomer which is a raw material is controlled. The timing of the common light diene compound can be β component (a): the content of the vinyl aromatic hydrocarbon in the block copolymer is 65 mass%, and the content of the conjugated diene is 5 to 35 mass%. Such composition In the step of the polymerization of the component (a): block copolymer 157712.doc -14-201213426, the amount of the vinyl aromatic compound or the yoke conjugated compound which is a monomer of the raw material may be adjusted. , component (a): block bismuth polymer containing at least one aromatic group containing a group of aromatics; mass content of 7 〇 mass. / 〇 or more up to (10) mass% 'preferably 7 mass% 卩 98% by mass or less of ethylene In order to obtain such a configuration, the aromatic hydrocarbon and the conjugated diene are formed in a random manner in the polymerization step (four) of the component (a)·block copolymer. The amount of the monomer of the raw material may be. <Component (a): Physical properties of the block copolymer> As described above, in the component (a). Block copolymer, the dynamic viscoelasticity measurement is 3 〇 ° C The storage elastic modulus (E,) is 3x1 〇 8 pa or more and 2 35 χΐ〇 9 & below, and the peak temperature of the function of the dynamic viscoelasticity measurement tan § is at least one of 85 or more and 125 ° C or less. Therefore, the storage elastic modulus (ε·) at 30t in the dynamic viscoelasticity measurement is 5xl08 Pa or more 2.33xlG9 P a is below, and the peak temperature of the function of the dynamic viscoelasticity measurement taM is 9 (rc or more 125. There is at least a solid below the 。. The temperature indicating the peak of the above tan 5 is the first change in the value of tan § with respect to temperature. The temperature at which the sub-differential value is zero. In the dynamic viscoelasticity measurement of the component (a). The block copolymer has a storage modulus (E') of 3xl08 Pa or more and 2'35xl09 Pa or less, and dynamic When the peak temperature of the function of the viscoelasticity measurement is at least one of 85 ° C or more and I25 ° C or less, the foam of the present embodiment is excellent in the balance of hardness, elongation, and thermoformability, and is suitable for the sole. 1577I2.doc -15·201213426 The storage elastic modulus (£, ) and ^ in the dynamic viscoelasticity measurement of the component (a) can be measured by the method described in the examples below. For example, it can be measured by the viscoelasticity measuring and analyzing device DVE-V4 manufactured by Rheology, or the Rhe〇vibr〇n DDV3 type manufactured by TOYO Baldwin Co., Ltd., etc., specifically, the oscillation frequency is 35 Hz, and the temperature is raised. The test piece having a thickness of 〇5 to 2 mm was measured under the conditions of a speed of 3 ° C/min. The storage elastic modulus (E,) at 30 ° C in the above dynamic viscoelasticity measurement can be improved by, for example, the block A containing the ethylene-based aromatic hydrocarbon polymer constituting the above component (4), and In the ratio of the block B containing the copolymer of the common diene and the ethylene aromatic hydrocarbon, the block is increased, that is, by appropriately adjusting the ratio of the block A to the block B of the component (a), The storage elastic modulus (E,) at 3 ° C can be controlled to a value range of 3 χ 1 〇 8 Pa or more and 2 35 χΐ〇 9 Pa or less. The peak temperature of the function of dynamic viscoelasticity of the component (a) can be controlled to a high degree by, for example, increasing the molecular weight of the ethylenic aromatic smoulder of the component (4) to increase the component (a). The ratio of the vinyl-containing (4) component of the component (4) to the ethylene-based aromatic hydrocarbon of the copolymerized (four) segmented towel is 70% by mass or more and less than 1% by mass, preferably 75 Å/y. . The range of the above % by mass or less, in which the ratio of the ethylene-based aromatic hydrocarbon is increased; on the contrary, the ethylene-containing aromatic smoke of the constituent (a) is controlled to a lower degree by the following means. The ratio of the vinyl aromatic hydrocarbon in the divalent random polymer enthalpy is not more than 1% by mass, more preferably 75% by mass or more, and 5% by mass or less. 16·201213426, in which the ratio of the ethyl ketone aromatic smoke is reduced, and the ratio of the random copolymer block to the vinyl aromatic hydrocarbon homopolymer block is increased. That is, by performing the above various adjustments, the peak temperature of the function tan6 of the dynamic viscoelasticity measurement of the component (a) can be controlled to 85. 〇 Above 125t. The molecular weight of the component (a) is not particularly limited, and the number average molecular weight in terms of polystyrene in the gel permeation chromatography (GPC method) is preferably 30,000 to 1, 〇〇〇, 〇〇〇, and more. The foam having a fluidity and workability can be obtained by setting the molecular weight of the component (a) to the above range, preferably from 40 Å to 5 Torr, and more preferably from 5 Å to 300,000 Å. Use the composition. (Component (b): Isoprene-based rubber and/or diene-based rubber) δ-gas isoprene-based rubber, natural rubber and isoprene rubber, so-called diene rubber, stupid ethylene • Butadiene copolymerized rubber, polybutadiene rubber, acrylonitrile butadiene copolymerized rubber, ethylene/propylene/diene copolymerized rubber, etc., as component (b) constituting the foam of the present embodiment, These may be used alone or in combination of two or more. Ingredient (b) may contain oils such as paraffin oil, naphthenic oil, aromatic oil, or dioctyl phthalate, dibutyl phthalate, dioctyl sebacate, dioctyl adipate. And other plasticizers. As the above-mentioned stone ring oil, the Diana manufactured by Idemitsu Kosan Co., Ltd. can be cited.

Process Oil pw-90, pw-380, PS-32, PS-90, PS-430, Fukkol Process P-100, P-200, p_3〇〇, 157712.doc -17- 201213426 P_4〇〇, P-500, Kyoseki Process P-200, P-300, P-500, Kyoseki EPT750, Kyoseki 1000, Kyoseki Process S90 manufactured by Yankuang Co., Ltd., Lubrex 26 'Lubrex 100 manufactured by Shell Chemicals Co., Ltd. Lubrex 460, Esso Process Oil 815 'Esso Process Oil 845 ' manufactured by Exxon Mobil Co., Ltd. Esso Process Oil Bl, Naprex 32 manufactured by Exxon Mobil Co., Ltd., Mitsubishi 10 Light Process Oil, manufactured by Nippon Oil Corporation. As the above naphthenic oil, Diana manufactured by Idemitsu Kosan Co., Ltd. can be cited.

Process Oil NS-24, NS-100, NM-26, NM-280, NP-24, Naprex 38 manufactured by Exxon Mobil, Fukkol FLEX # 1060N, # 1150N, # 1400N ' # 2040N, manufactured by Fujising Co., Ltd. # 2050N, Kyoseki Process R25, R50 'R200 ' R1000 manufactured by Nippon Mining & Co., Ltd. R1000 9 Shellflex 371JY, Shellflex 371N, Shellflex 451, Shellflex N-40, Shellflex 22, Shellflex 22R, Shellflex 32R, Shellflex 100R manufactured by Shell Chemicals , Shellflex 100S, Shellflex l〇〇SA, Shellflex 220RS, Shellflex 220S, Shellflex 260, Shellflex 320R, Shellflex 680, Koumorex No. 2 Process Oil manufactured by Nippon Oil Corporation, Esso Process Oil L-2 manufactured by Exxon Mobil, Esso Process Oil 765 'Mitsubishi 20 Light Process Oil manufactured by Nippon Oil Corporation. As the above-mentioned aromatic oil, Diana Process Oil AC-12 'AC460 ' AH-16 ' AH-58 ' Exxon manufactured by Idemitsu Kosan Co., Ltd.

Mobil's Mobile Sol K, Mobile Sol 22, Mobile 157712.doc -18- 201213426

Sol 130, Kyoseki Process X50, X100, X140 manufactured by Nippon Mining & Co., Ltd. 'Rezox Νο·3, Dutorex 729UK, manufactured by Shell Chemicals, Koumorex 200, 300, 500, 700 manufactured by Nippon Oil Corporation, manufactured by Exxon Mobil Esso Process Oil 110, Esso Process Oil 120, Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, Mitsubishi 39 Heavy Process Oil, etc. manufactured by Nippon Oil Corporation. The compounding amount of the plasticizer is preferably from 1 to 200 parts by mass, more preferably from 10 to 100 parts by mass, even more preferably from 15 to 8 parts by mass, per 100 parts by mass of the component (b). When the amount of the plasticizer is from 1 to 200 parts by mass, the foam of the present embodiment is excellent in workability. As the component (b), polybutadiene is preferred, and as the polybutadiene rubber, the inclusion of the 1,2-bond (vinyl) 5% to 20%, and the inverse 1,4 bond 0~ 3%, the rest of the ingredients are Shun, 4 bonds of vinyl cis-polybutadiene rubber ' or more than 92% of cis 1,4 bonds, including ι, 2 bonds 〇%~3%, the remaining components are anti-1,4 High-poly butadiene rubber of the rubber of the key. In the foam of the first embodiment of the present embodiment, the mass ratio of the component to the component (b) (component (a) / component 〜 3 〇) / (7 〇 to 99) is preferably (2~). 25) / (75 ~ 98), more preferably (5 ~ 20) / (80 ~ 95). When the mass ratio of the component (a) to the component (b) is (1 to 30) / (70 - 99), the foam can obtain excellent hardness and dimensional stability. (Ingredient (c): Filler) 157712.doc -19- 201213426 : For the filler 'For example, it can be exemplified by dioxic carbonate, clay, strontium, sulphuric acid, broken acid town, glass woven, glass beads, and acid. Unloading carbon black, stone anaerobic dioxide, dual phase filler, etc. In the foam of the first embodiment, the blending amount of the filler in the foam is 1 to 100 parts by mass based on the total amount of (a) and the component (b). Preferably, it is 2 to 90 parts by mass, more preferably 3 7 曰, 尺佳马 3 75 份份份, and particularly preferably 5 to 50 parts by mass. 0, if the component (4): the amount of the filler is Η. . In the case of parts by mass, the foam of this embodiment can obtain a preferable hardness and a preferable specific gravity. (Component (d): foaming agent) As the foaming agent, for example, an inorganic foaming agent or an organic foaming agent known per se can be used. For example, sodium bicarbonate, bicarbonate to anti-failure, sodium citrate, ammonium carbonate, azo-nitramine, diazepam. 3⁄4. X nm brothers, quinones, quinones, tetraamines, two The nitro group is a stupid amine, azobisisobutyronitrile, azodicarboxylic acid, and the like. More preferably, it is azo dimethylamine, dinitrosium pentylene = stilbene, sulfonium, sodium bicarbonate. These blowing agents may be known as a foaming aid such as a derivative. Further, as the foaming agent', a heat-expandable microcapsule can be used. The heat-expandable microcapsules include a shell of thermoplastic hollow spheres and a shell containing a thermoplastic resin enclosing the gas. When the heat-expandable microcapsules are heated, the thermoplastic shell is filled, and the gas increases the pressure. As a result, the sphere expands to function as a foaming agent as a thermoplastic resin constituting the shell of the microcapsule, for example, List: 157712.doc •20- 201213426 Vinylidene chloride-acrylonitrile copolymer, vinylidene chloride_methyl methacrylate total compound, partial chloroethene _ sub-based propyl ethyl benzoate B Dilute nitrile-methyl propyl methyl acrylate copolymer, acrylonitrile-f-based ethyl acrylate, and the like. Further, examples of the compound which becomes a gas by heating include isopentane, isobutane, isopropane and the like. The mass average particle diameter of the heat-expandable microcapsules is usually from 0 to 00 pm, preferably from about 20 to 80 μηι. Examples of the heat-expandable microcapsules include expancel DU manufactured by JApAN fillite Co., Ltd., wu system 歹J, Microsphere F-30, F-50, F-80S, F-85 manufactured by Matsumoto Oil & Fats Co., Ltd., and the like. When the heat-expandable microcapsules are used as a foaming agent, by heating, the gas-forming components contained in the respective microcapsules are gasified to be uniformly swollen, and a homogeneous foam can be obtained. The endothermic foaming agent is preferred for foaming. The dimethyl hydrazine dimer nitro pentoxide can be used as a heat-generating foaming agent by suppressing heat generation during foam molding by using a heat-generating foaming agent and agent, and azomethylenetetramine is exemplified. Wait. Further, as the endothermic foaming agent, it is possible to list sodium citrate or the like, and in this case, the generated gas is carbon dioxide. In the foam of the first embodiment, the amount of the component knives (d) and the foaming agent is preferably 0.1 to 30 parts by mass, based on the weight of the components (4) and (8). It is preferably 5 to 2 parts by weight, more preferably 1 to 15 parts by mass. If the component (d): the amount of the foaming agent is from 1, part by mass, the present embodiment is 157712.doc.21·201213426 The foam has excellent hardness and a specific gravity is obtained. (Component (e): Thermoplastic Elastomer and/or Thermoplastic Resin) The foam of the present embodiment may further contain the component (e): a thermoplastic elastomer and/or in addition to the above components (a) to (d). Thermoplastic resin. As the thermoplastic elastomer, for example, according to the classification of the chemical composition of the hard segment, a thin-smoke thermoplastic elastomer (TPO), a urethane-based thermoplastic elastomer (TPU), or an ester-based thermoplastic elastomer ( TpEE), a styrene-based thermoplastic elastomer (TPAE), and the like. In addition, a gas-based thermoplastic elastomer (Tpvc) or an ion cluster-type thermoplastic elastomer (ionomer) contains a fluororesin as a fluorine-based thermoplastic elastomer as a restraining block (again, it may be used by In the thermoplastic elastomer in which the resin/rubber is mixed, the rubber which is a soft segment is cross-linked while being kneaded, and the rubber dispersed particle diameter is refined, and the dynamically crosslinked TPO which improves the performance is called TPV). The above thermoplastic elastomer can be used alone! Two or more kinds may be used in combination. Further, as the other thermoplastic elastomer, a synthetic rubber other than the above component (a) or component (b) may be used, and examples thereof include a fluororubber and a polyoxyethylene rubber 'South 2 butyl rubber (for example, chlorobutyl rubber, bromine The butyl rubber or the like may be used alone or in combination of two or more. The thermoplastic resin is not particularly limited as long as it is a thermoplastic resin having a plasticizing temperature of 5 Torr to 3 Torr (for example, a styrene resin (for example, polystyrene, acrylonitrile, styrene copolymer). 'Acrylonitrile-butadiene-styrene copolymer, ABS (AcryI〇nitrile Butadiene Styrene, acrylonitrile_丁二妇乙乙 I57712.doc •22- 201213426) resin, AES (Acrylonitrile-Ethylene-Styrene) , propylene guess, ethylene-epoxy resin, AAS (Acrylnitrile-Acrylicester-Styrene, acrylonitrile acrylate) resin, polyethylene, polypropylene, ethylene, propylene resin, ethylene-ethyl acrylate resin, poly Vinyl chloride, polyvinylidene gas, polybutene, polycarbonate, polyacetal, polyphenylene ether, polymethyl methacrylate, saturated polyester resin (for example, hydroxycarboxylic acid condensate such as polylactic acid, poly a condensate of a diol such as butyl succinate and a dicarboxylic acid, or the like, a polyamide resin, a fluororesin, a polysulfone, a polyether sulfone, a polyarylate, a polyetheretherketone liquid crystal polymer, or the like. One can be used alone, or Two or more kinds are used. Among the thermoplastic resins, polystyrene, acrylonitrile, styrene copolymer, ABS resin, AES resin, AAS resin, polyethylene, polypropylene, polyethylene oxide, saturated polyester resin, poly The phthalamide resin is preferably formed by preventing the dent or deformation in the molded body of the foam of the present embodiment by blending the thermoplastic resins. As for the component (e): thermoplastic elastomer and/or thermoplastic The blending amount of the resin is preferably 1 to 1 part by mass, more preferably 3 to 75 parts by mass, more preferably 5 to 75 parts by mass, based on 1 part by mass of the total of the component (a) and the component (b). 5 parts by mass. If the component (e): the thermoplastic elastomer and/or the thermoplastic resin is blended in an amount of from 1 to 100 parts by mass, the foam of the present embodiment can obtain a preferable mechanical strength. The foam composition for obtaining the foam of the first embodiment of the present embodiment comprises the above components (a) to (d), and the component (a) block is 157712.doc - 23· 201213426 Polymer and the above (b) different &amp; two association rubber and / or: the quality of rare rubber The ratio (former (a) / component (b)) is (1 to 3 〇) / (7 〇 to 99), preferably (2 to 25) / (75 to 98), more preferably (5~) 20) / (80 to 95), the above (c) is contained in the total amount (10) by mass of the above (a) block copolymer and the above (b) isoprene-based rubber and/or diene rubber. The filler is 1 to 100 parts by mass, preferably 2 to 9 parts by mass, more preferably 3 to 75 parts by mass, particularly preferably 5 to 5 parts by mass, and contains the above (sentence foaming d 0.1 to 30 mass parts) Preferably, it is 5 to 2 parts by mass, more preferably 丨 to parts by mass. Further, the component (e)' may be preferably contained in an amount of 100 parts by mass based on the α of the component (a) and the component (1?), and further contains 3 parts by mass, more preferably 3 to 75 parts by mass. Good for 5 to 50 parts by mass. When preparing a composition for a foam, a conventionally known kneader, extruder, or the like can be used. In addition, as a method of blending (c) a filler, (d) a foaming agent, and the like, for example, the component (a) and the component 〇3) are 100 to 180 in advance by a Banbury mixer or the like. After the mixture is kneaded by kneading, the obtained product is blended with a filler (C) using a Banbury mixer or the like, and then a method of adding (d) a foaming agent, a crosslinking agent or the like using a roll or the like is used, but the invention is not limited thereto. [Foam] [Foam according to the second embodiment] The foam of the second embodiment contains the following components (a,) to (sentence. (a1) block copolymer which contains at least 2 ethylene. a base aromatic hydrocarbon polymer block, and at least one copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon, and the content of the '157712.doc -24-201213426 ethylene-based aromatic hydrocarbon is 65~ The mass of 95 is 5 to 35 mass%, and the mass of the block copolymer containing a total of diene is contained in the B-county (4) 40 to 98% by mass. The job is only (b) isoprene Rubber and/or diene rubber (c) Filler (d) Foaming agent. The foam of the second embodiment has a specific gravity of 〇1 n ^ 〇*7 g/cc. The hardness of the test is 45~98, and the hardness is 〇8~〇^. The hardness of the model 8 is 6〇~98. 'gee' is wrong (component (a'): block copolymer) composition (a' A block copolymer containing an ethylene-based aromatic (IV) as described above. The content of the ethylene-based aromatic hydrocarbon in the octa-ene component (8) is ～~95 mass. 4 is preferably 68 to 93% by mass. More preferably 70~90 The content of the conjugated diene in the component (a,) is, in the range of 7 to 32 mass%, more preferably 10 to 30 mass%. Preferably, if the vinyl aromatic hydrocarbon When the content is in the range of from 5 to 35% by mass in the range of from 65 to 95, the balance between the hardness of the foam and the thermoformability of the foam is excellent, and the vinyl is suitable for the elongation component (4) of the shoe. Aromatic hydrocarbon content, w inclusions. The amount is determined by measuring the absorbance of the light by using an ultraviolet spectrophotometer. Searching for the wavelength The component ratio of the Ethylene-based aromatic smoke polymer contained in the component (8) is 5 157712.doc -25- 201213426 4 0~98% by mass, preferably. If the mother-in-law is intended. More preferably 6〇~90% by mass. The base ratio of the base of the tobacco polymer is 4, which is a foam with a stable size and a heat (4). The block ratio of i σ as a vinyl aromatic hydrocarbon polymer for shoes can be determined by the weight of the random copolymer chain of the aromatic cigarette and the common light bismuth in the component (8) and the content of the vinyl scented hydrocarbon. (% by mass) to adjust. The component (the amount of the ethylene-based aromatic hydrocarbons occupied by the random copolymer chain of the A-pure copolymer is decreased as the block ratio of the vinyl aromatic hydrocarbon polymer is decreased, and the block rate is increased as the ratio is decreased. The block ratio of the aromatic hydrocarbon polymer of the county can be determined by the same method as the above component (4). The formed blade (a) has at least two vinyl aromatic hydrocarbon polymer blocks' and at least one contains a total of A copolymer of diterpene and anthracene-based aromatic hydrocarbon. The polymer structure of the component 〇') is not particularly limited, and for example, a linear block copolymer or a radial block represented by the following formula may be used. a copolymer, or any mixture of such polymer structures. Further, in the radial block copolymer represented by the following formula, further than at least one block VIII or block 3 may be bonded to X. (AB)n+1, A-(BA)n, B-(AB)n+丨, [(AB)k]m+1-X &gt; [(AB)kA]m+,-X &gt; [(BA k]m+1-X, [(BA)kB]m+1-X, in the above various formulas, 'block A is composed of a vinyl aromatic hydrocarbon polymer, and Xin B and B are composed of a total of two women. It is composed of a copolymer of an aromatic hydrocarbon. 157712.doc -26- 5 201213426 'x" in the above formula, for example, represents tetrachloride, tin tetrachloride, u bis (N'N-glycidylaminomethyl) cyclohexan, epoxidized soybean oil, etc. The residue of the coupling agent or the residue of the polyfunctional compound. n, k & m are integers of 1 or more, and are usually integers of 5 . Further, the structure of the plurality of bonded polymer chains may be the same or different. The above-mentioned component (a,) contained in the foam: the vinyl aromatic smoke in the copolymer of the vinyl aromatic hydrocarbon and the conjugated diene in the block B of the block copolymer may be uniformly distributed, or Formed (decreasing) distribution. Further, in the copolymer, a portion of a plurality of vinyl aromatic smoke homogenous sentence distributions and/or a wedge-shaped distribution portion may be coexisted in the block. The knives (a). 肷 & copolymer preferably contain at least (10) random copolymers of the age of 'the content of the ethyl succinyl aromatic fumes is 7 〇 mass%, not more than 10% by mass, preferably 75 A vinyl aromatic hydrocarbon having a mass% or more and 98% by mass or less is co-boiled. Thereby, a foam having good hardness and dimensional stability can be obtained. &lt;Component (a) Method for producing a segment copolymer> The component (a') can be produced by the same method as the above component (4). The ethylene-based hydrocarbon, silk:ene, hydrocarbon solvent, and polymerization starting material which are raw materials may be the same as the component (4). Further, the polymerization conditions such as the polymerization temperature and the ambient gas may be selected under the same conditions as the component (a). &lt;Component (a). Physical properties of the block copolymer > The knives (a) inlaid copolymer is preferably 3 Å in the dynamic viscoelasticity measurement. The elastic modulus of elasticity under the armpit (10) is 3xl 〇 8 pa or more and 2.35 χΐ〇 9 or less, and 157712.doc -27- 201213426 is preferably the dynamic viscoelasticity measurement. The peak temperature is at least 1 below 150C. One. More preferably, the dynamic viscoelastic wave is set to φ ^ η. The storage elastic modulus (Ε,) at 30 C in Guangli 为 is 5xl08 Pa or more and 2.33x1 〇 9 Pa or less, B s „ upper 乂 and better as a function of dynamic viscoelasticity measurement. The peak temperature of tan5 is 9 ( There is at least ι above U5t in rc. The 'foaming body is excellent in the balance between hardness and elongation and thermoformability'. It is suitable for the sole. The molecular weight of the component (a,) is not particularly limited. The polystyrene-equivalent number average molecular weight in the gel permeation chromatography (GPC method) is preferably 30.000 1, 〇〇〇, 〇〇〇 ' more preferably 4 〇, 〇〇〇 〜 5 〇〇〇〇〇 In particular, the composition for a foam having excellent fluidity and workability can be obtained by setting the molecular weight of the component (a') to the above range in the range of 5 Å to 300.000 Å. In the foam of the second embodiment, the foam of the second embodiment can be used as the component (b), the component (c), and the material (d). The component (e) may be contained. [Method for Producing Foam] First Embodiment of the Present Embodiment In the foaming system, the component (a), the component (b), the component (c), and the component (d) are essential components, and the foaming system of the second embodiment has the component (a), the component (b), and the component. (c) and (d) as an essential component, each component (e) is added as needed to prepare a composition for a foaming body', and the foaming composition is subjected to a foaming/crosslinking treatment to obtain 157,712. Doc -28-201213426. (Foaming and cross-linking treatment) In the step of the above-mentioned composition for foams, liuzan/a, a foam can be obtained by adding a mold to the (four) mold. After foaming by raising the temperature, or molding into an arbitrary shape using an extrusion molding machine, it is heated in a heating tank to foam. At this time, the foaming is performed once after foaming, and the foaming may be performed twice. The foaming condition is preferably increased. The heating temperature is preferably set to ΐ2〇~3() (η:, more preferably in the range of 140-200 C, preferably the heating time is set to 3 minutes, more preferably It is set to a range of 5 to 60 minutes. In the above foaming process, crosslinking can be carried out at the same time. The cross-linking form of the foam is not particularly limited, and for example, sulfur cross-linking, peroxide cross-linking, etc. may be applied. From the viewpoint of cost and strength of the foam, sulfur cross-linking is preferred. The body may be appropriately formulated with an appropriate amount of alkane alkylating agent, an anthracene coupling agent, an anti-aging agent, a vulcanization accelerator, and a crosslinking auxiliary agent. [The physical properties of the foam] The proportion of the foam of the embodiment is in the i-th In the foam of the embodiment and the second embodiment, 0.1 to 0.98 g/cc' is preferably 〇% g/cc. The specific gravity can be measured by the method described in the examples below. Measured in JIS K 7 112. The foam having a specific gravity of 0·b 0.7 g/cc is suitable for use in applications requiring cushioning properties such as cushioning properties, cushioning properties, and light weight, such as midsole materials such as sports shoes. § 157712.doc -29- 201213426 Foams with a specific gravity of 0·8 to 0.98 g/cc are suitable for applications requiring characteristics of hardness, dimensional stability and mechanical strength, such as outsole materials for shoes. The specific gravity of the foam can be controlled by adjusting the composition of the compound (c): the amount of the filler, and the component (d): the amount of foaming. By increasing the component (c): the filling dose and the specific gravity becomes large, the specific gravity can be reduced by increasing the component (d): the foaming amount. Further, in the foam of the present embodiment, when the specific gravity is 〇"~〇7 §/", the hardness measured by the model C is 45 to 98', preferably 48 to 90, more preferably 5 to 85. When the specific gravity is 0.8 to 0.98 g/cc, the hardness measured by the model a is 60 to 98', preferably 63 to 90, more preferably 65 to 85. Further, the hardness measured by the model c means the thickness used. 12 mm test piece, hardness measured by ASKER C type hardness tester (model C). 'Density measured by type A means a plate test piece with a thickness of 12 mm, according to JIS K 6301 spring type The hardness measured by the hardness tester A-shape (model A). The hardness of the above-mentioned foam can be controlled by adjusting the composition and specific gravity of the above components (a) to components, components (a') to (d). By increasing the content of the component (c): the filler, the hardness can be increased, and the foaming ratio can be increased by increasing the content of the component (d): the amount of the foaming agent, and the hardness can be lowered. That is, by adjusting the above components, The strength of the foam having a specific specific gravity is controlled to the above specific numerical value. [Use of Foam] This embodiment The foam can be effectively used as: midsole, insole or outsole material for shoes. Specifically, men's shoes, ladies' shoes, rest shoes, running shoes, jogging 157712.d〇C.30. 5 201213426 shoes, various athletic shoes, The soles of the footwear, the dress shoes, the golf sole U, the slippers, the beach shoes, etc. are the midsole, the insole or the outsole material. The foam of the embodiment can also be used for the parts, building materials as needed. Parts, industrial parts, toys, "parts sports, health parts, care products, and other molded products, or various sheets, films, other industrial supplies, cushioning materials, packaging materials, etc. Further, the foam of the present embodiment is excellent in dimensional accuracy, excellent in durability and cushioning property, and can be applied to a thermoformed sponge, and can be used for the above various applications after being processed into the thermoformed sponge. The so-called thermoformed sponge is prepared by cutting the foam into a desired shape and heating it in a mold heated to loo~i5〇〇c (4), after forming a firm molten film on the outer surface of the foam: The mold is cooled and the foam is taken out and produced. EXAMPLES Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited to the examples described below. (Component (a): Production Example of Block Copolymer) &lt;Block Copolymer A-1&gt; Using an autoclave equipped with a stirrer, in a cyclohexane solution containing 18 parts by mass of styrene under a nitrogen atmosphere, 91 parts by mass of n-butyllithium ruthenium was added, and 四.1 mol of tetrakis-ethylideneamine was added to n-butyl group, and the mixture was continuously supplied at 70 ° C for 25 minutes to carry out polymerization. Then, a solution containing 21 parts by mass of styrene and 32 parts by mass of 1,3-butadiene was used at 70. (: Polymerization was carried out continuously for 65 minutes. 1577l2.doc • 31 - 201213426 Then, a cyclohexane solution containing 29 parts by mass of styrene was continuously supplied at 70 ° C for 35 minutes for polymerization. Then, in the polymerization vessel, Adding a molar amount of methanol to n-butyllithium, and adding 0.3 parts by mass of 2-[1-(2_hydroxy_3,5_2, third) as a stabilizer with respect to 100 parts by mass of the block copolymer Butyl phenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate. Then, solvent removal was carried out to obtain block copolymer A-1. &lt;Block copolymer A-2&gt; The high pressure enthalpy of the stirrer was added to 0.087 parts by mass of n-butyllithium in a cyclohexane solution containing 24 parts by mass of styrene under nitrogen atmosphere, and 0.4 times of moles of moles of n-butyllithium was added. The mercaptoethylenediamine was continuously supplied at 70 ° C for 30 minutes to carry out polymerization. Then, a cyclohexane solution containing 22 parts by mass of styrene and 27 parts by mass of 1,3-butadiene was continuously dried at 70 ° C. The polymerization was carried out for 60 minutes. Then, a cyclohexane solution containing 27 parts by mass of styrene was continuously supplied at 35 ° C for 35 minutes. Then, in the polymerizer, isomolar sterol is added to n-butyllithium, and 0.3 parts by mass of 2-[1-(s) as a stabilizer is added to 100 parts by mass of the block copolymer. 2-Hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate. Then, solvent removal was carried out to obtain block copolymer A-2. Block copolymer A-3&gt; Using an autoclave equipped with a stirrer, under a nitrogen atmosphere, in a cyclohexane solution containing 31 parts by mass of styrene, n-butyllithium 0.082 mass 157712.doc -32- 8 201213426 was added. The amine and the butyl oxime are continuously supplied for 40 minutes at 70 ° C for polymerization with respect to n-butyllithium. The tetramethylethylene 2 will then contain 20 parts by mass of styrene, 盥 ^ ” 2 parts by mass of a cyclohexane solution was continuously supplied at 7 (TC) for polymerization for 50 minutes. Then, a cyclohexane solution containing 6 parts by mass of styrene and 2 parts by mass of 丨3_d'-ene was continuously dried at 701. Supply for 15 minutes for concentration. Then '21 parts by mass of styrene containing styrene, lysine and hexane solution at 70 ° C The polymerization was continued for 30 minutes, and then, in the polymerization reactor, isomolar methanol was added to the n-butyl group, and 3 parts by mass of the stabilizer was added to 100 parts by mass of the block copolymer. Π_(10)yl_3,5-di-di-pentylphenyl)ethyl]- 4,6-di-di-p-based acrylic acid g. Then, solvent removal is carried out to obtain block copolymer A &lt;A-4&gt; Using a high pressure condensate equipped with a stirrer, a 0.076 mass loss of n-butyllithium and a ruthenium addition to n-butyllithium were added to a hexane solution containing 32 Å of styrene in a nitrogen atmosphere. .3 times mole of tetradecylethylenediamine was continuously supplied at 70 ° C for 4 minutes to carry out polymerization. Then, a cyclohexane solution containing 21 parts by mass of styrene and 12 parts by mass of hydrazine and 3-butane dilute was continuously supplied at 70 ° C for 40 minutes to carry out polymerization. Then, a cyclohexane solution containing 8 parts by mass of styrene and 3 parts by mass of butadiene was continuously supplied at 70 ° C for 15 minutes to carry out polymerization. Then, 24 parts by mass of a styrene solution containing styrene was placed at 7 Torr. The mixture was continuously supplied for 30 minutes for polymerization. § 157712.doc •33·201213426 Then, in a polymerizer, isomolar methanol is added to n-butyllithium, and 0.3 parts by mass of a stabilizer 2 is added to 100 parts by mass of the block copolymer. [1-(2-Hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate. Then, solvent removal was carried out to obtain block copolymer A-4. &lt;Block Copolymer A-5&gt; Using a high pressure crucible equipped with a stirrer, 0.052 parts by mass of n-butyllithium was added to a cyclohexane solution containing 26 parts by mass of styrene under a nitrogen atmosphere, and To the n-butyllithium, 0.4 M mole of tetramethylethylenediamine was added, and the mixture was continuously supplied at 70 ° C for 35 minutes for polymerization. Then, a cyclohexane solution containing 30 parts by mass of styrene and 6.5 parts by mass of 1,3-butadiene was continuously supplied at 70 ° C for 45 minutes to carry out polymerization. Then, a cyclohexane solution containing 10 parts by mass of styrene and 1,5 parts by mass of 1,3-butadiene was continuously supplied at 70 ° C for 15 minutes to carry out polymerization. Then, a cyclohexane solution containing 26 parts by mass of styrene was continuously supplied at 70 ° C for 30 minutes to carry out polymerization. Then, in the polymerization vessel, isomolar methanol was added to n-butyllithium, and 0.3 parts by mass of 2-[1-(2-hydroxy-) as a stabilizer was added to 100 parts by mass of the block copolymer. 3,5-Di-t-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate. Then, solvent removal was carried out to obtain block copolymer A-5. &lt;Block copolymer A-6&gt; Using an autoclave equipped with a stirrer, n-butyllithium 0.092 mass 157712.doc -34-8 was added to a cyclohexane solution containing 15 parts by mass of styrene under a nitrogen atmosphere. 201213426 Injury and addition of 0.1 times mole of tetrakis-ethylenediamine to n-butyllithium, and continuous polymerization for 20 minutes at 7 〇t: for polymerization. Then, a cyclohexane solution containing 16 parts by mass of styrene and 38 parts by mass of butyl bismuth was continuously supplied at 7 (TC) for polymerization for 6 minutes. Then, 6 parts by mass of styrene and 1}3 were contained. 2 parts by mass of a cyclohexane solution was continuously supplied at 7 (TC for 15 minutes for polymerization. Then, a solution containing 23 parts by mass of styrene in cyclohexane was continuously supplied at 7 Torr (&gt;c). Then, in the polymerization H, (4) adding a molar amount of methanol to the positive τ group (tetra), and adding 03 parts by mass of the 2-[Η2-perylene group as a stabilizer with respect to 100 parts by mass of the block copolymer. _3,5_2,3,3,5-pentyl)ethyl]_4,6-di-p-pentyl phenylpropanate vinegar. Then, solvent removal is carried out to obtain a block copolymer Α_6. &lt;block copolymerization Α-7&gt; Using a high-powered dad with a machine, in a nitrogen atmosphere, in a cyclohexane solution containing 39 parts by mass of styrene, &amp; plus (4) parts by mass, and relative to n-butyl group Lithium was added with 3 times moles of tetramethylethylenediamine, and the mixture was continuously supplied at 7 ° C for 45 minutes for polymerization. Then, 20 parts by mass of styrene was contained. 2 parts of butadiene, 2 parts by mass of cyclohexane calcined / gluten solution was continuously supplied for 30 minutes at 70 C for polymerization. Then, a cyclohexane solution containing 39 parts by mass of styrene was continuously supplied for 45 minutes at 7 Torr: Then, in the polymerization reactor, isomolar methanol is added to n-butyllithium, and 3 parts by mass of ruthenium is added to 1 part by mass of the block copolymer as 157712.doc -35·201213426 Stabilizer 2-[l-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate. Block copolymer A-7. &lt;Block copolymer A-8&gt; Using an autoclave equipped with a stirrer, n-butyllithium 0.090 was added to a cyclohexane solution containing 20 parts by mass of styrene under a nitrogen atmosphere. The mass fraction and the tetramethylethylenediamine added with 0.1 times mole of n-butyllithium were continuously supplied at 70 ° C for 25 minutes for polymerization. Then, 16 parts by mass of styrene and 1,3- were contained. 32 parts by mass of butadiene solution of butadiene was continuously supplied at 55 ° C for 55 minutes for polymerization. Then, styrene 8 was contained. The mixture was continuously supplied with a cyclohexane solution of 2 parts by mass of 1,3-butadiene at 70 ° C for 15 minutes. Then, a cyclohexane solution containing 22 parts by mass of styrene was continuously supplied at 70 ° C. The polymerization was carried out for 30 minutes. Then, in the polymerization apparatus, isomolar methanol was added to n-butyllithium, and 0.3 parts by mass of 2-[1- as a stabilizer was added to 100 parts by mass of the block copolymer. (2-Hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate. Then, solvent removal was carried out to obtain block copolymer A-8. &lt;Block copolymer A-9&gt; Using an autoclave equipped with a stirrer, 0.074 parts by mass of n-butyllithium was added to a cyclohexane solution containing 15 parts by mass of styrene under a nitrogen atmosphere, and relative to n-butyl To the base lithium, 0.3-mole of tetradecylethylenediamine was added, and the mixture was continuously supplied at 70 ° C for 20 minutes for polymerization. 157712.doc -36-201213426 Then, 10 parts by mass of a cyclohexane solution containing 1,3-butadiene was continuously supplied under grasping for 20 minutes for polymerization. Then, 57 parts by mass of phenylethyl women and 18 parts by mass of a cyclohexane solution of butyl women were continuously supplied at 7 (TC for 8 minutes to carry out polymerization. Then, in the polymerizer, 'relative to the n-butyl group And adding the molar amount of methanol of the molar amount of 2-[1-(2-pyridyl_3,5-di-p-pentylphenyl) as a stabilizer with respect to 100 parts by mass of the block copolymer Ethyl]_4,6_di-p-pentyl phenyl acrylate vinegar. Then, solvent removal is carried out to obtain block copolymer A_9. <Block copolymer Al 〇> Using a high-pressure dad with (4) machine, To a cyclohexane solution containing 47 parts by mass of styrene, a n-butyl (tetra) portion by mass, and a tetramethylethylenediamine having a molar ratio of 3 times moles to n-butyllithium were added under a nitrogen atmosphere. The polymerization was carried out by continuously supplying at 55 ° C for 55 minutes. Then, a solution of 6 parts by mass of 1,3-butadiene in a cyclohexane solution was continuously supplied to the thief for 1 minute to carry out polymerization. The portion of the cyclohexane solution is continuously supplied for 5 to 5 minutes for polymerization. Then, in the polymerization device, it is added with respect to n-butyllithium. The methanol of the ear is added with 〇·3 parts by mass of 2-Π ♦ methoxy- 3,5•di-t-amylphenyl)ethyl]_4 as a stabilizer with respect to 1 part by mass of the block copolymer. 6_two second decyl phenyl acetoin g. Then, solvent removal was carried out to obtain a block copolymer Α_ι〇. &lt;Block copolymer A-ll&gt; 157712.doc -37- 201213426 An autoclave equipped with a stirrer is added with n-butyl dibasic in an amount of a cyclohexane solution in a nitrogen atmosphere, and The addition of 0.3 times mole of tetra-p-ethylene ethylenediamine to n-butyllithium was continuously supplied at 70 ° C for 30 minutes to carry out polymerization. Then, a cyclohexane solution containing 10 parts by mass of styrene and 26 parts by mass of 153-butadiene was continuously supplied at 70 ° C for 45 minutes to carry out polymerization. Then, a cyclohexane solution containing 12 parts by mass of styrene and 3 parts by mass of butadiene was continuously supplied at 70 ° C for 20 minutes to carry out polymerization. Then, a cyclohexane solution containing 22 parts by mass of styrene was polymerized at 7 (continuously supplied for 25 minutes). Then, in the polymerization vessel, isomolar methanol was added with respect to n-butyllithium. Adding 0.3 parts by mass of 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]- 4,6-di Tripentyl phenyl acrylate vinegar. Then 'desolvation to obtain block copolymer A_丨j. The composition of component (a) '肷 segment copolymer a-1~a-11, styrene content ( The storage elastic modulus (E,) of 30%, the peak temperature of the function of dynamic viscoelasticity measurement, and the block ratio of styrene contained in the block copolymer are shown in Table 1 below. (Component (a): Method for measuring physical properties of block copolymer) &lt;(1) Styrene content (mass/〇)&gt; Using an ultraviolet spectrophotometer (Hitachi UV200), it was calculated from the absorption intensity at 262 nm. &lt;(2) Storage elastic modulus at 30 ° C (Ει) and function of dynamic viscoelasticity measurement 157712.doc 8 •38- 201213426 peak temperature of tan5> Using R The viscoelasticity measuring and analyzing device DVE-V4 manufactured by heology is used to measure the temperature range of -50 ° C to 150 ° C under the conditions of an oscillation frequency of 35 Hz and a temperature increase rate / min. &lt;(3) Block rate of styrene contained in block copolymer&gt; Method for oxidative decomposition of block copolymer by using perylene tetroxide as a catalyst by peroxidizing tert-butanol Decomposition method: IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946), the block chain component of styrene (the styrene block having an average degree of polymerization of about 30 or less) The components are separated, and the weight of the styrene block chain is determined according to the following formula: Block ratio of styrene (% by mass) = (weight of styrene block polymeric chain in the block copolymer / The total weight of styrene in the block copolymer) x 100 157712.doc 39- 5 201213426

[II Block rate of stupid ethylene (% by mass) ON Ο VO VO Ό VO mv〇so 〇 \ v〇tan5 peak temperature (°C) T—Η oo 1—H CN CN g 1—H TH 〇\ g 30 °C Ε · (χΙΟ8 Pa) inch cn oo 12.8 23.4 CN cn 28.3 o CN — 29.2 CN VO styrene content (% by mass) oo cn oo OO § VO CM component (a): structure of block copolymer A1-B-A2 A1-B-A2 A1-B1-B2-A2 A1-B1-B2-A2 A1-B1-B2-A2 A1-B1-B2-A2 A1-B-A2 A1-B1-B2-A2 ACB A1-C-A2 A1-B1-B2-A2 block copolymer &lt; CN &lt; A-3 A-4 yr^ &lt; A-6 ... _ 1 A-7 A-8 &lt; A-10 A -ll -40- 157712.doc 201213426

The added word (number) is used to distinguish each part. The A in the structure of A-ll indicates that the random copolymer block of the diene shows a polystyrene block, and the structure of the C table can be the same (the characteristics of the foam) Measurement method and evaluation method) The method and evaluation method of the characteristics of the foam produced in the examples and the comparative examples will be described. 7 &lt;(4) Specific Gravity&gt; Measurement was carried out in accordance with JIS K 7112. &lt;(5) Hardness (Model A)&gt; Using a plate-shaped test piece having a thickness of 12 mm, it was measured in accordance with a JIS κ 63〇ι spring type hardness tester (model Α). '》 &lt;(6) Hardness (Model C)&gt; A plate-shaped test piece having a thickness of 12 mm was used, and measurement was performed by an Asker c-type hardness tester (Model C). &lt;(7) Tensile strength (Tb), elongation at the time of cutting (Eb)> A plate-shaped test piece having a thickness of 2 mm was measured in accordance with JIS K 6251.

The unit of Tb is set to (MPa) ’ The unit of Eb is set to (%). &lt;(8) Dimensional stability (α)&gt; The 24-hour shrinkage ratio of the sheet which was formed twice by a mold of 150 (vertical) 150 (horizontal) χ 4 mm (thickness) was measured. Further, the index was calculated by setting Comparative Example 1 to 1 〇〇. The smaller the index, the smaller the shrinkage ratio and the more excellent the dimensional stability. Further, the shrinkage ratio after the foaming in Comparative Example 1 was 丨.8%. 157712.doc -41 - 201213426 &lt;(9) Dimensional stability (β)&gt; Measurement by! The shrinkage rate of the vulcanized foamed sheet after 5 hours (vertical) χ 150 (horizontal) x 4 mm (thickness) was measured. Further, the index was calculated by setting Comparative Example 10 to 1 〇〇. The smaller the index, the smaller the shrinkage ratio and the more excellent the dimensional stability. Further, the shrinkage ratio after foaming in Comparative Example 10 was 12%. &lt;(10) Thermoformability&gt; The state of the molded article after the second heat molding was visually investigated. The table is not practical and has no problem, and x indicates that the uneven state is poor and the product is in a bad state. [Examples 1 to 6] and [Comparative Examples 1 to 5] The block copolymer of the component (a) and the BR and SBR as the component (b) were used, and as the component (4), cerium oxide was used, and The foaming agent of the component (4) and other additives were used, and the composition and the physical properties of the foam were shown in Table 2 below. The maximum temperature was adjusted to 170 to 180 ° C using a 1.7 L test Banbury mixer, and the blending materials other than the foaming agent and other additives in the blending composition shown in Table 2 were kneaded. Then, the kneaded material is kneaded by adding a foaming agent and other additives to a size of 10, and the mixture is kneaded into a sheet shape, and then subjected to heat-press molding (cross-linking, foaming) at 14 (r). The condition is appropriately adjusted in such a manner that the internal hardness of the molded article is 35 to 5 〇 (model c). The molding of the molded product produced by the conditions is performed at a compression ratio of 30% (at 150 C). The film was heated and pressed for 7 minutes and cooled for 15 minutes to obtain a foam. 157712.doc -42- 201213426

CN Comparative Example 5 A-10 yn v〇inchcn I 0.45 ίο 00 s 〇Comparative Example 4 A-9 Ό ^Ti ΓΛ inch cn 0.41 m (N rS 400 g X Comparative Example 3 A-8 in wn v〇m cn 0.42 丨沄 (N 440 (NX Comparative Example 2 A-7 in v〇m inch 0.45 1 cn — § 〇 Comparative Example 1 A-6 in v〇«-Η cn inch CO 0.38 1 wear \o &lt;N 440 〇 X Example 6 A-11 κη in v〇in m inch CO 0.43 1 VO (N cn 370 On 00 〇 Example 5 A-5 in v〇cn inch c〇0.44 VO VO CO — 290 00 〇 Example 4 A -4 v〇m inch m 0.43 CN VO 00 CO 340 (7) 00 〇 Example 3 A-3 v〇ό m inch CO 0,42 00 (N rn 380 OS 60 〇Example 2 A-2 in iri VO m inch Ro 0.42 */) CO 390 (S On 〇Example 1 1 &lt; \〇cn rf CO 0.39 &lt;N 00 CN 420 Type of 〇 block copolymer (% by mass) BR(fi%) SBR (mass./ 〇) cerium oxide (parts by mass) Foaming agent 1 (parts by mass) Foaming agent 2 (parts by mass) Other additives (parts by mass) Specific gravity (g/cc) Hardness (model c) Tb (MPa) Eb (%) Dimensional stability (a) Thermoformability component (8) Component (b) Component (C) Component (d) 1 hair Physical properties 43 - 157712.doc 201213426 The details of the symbols in Table 2 above are as follows: BR; polybutadiene ("Nipol BR1220" manufactured by 曰本瑞翁(ΖΕΟΝ))) SBR; styrene - Butadiene copolymer ("SBR1502" manufactured by KUMHO Co., Ltd.) cerium oxide; "Nipsil VN3" foaming agent 1 manufactured by Tosoh Silica Co., Ltd.; Ρ, Ρ'-oxybisbenzene sulfonate (OBSH) ) foaming agent 2; azodiamine (ADCA) other additives; polyethylene glycol (manufactured by Shanyang Chemical Industry Co., Ltd., trade name "PEG# 4000") 1 part by mass of stearic acid (Acacia ( (manufactured by the company) 1 part by mass of foaming auxiliary (urea derivative, manufactured by Sankyo Chemical Co., Ltd., trade name "Selton NF") 1 part by mass of DCP (98% dicumyl peroxide, sakamoto grease) (Stock) company, product name "PERCUMYL D" 0.4 parts by mass [Examples 7 to 10], [Comparative Examples 6 to 9] As shown in Table 3, the type, amount and composition of component (a) were changed (b) The amounts of (c) and (d) were obtained by the same method as in Example 1. The details of the symbols and the like in Table 3 are the same as those in Table 2, and the measurement method of the physical properties is also the same as described above. 157712.doc -44- 8 201213426 Comparative Example 9 Α-3 in in VO in 卜 inch 0.08 inch 〇420 CN cn X Comparative Example 8 Α-3 m \〇ot-HT*~H cn inch m -1 0.58 ( N § a\ 00 〇Comparative Example 7 1 g in m inch cn 0.43 Ο) 510 卜r-H 1—HX Comparative Example 6 Α-3 ο m !/&quot;&gt; m inch cn 0.44 yn m cn 230 m 00 〇Example 10 Α-3 VO iTi 寸 inch cn 0.39 (N (N 470 (N a 〇 Example 9 Α-3 m iT) m inch cn 0.44 \Τ) VjO port 370 〇 Example 8 Α-1 ( N in S vn 1-H cn inch rn 0.42 νΤ) m cn 370 00 00 〇 Example 7 Α-3 yr) IQ τ-Η cn inch cn 0.41 (N 440 v〇Ch 〇 block copolymer type (quality %) BR (% by mass) Lu 611 (% by mass) cerium oxide (parts by mass) Foaming agent 1 (parts by mass) 1_Blowing agent 2 (parts by mass) Other additives (parts by mass) Specific gravity (g/cc) Hardness (Model C) 1 Tb (MPa) Eb (%) Dimensional stability (a) Thermoformability component (4) Component (b) Component (C) Component (6) Foam physical property - 5 157712.doc .45 - 201213426 [Examples 11] With respect to the compounding composition of the above [Example 11], with respect to the component (a) and the component (b) 100 parts by mass, and 5 parts by mass of EVA (ethylene-vinyl acetate copolymer, manufactured by Tosoh Corporation, EVAUE 633, ethyl acetate content = 20%, MI = 20) was added. The other conditions were the same as in Example 1. A foam was obtained by the method. The obtained foam had a specific gravity of 0.39 g/cc, a hardness of 54, a Tb of 3 _0 MPa, an Eb of 390%, a dimensional stability of 93, and a thermoformability which is a property of 〇. The foams of Examples 1 to 11 were all foams excellent in hardness, dimensional stability, thermoformability, and mechanical strength. [Examples 12 to 17], [Comparative examples were used as the components (a). Segment copolymer a-1 to 1:1, BR (cis 1,4 polybutadiene) as component (b): high-cis polybutadiene & S_SBR, using cerium oxide as component (C) and as a component The foaming agent of (d) is further used with other additives, and the composition of the blend and the physical properties of the foam are shown in Table 4 below. The test banbury mixer is used in 1.7 L, and the maximum temperature is adjusted to 170-180. °C, will be under the 矣 dp; 匕 - Table 4 is not in the mix of the composition of the foaming agent, other additives Line kneading. Then, the foaming agent and other additives are added to the 10 size light μ I to knead the material, and the mixture is formed into a sheet, and then placed in a mold for sulfur-crosslinking and foaming. Smoke ^ / inclusion body. The vulcanization is at 160. (: proceeding under the clock) 1577l2.doc 8 -46 - 201213426 Comparative Example 14 A-10 (N »no 0.93 Μ 153 OS Comparative Example 13 A-9 &lt;Ν »〇&lt;Ti 10.1 0.91 1 〇11.4 S Comparison Example 12 A-8 in in ci 0.90 1 10.0 Ό (N &gt; - « o Comparative Example 11 A-7 «Λ CN to »〇10.1 1 0.93 1 CN 〇\ 'O VO Comparative Example 10 A-6 (N m 1··^ 10.1 0.89 io v© 10.5 o Example 17 A-11 ui (N in 10.1 0.90 cn 11.2 〇Example 16 A-5 VV CN ^—4 *Ti o 0.93 ] g 14.2 ON Example 15 A- 4 (N o 0.92 r- 12.2 is 00 Example 14 A-3 (N 10.1 0.91 1 S 11.2 v〇ON 00 00 Example 13 A-2 (N iTi o 0.91 CN 11.4 s 5; Example 12 1 &lt; (N in 10.1 1 0.90 o Ό 10.3 o 1-H r*H ΙΛ Q\ Type of block copolymer (% by mass) BR (cis 1,4 polybutadiene) (% by mass) 5-5811 (% by mass) ) Cerium dioxide (parts by mass) Foaming agent 1 (parts by mass) Foaming agent 2 (parts by mass) Other additives (parts by mass) 1 Specific gravity (g/cc) Hardness (Model A) Tb (MPa) Eb (%) Dimensional stability (β) Component (8) Component (b) Component (6) Component (d) Foam • 47· 157712.doc 201213426 The details of the symbols in Table 4 above are as follows: BR (cis 1,4 polybutadiene); "BR- 18j S-SBR" manufactured by 曰本合成橡胶有限公司; styrene-butadiene copolymer ("Asaprene 303" manufactured by Asahi Kasei Chemicals Co., Ltd.) cerium oxide; "Nipsil VN3" foaming agent 1 manufactured by Tosoh Silica Co., Ltd.; P, P'-oxygen Bis-benzene sulfonate (0BSH) foaming agent 2; azodiamine (ADCA) Other additives, polyethylidene alcohol (manufactured by Shanyang Chemical Industry Co., Ltd., trade name "PEG# 4000")1 3% by mass of zinc oxide (manufactured by Asahi Kasei Co., Ltd.), 1 part by mass of titanium oxide (anatase type), 4 parts by mass of a foaming auxiliary (urea derivative, manufactured by Sankyo Chemical Co., Ltd.) , product name "SeltonNF") 1 part by mass of DCP (98% dicumyl peroxide, sakamoto oil company), trade name "PERCUMYL D" 0.05 parts by mass sulfur 0.05 parts by mass [Examples I8 to 21] [Comparative Examples 15 to 18] As shown in Table 5 below, 'Change the type and amount of component (a) and components (b), (c), d) The amount 'by the same procedures as in Example 12 to obtain the above-described foam. The details of the symbols in Table 5 are the same as those in Table 4, and the measurement method of physical properties is also the same as above. 157712.doc -48-201213426 Comparative Example 18 A-3 (N in 10.1 0.73 CN V&quot;) &lt;N inch ϊ- Η (N CS Comparative Example 17 A-3 (N m 〇τ-Η T-Η &lt;ό 0.95 00 00 13.8 &lt; N 00 Comparative Example 16 Sun % o 0.89 VO ON VO iim Comparative Example 15 A-3 cs y -^ 10.1 0.92 〇\ (N cK CN VO z Example 21 A-3 (Ν m &lt;N i〇〇0.86 Os o Example 20 A-3 CN yr\ \r\ 〇in 10.1 丨0.93 § Oi 00 QO Example 19 A-1 mmi/Ί in 〇10.1 0.91 Os 12.8 m 00 Example 18 A-3 00 in 10.1 0.90 Ό VO 〇\ 00 om Type of block copolymer (% by mass) BR (cis 1,4 Polybutadiene) (% by mass) 8 311 (% by mass) cerium oxide (parts by mass) Foaming agent l (parts by mass) Foaming agent 2 (parts by mass), other additives (parts by mass) Specific gravity (g/ Cc) Hardness (Model A) Tb (MPa) Eb (%) Dimensional stability (β) Component (a) Component (b) Component (C) Component (d) 1 Foam physical property -49- 157712.doc 201213426 [ Example 22] For the compounding composition of the above [Example 18], 5 parts by mass of EVA (ethylene-vinyl phthalate copolymer, manufactured by Tosoh, EVAUE 63 3, ethyl acetate content = 20%, MI =) was added to 100 parts by mass of the component (a) and the component (b). 20) A foam was obtained by the same method as [Example 18] under other conditions. The obtained foam had a specific gravity of 〇.9〇g/cc, a hardness of 68, and a Tb of 9.2 MPa. Eb was 110%, and the dimensional stability was 95. The foams of Examples 12 to 22 were all foams excellent in hardness, dimensional stability, and mechanical strength. Industrial Applicability Suitable for shoe midsole, shoe last or outsole material, material 5:: men's shoes, ladies' shoes, casual shoes and other footwear materials, but with industrial availability. 157712.doc 8 •50-

Claims (1)

201213426 VII. Application for Patent Park: - A type of foam which is obtained by crosslinking a composition containing a foam having the following components: (4) a block copolymer containing at least two ethyl women's aromatic hydrocarbons a polymer block, and at least i copolymer blocks comprising a total of dilute and ethylene-based aromatic hydrocarbons, and the content of the vinyl-containing aromatic hydrocarbons of the mass % and the conjugated diene is 65 to 95. 5 to 35 mass%, the vinyl aromatic hydrocarbon polymer contained in the block copolymer is 40 to 98% by mass, and the storage elastic modulus (E,) is 3x10 〇 in the dynamic viscoelasticity measurement 3〇°c P a The above 2·35&gt;&lt;1〇9p is less than or equal to *Pa, and the peak temperature of the function of the dynamic viscoelasticity measurement is 85. (: 125 以上 above: at least one of the following; (b) isoprene-based rubber and/or diene-based rubber; 0) filler; (d) foaming agent; (4) block copolymer and the above (b) The ratio of the amount of the isoprene-based rubber and/or the di-thin rubber ((4)/(8)) is ((4) to 99); compared with the above (4) block copolymer and the above (8) glue and/or two The total amount of the rare rubber is 1G (four) denier 6" τ set iuo bei injury, and contains 1 to 100 parts by mass of the above (c) true charge, and the above (d) foaming agent 〇 1 to 3 parts by mass; The specific gravity of the foam is (U~0 98 g/cc. 2. The foam according to claim 1, wherein the upper layer is a function of the dynamic cohesive enthalpy of the block copolymer ίαηδ 9〇.〇125. [There is at least one of the following. 157712.doc 201213426 3. The foam of claim 1 or 2, wherein the (a) block copolymer contains to; one contains vinyl aromatic a random copolymer block of a total amount of 7% by mass or more and less than 7% by mass of the ethylene-based aromatic tobacco and a total of two women. 4. The foam according to any one of claims 1 to 3, The above (a) block copolymer contains at least i random copolymer blocks of a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of 75% by mass or more and 98% by mass or less. The foam according to any one of claims 1 to 4, wherein a total mass of 100 mass relative to the above (a) block copolymer and the above (b) isoprene-based rubber and/or diene rubber And a part of the above-mentioned (C) filler: 2 to 90 parts by mass, and the above (d) foaming agent 〇 5 to 20 parts by mass. 6. The foam according to any one of claims 1 to 5, wherein 100 parts by mass of the above-mentioned (&amp;) block copolymer and the above (b) isoprene-based rubber and/or diene-based rubber, and further contains: (e) thermoplastic elastomer and/or thermoplastic resin 1 The foam according to any one of claims 1 to 6, which has a specific gravity of 〇1 to 〇7 g/cc, or a specific gravity of 〇·8 to 0.98 g/cc. A shoe sole formed by molding the foam of any one of claims 1 to 7. 9. A composition for a foam comprising: (a) a block copolymer, There are at least two vinyl aromatic hydrocarbon polymer blocks, and at least one copolymer block comprising a total of a diene and a vinyl aromatic hydrocarbon, and the content of the 157712.doc 201213426 vinyl aromatic hydrocarbon is 65~ 95 mass. The content of the conjugated diene is 5 to 35% by mass, and the block ratio of the vinyl aromatic hydrocarbon polymer contained in the block copolymer is 40 to 98% by mass, ψ ίο. The next error is the elastic modulus (eWx1〇8 Pa or more and 2.35χ1〇pa or less, and the function of dynamic viscoelasticity measurement is at least one peak temperature above 85t and 125t; (b) isoprene (a) a filler; (d) a foaming agent; the mass of the above (a) block copolymer and the above (b) isoprene-based rubber and/or diene rubber It is contained in the total mass fraction of the above-mentioned (b) isocyanate rubber and/or the diene rubber, and is contained in the above-mentioned (4) toluene copolymer and the above (b) isoprene rubber and/or diene rubber. The above (c) filler is 1 to 100 parts by mass, and the above (d) foaming agent 〇 is 30 parts by mass. A foam comprising: (ai) a block copolymer comprising at least two vinyl aromatic hydrocarbon polymer blocks, and at least one copolymer comprising a conjugated dilute and a vinyl aromatic hydrocarbon And the content of the vinyl aromatic hydrocarbon is 65 to 95% by mass, the content of the conjugated diene is 5 to 35% by mass, and the block ratio of the vinyl aromatic hydrocarbon polymer contained in the copolymer 40 to 98% by mass; (b) Isoprene-based rubber and/or diene-based rubber; (c) Filler; 157712.doc 5 201213426 (d) Foaming agent; Specific gravity: 0.1 to 0.7 g/cc The hardness measured by the model C is 45 to 98; when the specific gravity is 0.8 to 0.98 g/cc, the hardness measured by the model A is 60 to 98 〇 157712.doc -4- 8 201213426 4. Designation: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 157712.doc 5 * *