WO2012026376A1 - Mousse, et composition pour mousse - Google Patents

Mousse, et composition pour mousse Download PDF

Info

Publication number
WO2012026376A1
WO2012026376A1 PCT/JP2011/068631 JP2011068631W WO2012026376A1 WO 2012026376 A1 WO2012026376 A1 WO 2012026376A1 JP 2011068631 W JP2011068631 W JP 2011068631W WO 2012026376 A1 WO2012026376 A1 WO 2012026376A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
parts
block copolymer
aromatic hydrocarbon
vinyl aromatic
Prior art date
Application number
PCT/JP2011/068631
Other languages
English (en)
Japanese (ja)
Inventor
星　進
一夫 森藤
Original Assignee
旭化成ケミカルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2010186369A external-priority patent/JP5597478B2/ja
Priority claimed from JP2010186441A external-priority patent/JP5597479B2/ja
Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to CN201180037240.3A priority Critical patent/CN103038275B/zh
Priority to KR1020137002495A priority patent/KR101500248B1/ko
Publication of WO2012026376A1 publication Critical patent/WO2012026376A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a foam suitable for a material for a shoe midsole, inner sole or outsole, and a composition for foam.
  • the foam material used for sports shoes and the like is required to have cushioning properties, impact buffering properties, lightness, and the like.
  • EVA ethylene-vinyl acetate copolymer
  • PU polyurethane
  • silica silica
  • a cross-linked foam for shoes is used in which bubbles are contained in a rubber composition containing a filler such as carbon black.
  • the air bubbles can be contained by foaming of a foaming agent, blending of fine hollow spheres, and the like, but further reduction in weight has been studied for the crosslinked foam for shoes.
  • Patent Document 1 discloses a material containing syndiotactic 1,2-polybutadiene as a foamed rubber sole that is excellent in wear resistance, light and non-slip.
  • Patent Document 2 discloses a block copolymer-based cross-linked foam that is lightweight and has a cushioning breathability, a sound insulation property, and the like.
  • Patent Document 3 contains a styrene-butadiene block copolymer having a styrene content of 60% or less as a foam having a small hardness change even under high temperature and low temperature environments and having excellent cushioning properties and shock buffering properties.
  • a foam of material is disclosed.
  • Patent Document 4 discloses a composition containing a radial type thermoplastic elastomer, a linear type thermoplastic elastomer, and 1,2-polybutadiene as a molding composition having excellent moldability and excellent flexibility and moldability.
  • Patent Document 5 discloses a hydrogenated block copolymer for producing a foam excellent in tear strength, compression set resistance, low rebound resilience, and abrasion resistance.
  • JP 63-200702 A Japanese Unexamined Patent Publication No. 63-225638 JP 2001-340105 A Japanese Patent Application Laid-Open No. 2004-217846 International Publication No. 2007/094216
  • an object of the present invention is to provide a foam excellent in hardness, dimensional stability, thermoformability and mechanical strength, and particularly suitable for a midsole for shoes, an inner sole and an outsole.
  • the present inventors have obtained a block containing a vinyl aromatic hydrocarbon having a specific viscoelastic behavior and a conjugated diene.
  • Copolymer, a predetermined rubber component, a filler, and a foam containing a foaming agent in a predetermined ratio, or a block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene, a predetermined rubber component, and a filler The inventors have found that a foam containing a foaming agent and having a specific hardness in a specific gravity within a predetermined range can achieve the above object, and has completed the present invention. That is, the present invention is as follows.
  • the vinyl aromatic hydrocarbon content is 65 to 95% by mass
  • the conjugated diene content 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
  • the storage elastic modulus (E ′) at 30 ° C. in dynamic viscoelasticity measurement is 3 ⁇ 10 8 Pa or more and 2.35 ⁇ 10 9 Pa or less
  • the peak temperature of the function tan ⁇ of dynamic viscoelasticity measurement is 85 ° C. or more.
  • the mass ratio of the (a) block copolymer to the (b) isoprene rubber and / or diene rubber is 1 to 30/70 to 99,
  • the filler (c) is added in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer (a) and the (b) isoprene rubber and / or diene rubber.
  • the (a) block copolymer contains at least one random copolymer block composed of a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon content of 70% by mass or more and less than 100% by mass and a conjugated diene.
  • the block copolymer (a) contains at least one random copolymer block comprising a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon content of 75% by mass to 98% by mass and a conjugated diene.
  • the vinyl aromatic hydrocarbon content is 65 to 95% by mass
  • the conjugated diene content 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
  • the storage elastic modulus (E ′) at 30 ° C. in dynamic viscoelasticity measurement is 3 ⁇ 10 8 Pa or more and 2.35 ⁇ 10 9 Pa or less
  • the peak temperature of the function tan ⁇ of dynamic viscoelasticity measurement is 85 ° C. or more.
  • the mass ratio of the (a) block copolymer to the (b) isoprene rubber and / or diene rubber is 1 to 30/70 to 99,
  • the filler (c) is added in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer (a) and the (b) isoprene rubber and / or diene rubber.
  • a foam composition containing 0.1 to 30 parts by mass of a foaming agent.
  • a ′ a block copolymer containing at least two vinyl aromatic hydrocarbon polymer blocks and at least one copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon,
  • the vinyl aromatic hydrocarbon content is 65 to 95% by mass
  • the conjugated diene content is 5 to 35% by mass
  • a block copolymer in which the block ratio of the vinyl aromatic hydrocarbon polymer contained in the block copolymer is 40 to 98% by mass
  • B isoprene-based rubber and / or diene-based rubber
  • C a filler
  • D a foaming agent; Including When the specific gravity is 0.1 to 0.7 g / cc, the hardness measured with Type C is 45 to 98, A foam having a hardness measured by Type A of 60 to 98 when the specific gravity is 0.8 to 0.98 g / cc.
  • a foam which is excellent in hardness, dimensional stability, thermoformability and mechanical strength and suitable mainly for a midsole for shoes, an inner sole or an outsole can be obtained.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described.
  • this invention is not limited to the following description, In the range of the summary, various deformation
  • the foam of the first embodiment in the foam of this embodiment contains the following components (a) to (d).
  • the vinyl aromatic hydrocarbon content is 65 to 95% by mass
  • the conjugated diene content 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
  • the storage elastic modulus (E ′) at 30 ° C.
  • the mass ratio of the (a) block copolymer to the (b) isoprene-based rubber and / or diene-based rubber is 1 to 30/70 to 99
  • the filler (c) is added in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer (a) and the (b) isoprene rubber and / or diene rubber.
  • a foam composition containing 0.1 to 30 parts by mass of a foaming agent is crosslinked and has a specific gravity of 0.1 to 0.98 g / cc.
  • component (a) is a block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene.
  • the content of the vinyl aromatic hydrocarbon in the component (a) is 65 to 95% by mass, preferably 68 to 93% by mass, more preferably 70 to 90% by mass.
  • the content of the conjugated diene in the component (a) is 5 to 35% by mass, preferably 7 to 32% by mass, and more preferably 10 to 30% by mass.
  • the vinyl aromatic hydrocarbon content is in the range of 65 to 95% by mass and the conjugated diene content is in the range of 5 to 35% by mass, the balance between the hardness and elongation of the foam and the thermoformability is excellent. It becomes a foam suitable for shoes.
  • the content of the vinyl aromatic hydrocarbon and the content of the conjugated diene in the component (a) are determined by measuring the absorption light intensity with respect to light of a predetermined wavelength using an ultraviolet spectrophotometer.
  • the block ratio of the vinyl aromatic hydrocarbon polymer contained in component (a) is 40 to 98% by mass, preferably 50 to 95% by mass, more preferably 60 to 90% by mass.
  • the block ratio of the vinyl aromatic hydrocarbon polymer depends on the weight of the random copolymer chain composed of the vinyl aromatic hydrocarbon and the conjugated diene in the component (a) and the content (% by mass) of the vinyl aromatic hydrocarbon. Can be adjusted.
  • the block ratio of the vinyl aromatic hydrocarbon polymer decreases as the amount of vinyl aromatic hydrocarbon in the random copolymer chain constituting the component (a) block copolymer increases, and the block ratio increases as the amount decreases.
  • the block ratio of the vinyl aromatic hydrocarbon polymer is determined by a method in which component (a) block copolymer is oxidatively decomposed with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (oxidative decomposition method: IM KOLTHOFF, etal. , J. Polym.Sci.
  • Block ratio (mass%) (weight of vinyl aromatic hydrocarbon polymer in block copolymer / weight of block polymer chain / total weight of vinyl aromatic hydrocarbon in block copolymer) ⁇ 100
  • the “total weight of the vinyl aromatic hydrocarbon in the block copolymer” is determined from the charge ratio at the time of polymerization or by analysis such as NMR.
  • Component (a) has at least two vinyl aromatic hydrocarbon polymer blocks and at least one copolymer block composed of a conjugated diene and a vinyl aromatic hydrocarbon.
  • the polymer structure of component (a) is not particularly limited.
  • a linear block copolymer or a radial block copolymer represented by the following general formula, or any mixture of these polymer structures can be used.
  • at least one block A and / or block B may be bonded to X.
  • block A is composed of a vinyl aromatic hydrocarbon polymer
  • block B is composed of a copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon.
  • X is, for example, a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, or polyfunctional organic
  • a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, or polyfunctional organic
  • an initiator such as a lithium compound is shown.
  • n, k and m are each an integer of 1 or more, generally an integer of 1 to 5.
  • bonds together may be the same, or may differ.
  • Component (a) contained in the foam The vinyl aromatic hydrocarbon in the copolymer of vinyl aromatic hydrocarbon and conjugated diene in the block B constituting the block copolymer is uniformly distributed. May also be distributed in a taper (gradual decrease). In the copolymer, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed may coexist in the block.
  • the block copolymer comprises a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of less than 70% by mass and less than 100% by mass, preferably 75% by mass to 98% by mass. It is preferable to contain at least one random copolymer block. Thereby, a foam having good hardness and dimensional stability can be obtained.
  • the component (a) can be obtained by polymerizing a vinyl aromatic hydrocarbon and a conjugated diene in a hydrocarbon solvent using an organolithium compound as an initiator.
  • vinyl aromatic hydrocarbon examples include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene, N, N-dimethyl-p-aminoethyl styrene, N, N-diethyl-p-aminoethyl styrene and the like, among which styrene is particularly common. These may be used alone or in combination of two or more.
  • 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-1,3- Butadiene, 1,3-pentadiene, 1,3-hexadiene and the like, and particularly common ones include 1,3-butadiene, isoprene and the like. These may be used individually by 1 type, and may mix and use 2 or more types.
  • hydrocarbon solvent examples include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclohexane Alicyclic hydrocarbons such as heptane and methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can be used. These may be used individually by 1 type and may use 2 or more types together.
  • aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane
  • cyclopentane methylcyclopentane
  • an aliphatic hydrocarbon alkali metal compound or aromatic compound known to have anionic polymerization activity with respect to a conjugated diene and a vinyl aromatic compound generally, an aliphatic hydrocarbon alkali metal compound or aromatic compound known to have anionic polymerization activity with respect to a conjugated diene and a vinyl aromatic compound.
  • Group hydrocarbon alkali metal compounds, organic amino alkali metal compounds, and the like can be used. Examples of the alkali metal constituting these include lithium, sodium, potassium, and the like.
  • Suitable organic alkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, in one molecule. Examples thereof include a compound containing one lithium, a dilithium compound containing a plurality of lithium in one molecule, a trilithium compound, and a tetralithium compound.
  • organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to. These may be used alone or in combination of two or more.
  • the polymerization temperature for producing the component (a) is generally ⁇ 10 ° C. to 150 ° C., preferably 40 ° C. to 120 ° C. Although the time required for the polymerization varies depending on the conditions, it is usually within 10 hours, particularly preferably 0.5 to 5 hours.
  • the polymerization atmosphere is preferably replaced with an inert gas such as nitrogen gas.
  • the polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range. Furthermore, it is preferable to take care not to mix impurities that inactivate the catalyst and living polymer, such as water, oxygen, and carbon dioxide, into the polymerization system.
  • the block copolymer is a block copolymer containing at least two vinyl aromatic hydrocarbon polymer blocks and at least one copolymer block composed of a conjugated diene and a vinyl aromatic hydrocarbon. is there.
  • the timing of introducing the vinyl aromatic compound and the conjugated diene compound as the raw material monomer in the polymerization step of component (a): block copolymer may be controlled.
  • Component (a): The block copolymer has a vinyl aromatic hydrocarbon content of 65 to 95% by mass and a conjugated diene content of 5 to 35% by mass.
  • the amount of the vinyl aromatic compound or conjugated diene compound used as the raw material monomer in the polymerization step of component (a): block copolymer may be adjusted.
  • the component (a): block copolymer has a vinyl aromatic hydrocarbon content of 70% by mass or more and less than 100% by mass, preferably 75% by mass or more and 98% by mass or less, and a conjugated diene.
  • At least one random copolymer block comprising: In order to obtain such a configuration, the amount of monomer used as a raw material may be adjusted in the random block polymerization step during the production process of component (a): block copolymer.
  • the component (a): block copolymer has a storage elastic modulus (E ′) at 30 ° C. in dynamic viscoelasticity measurement of 3 ⁇ 10 8 Pa or more and 2.35 ⁇ 10 9 Pa or less, Moreover, at least one peak temperature of the function tan ⁇ of the dynamic viscoelasticity measurement exists at 85 ° C. or more and 125 ° C. or less. Preferably, the storage elastic modulus (E ′) at 30 ° C.
  • the storage elastic modulus (E ′) at 30 ° C. in the dynamic viscoelasticity measurement of the block copolymer is 3 ⁇ 10 8 Pa or more and 2.35 ⁇ 10 9 Pa or less, and the dynamic viscoelasticity measurement is performed.
  • the foam of this embodiment has an excellent balance of hardness, elongation and thermoformability, and is suitable for a shoe sole. is there.
  • the storage elastic modulus (E ′) and tan ⁇ in the dynamic viscoelasticity measurement of the component (a) can be measured by the method described in Examples described later.
  • it can be measured by a rheology viscoelasticity measuring and analyzing apparatus DVE-V4 manufactured by Rheology Co., Ltd. or Leo Vibron DDV-3 type manufactured by Toyo Baldwin Co., Ltd.
  • the vibration frequency is 35 Hz
  • the heating rate is 3 ° C.
  • Measurement can be performed using a test piece having a thickness of 0.5 to 2 mm under the condition of min.
  • the storage elastic modulus (E ′) at 30 ° C. in the dynamic viscoelasticity measurement is as follows: block A composed of vinyl aromatic hydrocarbon polymer constituting component (a), conjugated diene and vinyl aroma
  • the ratio of the block B to the block B composed of a copolymer composed of a group hydrocarbon can be increased by increasing the block A. That is, by appropriately adjusting the ratio of the block A and the block B constituting the component (a), the storage elastic modulus (E ′) at 30 ° C. is 3 ⁇ 10 8 Pa or more and 2.35 ⁇ 10 9 Pa.
  • the following numerical ranges can be controlled.
  • the peak temperature of the function (tan ⁇ ) of the dynamic viscoelasticity measurement of component (a) is, for example, increasing the vinyl aromatic hydrocarbon content of component (a), increasing the molecular weight of component (a), and increasing component (a)
  • the ratio of the vinyl aromatic hydrocarbon in the random copolymer block comprising the vinyl aromatic hydrocarbon and the conjugated diene constituting is 70% by mass or more and less than 100% by mass, preferably 75% by mass or more and 98% by mass or less, Within the range, it can be highly controlled by increasing the ratio of vinyl aromatic hydrocarbons.
  • the random copolymer block comprising the vinyl aromatic hydrocarbon and the conjugated diene constituting the component (a) is, for example, increasing the vinyl aromatic hydrocarbon content of component (a), increasing the molecular weight of component (a), and increasing component (a)
  • the ratio of the vinyl aromatic hydrocarbon in the random copolymer block comprising the vinyl aromatic hydrocarbon and the conjugated diene constituting is 70% by mass or more and less than 100% by mass, preferably
  • the ratio of the vinyl aromatic hydrocarbon is 70% by mass or more and less than 100% by mass, preferably 75% by mass or more and 98% by mass or less.
  • the random copolymer block may be controlled to be low by increasing the ratio of the vinyl aromatic hydrocarbon homopolymer block. That is, by performing the various adjustments described above, the peak temperature of the function (tan ⁇ ) of the dynamic viscoelasticity measurement of the component (a) can be controlled to 85 ° C. or more and 125 ° C. or less.
  • the molecular weight of component (a) is not particularly limited, but is preferably 30,000 to 1,000,000, more preferably 40, in terms of polystyrene in gel permeation chromatography method (GPC method). From 50,000 to 500,000, more preferably from 50,000 to 300,000. By setting the molecular weight of component (a) within the above range, a foam composition having excellent fluidity and processability can be obtained.
  • Isoprene rubber is natural rubber and isoprene rubber
  • diene rubber is styrene / butadiene copolymer rubber, polybutadiene rubber, acrylonitrile / butadiene copolymer rubber, ethylene / propylene / diene copolymer rubber, etc.
  • component (b) which comprises the foam of embodiment these may be used independently and 2 or more types may be used together.
  • Component (b) may contain various plasticizers such as oils such as paraffin oil, naphthenic oil, and aromatic oil, and dioctyl phthalate, dibutyl phthalate, dioctyl sepacate, and dioctyl adipate.
  • oils such as paraffin oil, naphthenic oil, and aromatic oil
  • the paraffin oil include Diana Process Oil PW-90, PW-380, PS-32, PS-90, PS-430 manufactured by Idemitsu Kosan Co., Ltd., Fukkoru Process P-100, P-200, P- manufactured by Fuji Kosan Co., Ltd.
  • aromatic oil examples include Diana Process Oil AC-12, AC460, AH-16, AH-58 manufactured by Idemitsu Kosan Co., Ltd., Mobilsol K manufactured by ExxonMobil Co., Ltd. X50, X100, X140, Resox No. 3, Dutrex 729UK, Nippon Oil Co., Ltd. Comolex 200, 300, 500, 700, ExxonMobil Esso Process Oil 110, 120, Nippon Oil Co., Ltd. Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 heavy process oil, Mitsubishi 39 heavy process oil, and the like.
  • the compounding amount of the plasticizer is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the component (b).
  • the blending amount of the plasticizer is 1 to 200 parts by mass, the foam of this embodiment has excellent processability.
  • polybutadiene is mentioned as a suitable example.
  • the polybutadiene rubber contains 5% to 20% of 1,2 bonds (vinyl), 0 to 3% of trans 1,4 bonds, and the remaining components.
  • High cis polybutadiene rubber and the like are also included.
  • the mass ratio of the component (a) to the component (b) is (1-30) / (70-99)
  • excellent hardness and dimensional stability can be obtained in the foam.
  • the filler examples include silica, calcium carbonate, clay, talc, mica, barium sulfate, magnesium carbonate glass fiber, glass beads, potassium titanate, carbon black, carbon-silica, dual phase filler, and the like.
  • the blending amount of the filler is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b) described above, preferably The amount is 2 to 90 parts by mass, more preferably 3 to 75 parts by mass, and still more preferably 5 to 50 parts by mass.
  • the blending amount of component (c): filler is 1 to 100 parts by mass, a suitable hardness and a preferred specific gravity can be obtained in the foam of this embodiment.
  • foaming agent for example, a publicly known inorganic foaming agent or organic foaming agent can be used.
  • sulfonyl hydrazides such as sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, azodicarbonamide, dinitrosopentamethylenetetramine, dinitrosoterephthalamide, azobisisobutyronitrile, azodicarboxylate barium, toluenesulfonylhydrazide And the like.
  • azodicarbonamide, dinitrosopentamethylenetetramine, sulfonyl hydrazides, and sodium bicarbonate are more preferable.
  • foaming agents may be used in combination with known foaming aids such as urea and urea derivatives.
  • thermally expandable microcapsules can be used as the foaming agent.
  • This thermally expandable microcapsule is made of foamed particles of a thermoplastic hollow sphere, and is composed of a shell made of a thermoplastic resin enclosing a gas.
  • the thermoplastic shell softens and the gas increases pressure, with the result that the sphere expands and acts as a foaming agent.
  • thermoplastic resin constituting the shell of the microcapsule examples include vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-methyl methacrylate copolymer, vinylidene chloride-ethyl methacrylate, acrylonitrile-methyl methacrylate copolymer, and acrylonitrile-ethyl. And methacrylate. Moreover, isopentane, isobutane, isopropane etc. are mentioned as a compound which becomes a gas by heating.
  • the mass average particle size of the thermally expandable microcapsule is usually 10 to 100 ⁇ m, The thickness is preferably about 20 to 80 ⁇ m.
  • thermally expandable microcapsule examples include EXPANCEL DU, WU series manufactured by Nippon Philite Co., Ltd., Microsphere F-30, F-50, F-80S, F-85 manufactured by Matsumoto Yushi Co., Ltd., and the like.
  • heat-expandable microcapsules are used as a foaming agent, the foams are uniformly expanded by heating according to the gasification of gas generating components contained in the individual microcapsules, and a homogeneous foam can be obtained.
  • an exothermic foaming agent and an endothermic foaming agent as the foaming agent because the exothermic action during foam molding can be suppressed.
  • the exothermic foaming agent include azodicarbonamide and dinitrosopentamethylenetetramine.
  • examples of the endothermic foaming agent include sodium bicarbonate, and in this case, the generated gas is carbon dioxide.
  • the blending amount of component (d): foaming agent is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (a) and component (b) described above. It is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass.
  • the blending amount of component (d): foaming agent is 0.1 to 30 parts by mass, excellent hardness is obtained in the foam of the present embodiment, and the specific gravity is a preferred value.
  • the foam of this embodiment may further contain component (e): a thermoplastic elastomer and / or a thermoplastic resin in addition to the components (a) to (d) described above.
  • component (e) a thermoplastic elastomer and / or a thermoplastic resin in addition to the components (a) to (d) described above.
  • thermoplastic elastomer for example, according to the chemical composition of the hard segment, olefin-based thermoplastic elastomer (TPO), urethane-based thermoplastic elastomer (TPU), ester-based thermoplastic elastomer (TPEE), amide-based thermoplastic An elastomer (TPAE) etc. are mentioned.
  • thermoplastic elastomer ion cluster-type thermoplastic elastomer (ionomer), fluorine-based thermoplastic elastomer containing a fluorine resin as a constraining block, etc.
  • TPO by dynamic crosslinking that improves the performance by kneading while crosslinking the rubber to be a soft segment and making the rubber dispersed particle size fine may be referred to as TPV).
  • the thermoplastic elastomer mentioned above may be used individually by 1 type, and may use 2 or more types together.
  • thermoplastic elastomers synthetic rubbers other than the above component (a) or component (b) can be used, such as fluorine rubber, silicone rubber, halogenated butyl rubber (for example, chlorinated butyl rubber, brominated butyl rubber). Etc.), etc., and these may be used alone or in combination of two or more.
  • thermoplastic resin any thermoplastic resin having a plasticizing temperature of 50 to 300 ° C. can be used without particular limitation.
  • styrene resin eg, polystyrene, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, etc.
  • ABS resin ABS resin
  • AES resin AAS resin
  • polyethylene polypropylene
  • ethylene-propylene resin ethylene-propylene resin
  • ethylene-ethyl acrylate Resin polyvinyl chloride, polyvinylidene chloride, polybutene, polycarbonate, polyacetal, polyphenylene oxide, polymethyl methacrylate, saturated polyester resin (for example, hydroxycarboxylic acid condensate such as polylactic acid, diol and dicarboxylic acid such as polybutylene succinate) Acid condensates), polyamide resins, fluororesins, polysulfone, polyether
  • thermoplastic resins polystyrene, acrylonitrile / styrene copolymer, ABS resin, AES resin, AAS resin, polyethylene, polypropylene, polyvinyl chloride, saturated polyester resin, and polyamide resin are preferable. By blending these thermoplastic resins, sinks and deformation can be prevented in the foamed molded product of this embodiment, which is preferable.
  • Component (e) The amount of the thermoplastic elastomer and / or thermoplastic resin is preferably 1 to 100 parts by weight, more preferably 3 to 100 parts by weight with respect to 100 parts by weight as the total of component (a) and component (b). 75 parts by mass, more preferably 5 to 50 parts by mass.
  • a suitable mechanical strength can be obtained in the foam of this embodiment.
  • the foam composition for obtaining the foam according to the first embodiment of the present embodiment includes the components (a) to (d) described above, the component (a) block copolymer, and the component (b).
  • the mass ratio (component (a) / component (b)) to isoprene-based rubber and / or diene-based rubber is (1-30) / (70-99), preferably (2-25) / (5-98 ), More preferably (5-20) / (80-95), and the total amount of the (a) block copolymer and the (b) isoprene rubber and / or diene rubber is 100 parts by mass.
  • the above (c) filler is contained in an amount of 1 to 100 parts by weight, preferably 2 to 90 parts by weight, more preferably 3 to 75 parts by weight, and further preferably 5 to 50 parts by weight. 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass.
  • the component (e) may be contained, preferably 1 to 100 parts by weight, more preferably 3 to 75 parts by weight, further preferably 100 parts by weight of the total amount of the components (a) and (b). 5 to 50 parts by mass.
  • a conventionally known kneader, extruder, or the like can be used.
  • the blending method and blending order of (c) filler, (d) foaming agent, etc. for example, the components (a) and (b) were previously melt-kneaded at 100 to 180 ° C. with a Banbury mixer or the like.
  • examples include, but are not limited to, a method of adding a foaming agent, a crosslinking agent, etc. using a roll or the like after blending the product with (c) a filler using a Banbury mixer or the like. .
  • the foam of the second embodiment contains the following components (a ′) to (d).
  • a ′ a block copolymer containing at least two vinyl aromatic hydrocarbon polymer blocks and at least one copolymer block comprising a conjugated diene and a vinyl aromatic hydrocarbon, The vinyl aromatic hydrocarbon content is 65 to 95% by mass, the conjugated diene content is 5 to 35% by mass, A block copolymer wherein the block ratio of the vinyl aromatic hydrocarbon polymer contained in the block copolymer is 40 to 98% by mass.
  • B Isoprene rubber and / or diene rubber.
  • C Filler.
  • D A foaming agent.
  • the foam of the second embodiment has a hardness measured by type C of 45 to 98 and a specific gravity of 0.8 to 0.98 g / cc.
  • the hardness measured with Type A is 60 to 98.
  • the component (a ′) is a block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene.
  • the content of the vinyl aromatic hydrocarbon in the component (a ′) is 65 to 95% by mass, preferably 68 to 93% by mass, more preferably 70 to 90% by mass.
  • the content of the conjugated diene in the component (a ′) is from 5 to 35% by mass, preferably from 7 to 32% by mass, more preferably from 10 to 30% by mass.
  • the vinyl aromatic hydrocarbon content is in the range of 65 to 95% by mass and the conjugated diene content is in the range of 5 to 35% by mass, the balance between the hardness and elongation of the foam and the thermoformability is excellent. It becomes a foam suitable for shoes.
  • the content of the vinyl aromatic hydrocarbon and the content of the conjugated diene in the component (a ′) are determined by measuring the absorption light intensity with respect to light of a predetermined wavelength using an ultraviolet spectrophotometer.
  • the block ratio of the vinyl aromatic hydrocarbon polymer contained in the component (a ′) is 40 to 98% by mass, preferably 50 to 95% by mass, more preferably 60 to 90% by mass.
  • the block ratio of the vinyl aromatic hydrocarbon polymer is determined by the weight of the random copolymer chain composed of the vinyl aromatic hydrocarbon and the conjugated diene in the component (a ′) and the content (% by mass) of the vinyl aromatic hydrocarbon. Can be adjusted.
  • the block ratio of the vinyl aromatic hydrocarbon polymer decreases as the amount of vinyl aromatic hydrocarbon in the random copolymer chain constituting the component (a ′) block copolymer increases, and the block ratio increases as the amount decreases.
  • the block ratio of the vinyl aromatic hydrocarbon polymer is determined by the same method as that for the component (a) described above.
  • Component (a ′) has at least two vinyl aromatic hydrocarbon polymer blocks and at least one copolymer block composed of a conjugated diene and a vinyl aromatic hydrocarbon.
  • the polymer structure of component (a) is not particularly limited.
  • a linear block copolymer or a radial block copolymer represented by the following general formula, or any mixture of these polymer structures can be used.
  • at least one block A and / or block B may be bonded to X.
  • block A is composed of a vinyl aromatic hydrocarbon polymer
  • block B is composed of a copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon.
  • X is, for example, a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, or polyfunctional organic
  • a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, or polyfunctional organic
  • an initiator such as a lithium compound is shown.
  • n, k and m are each an integer of 1 or more, generally an integer of 1 to 5.
  • bonds together may be the same, or may differ.
  • Component (a ′) contained in the foam The vinyl aromatic hydrocarbon in the copolymer of vinyl aromatic hydrocarbon and conjugated diene in the block B constituting the block copolymer is uniformly distributed. Alternatively, it may be distributed in a taper (gradual decrease). In the copolymer, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed may coexist in the block.
  • the block copolymer comprises a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of less than 70% by mass and less than 100% by mass, preferably 75% by mass to 98% by mass. It is preferable to contain at least one random copolymer block. Thereby, a foam having good hardness and dimensional stability can be obtained.
  • Component (a ′) can be produced by the same method as component (a) described above.
  • the same materials as those for component (a) can be used.
  • polymerization conditions such as superposition
  • the block copolymer preferably has a storage elastic modulus (E ′) at 30 ° C. of 3 ⁇ 10 8 Pa or more and 2.35 ⁇ 10 9 Pa or less in dynamic viscoelasticity measurement.
  • at least one peak temperature of the function tan ⁇ of the dynamic viscoelasticity measurement is in the range of 85 ° C. to 125 ° C.
  • the storage elastic modulus (E ′) at 30 ° C. in the dynamic viscoelasticity measurement is 5 ⁇ 10 8 Pa to 2.33 ⁇ 10 9 Pa and the peak of the function tan ⁇ of the dynamic viscoelasticity measurement.
  • at least one temperature exists between 90 ° C. and 125 ° C. Thereby, a foam becomes the thing excellent in the balance of hardness, elongation, and thermoformability, and becomes a thing suitable for a shoe sole.
  • the molecular weight of the component (a ′) is not particularly limited, but is preferably 30,000 to 1,000,000 in terms of polystyrene-reduced number average molecular weight in the gel permeation chromatography method (GPC method), more preferably It is 40,000 to 500,000, more preferably 50,000 to 300,000.
  • GPC method gel permeation chromatography method
  • the same material as the foam of the first embodiment described above can be used.
  • the foam of the first embodiment of the present embodiment includes the above-described component (a), component (b), component (c) and component (d) as essential components
  • the foam of the second embodiment comprises:
  • the component (a ′), the component (b), the component (c), and the component (d) described above are essential components
  • a component for the foam is prepared by adding the component (e) as necessary. It can be obtained by subjecting the foam composition to foaming / crosslinking treatment.
  • foaming is performed by raising the temperature in a predetermined mold or molding into an arbitrary shape using an extrusion molding machine, and then in a heating tank.
  • a foam can be obtained by foaming by heating.
  • foaming can be performed by performing secondary foaming after primary foaming to increase the foaming ratio.
  • the heating temperature is preferably 120 to 300 ° C., more preferably 140 to 200 ° C.
  • the heating time is preferably 3 to 120 minutes, and more preferably 5 to 60 minutes. To do.
  • crosslinking is performed simultaneously.
  • the form of crosslinking of the foam of the present embodiment is not particularly limited, and for example, sulfur crosslinking, peroxide crosslinking, or the like is applied. From the viewpoint of the cost and strength of the foam, sulfur crosslinking is preferred.
  • this foam may be blended with an appropriate amount of a silylating agent, a silane coupling agent, an anti-aging agent, a vulcanization accelerator, a crosslinking aid, a coloring agent, and the like, if necessary.
  • the specific gravity of the foam of this embodiment is 0.1 to 0.98 g / cc, preferably 0.1 to 0.95 g / cc in both the foams of the first embodiment and the second embodiment. It is.
  • the specific gravity can be measured by the method described in Examples described later. Specifically, it can be measured according to JIS K 7112.
  • a foam having a specific gravity of 0.1 to 0.7 g / cc is suitable for applications requiring characteristics such as cushioning properties, shock buffering properties, and lightness, for example, as a midsole material for sports shoes.
  • a foam having a specific gravity of 0.8 to 0.98 g / cc is suitable for applications requiring hardness, dimensional stability and mechanical strength, for example, as an outsole material for shoes.
  • the specific gravity of the foam can be controlled by adjusting (c) component: filler amount and (d) component: foaming agent amount of the blend composition.
  • the hardness measured by type C when the specific gravity is 0.1 to 0.7 g / cc, the hardness measured by type C is 45 to 98, preferably 48 to 90, more preferably. 50-85. When the specific gravity is 0.8 to 0.98 g / cc, the hardness measured with Type A is 60 to 98, preferably 63 to 90, and more preferably 65 to 85.
  • the hardness measured with Type C refers to the hardness measured with an Asker C-type hardness meter (Type C) using a plate-shaped test piece having a thickness of 12 mm.
  • the hardness measured by type A means the hardness measured based on JISK6301 spring type hardness tester A form (type A) using the plate-shaped test piece of thickness 12mm.
  • the hardness of the foam can be controlled by adjusting the composition and specific gravity of the components (a) to (d) and the components (a ′) to (d).
  • the hardness can be increased by increasing the content of component (c): filler, and the hardness can be decreased by increasing the expansion ratio by increasing the content of component (d): foaming agent.
  • the strength of the foam having a predetermined specific gravity can be controlled to the specific numerical value.
  • the foam of this embodiment is made of a shoe midsole, inner sole or outsole material, specifically men's shoes, women's shoes, casual shoes, running shoes, jogging shoes, tracking shoes, various competition shoes, and mountaineering shoes. It is useful as a sole for all footwear such as dress shoes, golf shoes, indoor shoes, slippers, beach sandals, etc., that is, a midsole, inner sole or outsole material.
  • the foam of the present embodiment may be a belt, an automobile part, a building material part, an industrial part, a toy / miscellaneous part, a sports / health part, a care product, various molded products, various sheets, films, It can also be used for other industrial products, cushioning materials, packaging materials, and the like.
  • the foam of this embodiment has excellent dimensional accuracy, durability and cushioning properties, and can also be applied to thermoformed sponges. it can.
  • the thermoformed sponge is pre-cut into a required shape and heated and pressurized in a mold heated to 100 to 150 ° C. to form a strong melt film on the outer surface of the foam. It is produced by cooling the mold and taking out the foam.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 27 parts by mass of styrene at 70 ° C. for 35 minutes. Thereafter, methanol is added in an equimolar amount to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6- 0.3 parts by mass of di-t-pentylphenyl acrylate was added to 100 parts by mass of the block copolymer. Thereafter, the solvent was removed to obtain a block copolymer A-2.
  • polymerization was performed by continuously supplying a cyclohexane solution containing 6 parts by mass of styrene and 2 parts by mass of 1,3-butadiene at 70 ° C. for 15 minutes.
  • a cyclohexane solution containing 21 parts by mass of styrene was continuously supplied at 70 ° C. for 30 minutes for polymerization.
  • ⁇ Block copolymer A-4> Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, 0.076 parts by mass of n-butyllithium and 0.3 times of tetramethylethylenediamine with respect to n-butyllithium in a cyclohexane solution containing 32 parts by mass of styrene Mole was added and polymerization was carried out by continuously supplying at 70 ° C. for 40 minutes. Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 21 parts by mass of styrene and 12 parts by mass of 1,3-butadiene at 70 ° C. for 40 minutes.
  • polymerization was performed by continuously supplying a cyclohexane solution containing 8 parts by mass of styrene and 3 parts by mass of 1,3-butadiene at 70 ° C. for 15 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 24 parts by mass of styrene at 70 ° C. for 30 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 10 parts by mass of styrene and 1.5 parts by mass of 1,3-butadiene at 70 ° C. for 15 minutes.
  • a cyclohexane solution containing 26 parts by mass of styrene was continuously supplied at 70 ° C. for 30 minutes for polymerization.
  • polymerization was performed by continuously supplying a cyclohexane solution containing 6 parts by mass of styrene and 2 parts by mass of 1,3-butadiene at 70 ° C. for 15 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 23 parts by mass of styrene at 70 ° C. for 30 minutes.
  • ⁇ Block copolymer A-7> Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 39 parts by mass of styrene, 0.054 parts by mass of n-butyllithium and tetramethylethylenediamine 0.3 times that of n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 70 ° C. for 45 minutes. Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 20 parts by mass of styrene and 2 parts by mass of 1,3-butadiene at 70 ° C. for 30 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 39 parts by mass of styrene at 70 ° C. for 45 minutes. Thereafter, methanol is added in an equimolar amount to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6- 0.3 parts by mass of di-t-pentylphenyl acrylate was added to 100 parts by mass of the block copolymer. Thereafter, the solvent was removed to obtain a block copolymer A-7.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 8 parts by mass of styrene and 2 parts by mass of 1,3-butadiene at 70 ° C. for 15 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 22 parts by mass of styrene at 70 ° C. for 30 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 57 parts by mass of styrene and 18 parts by mass of 1,3-butadiene at 70 ° C. for 80 minutes. Thereafter, methanol is added in an equimolar amount to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6- 0.3 parts by mass of di-t-pentylphenyl acrylate was added to 100 parts by mass of the block copolymer. Thereafter, the solvent was removed to obtain a block copolymer A-9.
  • a cyclohexane solution containing 47 parts by mass of styrene was continuously supplied at 70 ° C. for 55 minutes for polymerization. Thereafter, methanol is added in an equimolar amount to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6- 0.3 parts by mass of di-t-pentylphenyl acrylate was added to 100 parts by mass of the block copolymer. Thereafter, the solvent was removed to obtain a block copolymer A-10.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 12 parts by mass of styrene and 3 parts by mass of 1,3-butadiene at 70 ° C. for 20 minutes.
  • polymerization was carried out by continuously supplying a cyclohexane solution containing 22 parts by mass of styrene at 70 ° C. for 25 minutes.
  • Component (a) Structure of block copolymers A-1 to A-11, styrene content (% by mass), storage elastic modulus (E ′) at 30 ° C., and peak temperature of function tan ⁇ of dynamic viscoelasticity measurement Table 1 below shows the block ratios of styrene contained in the block copolymer.
  • Styrene content (% by mass)> It calculated from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).
  • Block ratio of styrene contained in block copolymer> A method in which a block copolymer is oxidatively decomposed with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (oxidative decomposition method: IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)
  • IM KOLTHOFF oxidative decomposition method: IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)
  • the styrene block chain component (however, the styrene block component having an average degree of polymerization of about 30 or less is excluded) is measured, the weight of the styrene block chain is measured, and the following formula is used: Asked.
  • Block ratio (% by mass) of styrene (weight of styrene block polymer chain in block copolymer / total weight of styren
  • A represents a polystyrene block
  • B represents a random copolymer block of styrene and butadiene
  • C represents a polybutadiene block.
  • the subscripts (numbers) are for distinguishing each part, and the structure may be the same or different.
  • ⁇ (9) Dimensional stability ( ⁇ )> The shrinkage after 24 hours of the sheet vulcanized and foamed with a 150 (vertical) ⁇ 150 (horizontal) ⁇ 4 mm (thickness) mold was measured. The index was calculated with Comparative Example 10 as 100. The smaller the index, the smaller the shrinkage rate and the better the dimensional stability. In addition, the shrinkage ratio after foaming in Comparative Example 10 is 1.2%.
  • Example 1 to 6 [Comparative Examples 1 to 5] Using block copolymers A-1 to A-11 of component (a), BR and SBR as component (b), silica as component (c), and blowing agent as component (d), Table 2 below shows the composition and the foam physical properties using other additives.
  • Table 2 shows the composition and the foam physical properties using other additives.
  • blending materials excluding the foaming agent and other additives were kneaded while adjusting the maximum temperature to 170 to 180 ° C. using a 1.7 L test Banbury mixer.
  • the kneaded product was kneaded by adding a foaming agent and other additives on a 10-inch roll, rolled out into a sheet, and then subjected to primary heating press molding (crosslinking, foaming) at 140 ° C.
  • the pressing conditions were appropriately adjusted so that the internal hardness of the primary molded product was 35 to 50 (type C).
  • the primary molded product produced under these conditions was subjected to secondary molding (heating press at 150 ° C. for 7 minutes, cooling for 15 minutes) at a compression rate of 30% to obtain a foam.
  • BR Polybutadiene “Nipol BR122” manufactured by Nippon Zeon Co., Ltd. 0 " SBR: Styrene-butadiene copolymer “SBR150” manufactured by KUMHO 2 " Silica: “Nipsil VN3” manufactured by Tosoh Silica Co., Ltd.
  • a foam was obtained in the same manner as in Example 1. The obtained foam had a specific gravity of 0.39 g / cc, hardness of 54, Tb of 3.0 MPa, Eb of 390%, dimensional stability of 93, and thermoformability as good as ⁇ .
  • the foams of Examples 1 to 11 were all found to be excellent in hardness, dimensional stability, thermoformability and mechanical strength.
  • a foaming agent and further using other additives, and their blending composition and foam physical properties are shown in Table 4 below.
  • Table 4 blending compositions shown in Table 4 below, blending materials excluding the foaming agent and other additives were kneaded by adjusting the maximum temperature to 170 to 180 ° C. using a 1.7 L test Banbury mixer.
  • this kneaded product is kneaded by adding a foaming agent and other additives on a 10-inch roll, and after rolling it into a sheet, it is placed in a mold and vulcanized (sulfur crosslinking) and foamed. A foam was obtained. Vulcanization was performed at 160 ° C. for 10 minutes.
  • BR cis 1,4 polybutadiene
  • BR-1 manufactured by Nippon Synthetic Rubber Co., Ltd. 8
  • S-SBR Styrene-butadiene copolymer (Asaprene 303 manufactured by Asahi Kasei Chemicals Corporation)
  • Silica “Nipsil VN3” manufactured by Tosoh Silica Co., Ltd.
  • Other additives Polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name “PEG # 4000”) 1 part by mass Zinc oxide 3 parts by mass Stearic acid (Asahi Denka Co., Ltd.) 1 part by mass Titanium oxide (anatase) Type) 4 parts by mass Foaming aid (urea derivative, Sankyo Kasei Co., Ltd., trade name “Selton NF”) 1 part by mass DCP (98% dicumyl peroxide, Nippon Oil & Fats Co., Ltd.) Product name "Park Mill D” 0.05 parts by mass Sulfur 0.05 parts by mass
  • Example 18 to 21 [Comparative Examples 15 to 18] As shown in Table 5 below, the type and amount of component (a) and the amounts of components (b), (c) and (d) were changed, and a foam was obtained in the same manner as in Example 12 described above. . The details of symbols and the like in Table 5 are the same as those in Table 4, and the physical properties are measured in the same manner as described above.
  • the foams of Examples 12 to 22 were all found to be excellent in hardness, dimensional stability, and mechanical strength.
  • the foam of the present invention is suitable for a midsole for shoes, an inner sole or an outsole material, and specifically, industrial use as a sole material for general footwear such as men's shoes, women's shoes, and casual shoes. It has a possibility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention permet d'obtenir une mousse appropriée pour une semelle intermédiaire, interne ou externe de chaussure, ou similaire, et qui se révèle excellente en termes de dureté, de stabilité dimensionnelle, d'aptitude au formage thermique, et de résistance mécanique. Plus précisément, l'invention concerne une mousse qui contient : (a) un copolymère séquencé dans lequel un hydrocarbure aromatique de vinyle représente 65 à 95% en masse, un diène conjugué représente 5 à 35% en masse, le rapport de séquence de copolymère d'hydrocarbure aromatique de vinyle représente 40 à 98% en masse, le module d'élasticité de stockage (E') à 30℃ pour une mesure de viscoélasticité dynamique est supérieur ou égal à 3×108Pa et inférieur ou égal à 2,35×109Pa, et qui présente à une température supérieure ou égale à 85℃ et inférieure ou égale à 125℃ une ou plusieurs températures de pic de fonction tanδ de mesure de viscoélasticité dynamique; (b) un caoutchouc à base d'isoprène et/ou un caoutchouc à base de diène; (c) une charge; et (d) un agent moussant. Le rapport massique composant (a) / composant (b) satisfait 1 à 30 / 70 à 99. Le poids spécifique avec une composition pour mousse réticulée comprenant 1 à 100 parties en masse de composant (c) et 0,1 à 30 parties en masse de composant (d) pour 100 parties en masse de la somme des composants (a) et (b), satisfait 0,1 à 0,98g/cc.
PCT/JP2011/068631 2010-08-23 2011-08-17 Mousse, et composition pour mousse WO2012026376A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180037240.3A CN103038275B (zh) 2010-08-23 2011-08-17 发泡体和发泡体用组合物
KR1020137002495A KR101500248B1 (ko) 2010-08-23 2011-08-17 발포체 및 발포체용 조성물

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010-186369 2010-08-23
JP2010186369A JP5597478B2 (ja) 2010-08-23 2010-08-23 発泡体
JP2010-186441 2010-08-23
JP2010186441A JP5597479B2 (ja) 2010-08-23 2010-08-23 発泡体

Publications (1)

Publication Number Publication Date
WO2012026376A1 true WO2012026376A1 (fr) 2012-03-01

Family

ID=45723378

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/068631 WO2012026376A1 (fr) 2010-08-23 2011-08-17 Mousse, et composition pour mousse

Country Status (4)

Country Link
KR (1) KR101500248B1 (fr)
CN (1) CN103038275B (fr)
TW (1) TWI441861B (fr)
WO (1) WO2012026376A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106589499A (zh) * 2016-11-22 2017-04-26 茂泰(福建)鞋材有限公司 一种抗油滑安全鞋橡胶鞋底及其制备方法
JP2017185771A (ja) * 2016-03-30 2017-10-12 積水化成品工業株式会社 車両用内装材
CN106832470B (zh) * 2017-01-06 2018-10-02 茂泰(福建)鞋材有限公司 一种防滑橡胶鞋底及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018025332A1 (fr) * 2016-08-02 2018-02-08 株式会社タイカ Composition amortisseuse de chocs pour chaussures, et élément amortisseur de chocs pour chaussures
WO2018033962A1 (fr) * 2016-08-16 2018-02-22 株式会社アシックス Semelles extérieures et chaussures
US20230093459A1 (en) * 2021-01-28 2023-03-23 Asics Corporation Injection molded article and shoe

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0859764A (ja) * 1994-08-23 1996-03-05 Bridgestone Corp ブロック共重合体
WO2008102761A1 (fr) * 2007-02-20 2008-08-28 Asahi Kasei Chemicals Corporation Composition d'absorption de choc
JP2008534702A (ja) * 2005-03-24 2008-08-28 クレイトン・ポリマーズ・リサーチ・ベー・ベー 発泡性熱可塑性ゲル組成物
WO2010073589A1 (fr) * 2008-12-22 2010-07-01 旭化成ケミカルズ株式会社 Composition réticulable et moussable, objet moussé réticulé et semelle intercalaire de chaussure le comprenant
JP2010163492A (ja) * 2009-01-13 2010-07-29 Asahi Kasei Chemicals Corp 架橋発泡用組成物及び架橋発泡体、並びにそれを用いた履物及び積層体

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040077789A1 (en) * 2002-01-10 2004-04-22 Keiichi Toda Block copolymer
CN104086900B (zh) * 2004-11-25 2016-10-26 三井化学株式会社 丙烯系树脂组合物及其用途

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0859764A (ja) * 1994-08-23 1996-03-05 Bridgestone Corp ブロック共重合体
JP2008534702A (ja) * 2005-03-24 2008-08-28 クレイトン・ポリマーズ・リサーチ・ベー・ベー 発泡性熱可塑性ゲル組成物
WO2008102761A1 (fr) * 2007-02-20 2008-08-28 Asahi Kasei Chemicals Corporation Composition d'absorption de choc
WO2010073589A1 (fr) * 2008-12-22 2010-07-01 旭化成ケミカルズ株式会社 Composition réticulable et moussable, objet moussé réticulé et semelle intercalaire de chaussure le comprenant
JP2010163492A (ja) * 2009-01-13 2010-07-29 Asahi Kasei Chemicals Corp 架橋発泡用組成物及び架橋発泡体、並びにそれを用いた履物及び積層体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017185771A (ja) * 2016-03-30 2017-10-12 積水化成品工業株式会社 車両用内装材
CN106589499A (zh) * 2016-11-22 2017-04-26 茂泰(福建)鞋材有限公司 一种抗油滑安全鞋橡胶鞋底及其制备方法
CN106589499B (zh) * 2016-11-22 2018-07-03 茂泰(福建)鞋材有限公司 一种抗油滑安全鞋橡胶鞋底及其制备方法
CN106832470B (zh) * 2017-01-06 2018-10-02 茂泰(福建)鞋材有限公司 一种防滑橡胶鞋底及其制备方法

Also Published As

Publication number Publication date
KR101500248B1 (ko) 2015-03-06
KR20130100094A (ko) 2013-09-09
CN103038275A (zh) 2013-04-10
CN103038275B (zh) 2014-07-09
TWI441861B (zh) 2014-06-21
TW201213426A (en) 2012-04-01

Similar Documents

Publication Publication Date Title
TWI441861B (zh) Foaming and foaming compositions
JP5597478B2 (ja) 発泡体
JP5142406B2 (ja) 衝撃吸収体組成物
WO2006054531A1 (fr) Procédé de fabrication de mousse moulée réticulée
WO2004003027A1 (fr) Copolymere hydrogene et composition sur la base de celle-ci
JP5394757B2 (ja) 架橋発泡用組成物及び架橋発泡体、並びにそれを用いた履物及び積層体
JP2003506550A (ja) 動的に加硫されたｔｐｕ／非極性ゴム配合物から得られる熱可塑性加硫ゴム
JP2019131795A (ja) 高分子重合体組成物
WO2002014423A1 (fr) Composition polymere
JP5597479B2 (ja) 発泡体
KR100642705B1 (ko) 수소 첨가 공중합체를 함유하는 중합체 발포체
JP2002363344A (ja) 靴底用架橋性重合体組成物および靴底
JP2006016518A (ja) 発泡体用組成物
JP2004346139A (ja) 熱可塑性重合体組成物およびその成形品
JP5634025B2 (ja) 架橋用組成物、架橋体及び架橋発泡体、並びにそれを用いた履物及び積層体
JP2005255856A (ja) 水添ジエン系共重合体及びその製造方法
JP2005002187A (ja) 貫通孔を有する押出シート、および吸音性マット、ならびにそれらの製造方法
JP2005008836A (ja) 重合体（組成物）および靴底
JP7039651B2 (ja) 靴底用ゴム発泡体
JP2005126657A (ja) 水添ジエン系共重合体、重合体組成物、及び該重合体組成物を用いた成形体
TWI637025B (zh) 熱塑性動態硫化彈性體之組成物及其製備方法與產品
JP2005007750A (ja) 吸音性マットの製造方法、および吸音性マット
EP2220159A1 (fr) Compositions thermoplastiques pour chaussures sans caractéristiques de marquage
JP2006063183A (ja) 熱可塑性重合体組成物
JPH0474375B2 (fr)

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180037240.3

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11819839

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20137002495

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11819839

Country of ref document: EP

Kind code of ref document: A1