WO2018230299A1 - Composition d'asphalte - Google Patents

Composition d'asphalte Download PDF

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Publication number
WO2018230299A1
WO2018230299A1 PCT/JP2018/020039 JP2018020039W WO2018230299A1 WO 2018230299 A1 WO2018230299 A1 WO 2018230299A1 JP 2018020039 W JP2018020039 W JP 2018020039W WO 2018230299 A1 WO2018230299 A1 WO 2018230299A1
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Prior art keywords
mass
copolymer
asphalt composition
asphalt
group
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PCT/JP2018/020039
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English (en)
Japanese (ja)
Inventor
隆行 城本
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旭化成株式会社
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Priority to JP2019525262A priority Critical patent/JP6776449B2/ja
Publication of WO2018230299A1 publication Critical patent/WO2018230299A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the present invention relates to an asphalt composition.
  • asphalt compositions have been widely used for road pavement, waterproof sheets, sound insulation sheets, roofing and the like.
  • asphalt composition is used for various purposes, many attempts have been made to add various polymers to the asphalt to improve its properties.
  • the polymer include an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a rubber latex, and a block copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon.
  • Patent Document 1 has a problem in that the low temperature physical properties are poor and the additive is not uniformly dissolved in asphalt, so that the high temperature storage stability may be deteriorated. Yes.
  • the technique described in Patent Document 2 has a problem that the balance between low-temperature physical properties and various characteristics is poor.
  • the technique described in Patent Document 3 has a problem that as the amount of the additive increases, the viscosity of the asphalt composition increases and the processability is inferior.
  • an object of the present invention is to provide an asphalt composition which is excellent in viscosity, low temperature physical properties, copolymer and polyphenylene ether solubility in asphalt, and excellent in high temperature physical properties.
  • the present inventors have found that a copolymer having a vinyl aromatic monomer unit and a conjugated diene monomer unit, and a predetermined reduced viscosity. It has been found that asphalt compositions containing a predetermined amount of polyphenylene ether and asphalt can solve the above-mentioned problems of the prior art, and the present invention has been completed. That is, the present invention is as follows.
  • the content of (a) is 2.5 to 14% by mass,
  • the content of (b) is 0.1 to 10% by mass,
  • the content of (c) is 80 to 97% by mass, An asphalt composition.
  • the polyphenylene ether (b) is It consists of at least one functional group selected from the group consisting of a carboxyl group and / or a group derived from a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group.
  • the content of (a) is 4 to 14% by mass, The content of (b) is 0.1 to 8% by mass, The content of (c) is 80 to 97% by mass, The asphalt composition according to any one of [1] to [3].
  • the content of (a) is 4 to 12% by mass, The content of (b) is 0.1 to 5% by mass, The content of (c) is 85 to 97% by mass, The asphalt composition according to any one of [1] to [4].
  • thermoplastic resin composition (d) has a sea-island structure composed of a sea phase composed of the copolymer (a) and an island phase composed of the polyphenylene ether (b),
  • the content of (d) is 3 to 15% by mass
  • the content of (c) is 85 to 97% by mass
  • thermoplastic resin composition (d) contains an antioxidant.
  • copolymer (a) having the vinyl aromatic monomer unit and the conjugated diene monomer unit is hydrogenated.
  • SBS styrene-butadiene-styrene copolymer
  • an asphalt composition excellent in high-temperature physical properties and excellent in viscosity, low-temperature physical properties, copolymer and polyphenylene ether solubility in asphalt it is possible to obtain an asphalt composition excellent in high-temperature physical properties and excellent in viscosity, low-temperature physical properties, copolymer and polyphenylene ether solubility in asphalt.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
  • the present invention can be implemented with various modifications within the scope of the gist.
  • Asphalt composition of this embodiment A copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit; Polyphenylene ether (b) having a reduced viscosity of 0.07 dL / g to 0.60 dL / g; Asphalt (c), Containing,
  • the content of (a) is 2.5 to 14% by mass,
  • the content of (b) is 0.1 to 10% by mass,
  • the content of (c) is 80 to 97% by mass.
  • the structural unit constituting the copolymer is referred to as “ ⁇ monomer unit”, and when describing as a polymer material, “unit” is omitted, and simply described as “ ⁇ monomer”. .
  • the asphalt composition of this embodiment is a copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit (hereinafter referred to as copolymer (a), component (a)). There is. ).
  • the copolymer (a) may be either a random copolymer or a block copolymer, both of which are preferred forms.
  • a block copolymer having a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units can be mentioned as a preferred embodiment.
  • Other monomer units may be included as long as the object of the present embodiment is not impaired.
  • “mainly” means that the content of a predetermined monomer unit in the block is 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Say something. Although there is no restriction
  • the asphalt composition of the present embodiment contains 2.5 to 14% by mass of the copolymer (a), so that it has excellent high-temperature properties, and the viscosity, low-temperature performance, and copolymer of the asphalt composition.
  • the properties of (a) solubility in asphalt are excellent, and the balance of these properties is excellent. From the viewpoint described above, the content of the copolymer (a) in the asphalt composition of the present embodiment is preferably 4 to 14% by mass, more preferably 4 to 12% by mass.
  • the copolymer (a) has a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units, as described above.
  • the block copolymer (hereinafter sometimes referred to as a block copolymer (a)) is a preferred form. Further, in addition to this, a copolymer block comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit may be included.
  • the block copolymer (a) preferably contains at least one block copolymer selected from the group consisting of the following formulas (i) to (xii).
  • S represents a polymer block mainly composed of vinyl aromatic monomer units
  • B represents a polymer block mainly composed of conjugated diene monomer units
  • R represents a copolymer block composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit
  • X represents a residue of a coupling initiator or a residue of a polymerization initiator such as polyfunctional organolithium.
  • M is an integer from 2 to 6
  • n and k are each independently an integer from 1 to 4.
  • the values of m, n and k in (i) to (vi) may be the same or different.
  • structures such as molecular weight and composition may be the same or different.
  • X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium, From the viewpoint of controlling the molecular weight of the block, X is preferably a coupling residue.
  • the coupling agent is not limited to the following, for example, silicon tetrachloride, tin tetrachloride, epoxy compounds, polyhalogenated hydrocarbon compounds, carboxylic acid ester compounds, polyvinyl compounds, alkoxysilane compounds, halogenated Examples include silane compounds and ester compounds.
  • the coupling agent is preferably an alkoxysilane compound or an epoxy compound, and more preferably an epoxy compound. preferable.
  • alkoxysilane compounds include, but are not limited to, for example, tetraalkoxysilane compounds such as tetramethoxysilane and the like; tetraaroxysilane compounds such as tetraphenoxysilane and the like; methyltriethoxysilane and the like Alkylalkoxysilane compounds having two or more alkoxy groups such as the same; alkyltrioxysilane compounds having two or more aryloxy groups such as methyltriphenoxysilane and the like; vinyltrimethoxysilane And alkenylalkoxysilane compounds having two or more alkoxy groups such as the same; and halogenoalkoxysilane compounds such as trimethoxychlorosilane and the like It is. Of these, alkylalkoxysilanes having 2 to 4 alkoxy groups are preferred from the viewpoints of heat deterioration resistance and the productivity of the block copolymer (a).
  • epoxy compounds include, but are not limited to, polyepoxidized vegetable oils such as epoxidized soybean oil or epoxidized linseed oil; epoxidized polybutadiene, epoxidized tetraallyl ether pentaerythritol, epoxy compounds having a phenyl group, and the like. Can be mentioned. In these, the epoxy compound which has a phenyl group from a viewpoint of heat-resistant deterioration and the manufacture property of a block copolymer is preferable.
  • the number of alkoxysilyl groups or epoxy groups in the alkoxysilane compound or epoxy compound is such that the mixing temperature of the asphalt composition of the present embodiment is low, the viscosity of the asphalt composition is low, and the copolymer (a) in the asphalt composition is small. From the viewpoint of deterioration and high peeling resistance of the aggregate when it is made into a mixture of the asphalt composition and the aggregate, 2 to 5 is preferable per molecule, and 2 to 4 is more preferable.
  • the copolymer (a) used in the asphalt composition of the present embodiment includes a high temperature physical property of the asphalt composition, a low viscosity of the asphalt composition, a low temperature physical property of the asphalt composition, and a polyphenylene ether (b) and a copolymer (a ) From the viewpoint of solubility in asphalt, [(SB) k ] m -X (m is an integer of 2 to 4, k is an integer of 1 to 4, and S is a vinyl aromatic monomer.
  • B is a polymer block mainly comprising a conjugated diene monomer unit
  • X is a residue of a coupling agent or a residue of a polymerization initiator).
  • B is a polymer block mainly composed of a conjugated diene monomer unit.
  • R is a copolymer block composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit
  • X is a residue of a coupling agent or a residue of a polymerization initiator. It is preferable to contain the block copolymer which has.
  • the weight average molecular weight (Mw) of the copolymer (a) used in the asphalt composition of this embodiment is high as the softening point of the asphalt composition, and high peeling of the aggregate when the asphalt composition and the aggregate are mixed. From the viewpoint of resistance, it is preferably 40,000 or more, more preferably 60,000 or more, and even more preferably 100,000 or more. Further, from the viewpoint of the low viscosity of the asphalt composition and the small deterioration of the copolymer (a) in the asphalt composition, it is preferably 400,000 or less, more preferably 350,000 or less, and 300,000 or less. More preferably it is.
  • the weight average molecular weight of a copolymer (a) can be calculated
  • the content of the vinyl aromatic monomer unit in the copolymer (a) used in the asphalt composition of the present embodiment is a high softening point of the asphalt composition, and a mixture of the asphalt composition and the aggregate. From the viewpoint of high peeling resistance of the aggregate, it is preferably 10% by mass or more, more preferably 14% by mass or more, further preferably 20% by mass or more, and further more preferably 25% by mass or more. Further, from the viewpoint of low viscosity of the asphalt composition, little deterioration of the copolymer (a), and flexibility of the asphalt composition, it is preferably 60% by mass or less, more preferably 55% by mass or less, and 52% by mass. The following is more preferable, and 45% by mass or less is even more preferable.
  • the content of the vinyl aromatic monomer unit in the copolymer (a) refers to the content of the vinyl aromatic monomer unit as the entire copolymer (a).
  • the copolymer (a) there are a plurality of components, that is, when the copolymer (a) is a mixture of a plurality of types of copolymers, the vinyl aromatic monomer unit of each copolymer When the contents are different, it is the average value of the contents of the respective vinyl aromatic monomer units.
  • content of the vinyl aromatic monomer unit in a copolymer (a) can be measured by the method as described in the Example mentioned later.
  • the vinyl aromatic monomer unit is included in the coalesced block in an amount of 80% by mass to 100% by mass.
  • the copolymer (a) is preferably 50% by mass or less, more preferably 45% by mass or less, It is further preferably 40% by mass or less, and further preferably 35% by mass or less.
  • the content of the polymer block mainly composed of the vinyl aromatic monomer unit in the copolymer (a) is described in the examples described later, and the vinyl aromatic monomer in the block copolymer. It can be measured by a method for measuring the body block content.
  • the copolymer (a) used in the asphalt composition of the present embodiment has a high softening point of the asphalt composition, high heat deterioration resistance of the copolymer (a), and extrusion blending with polyphenylene ether (b) described later. From the viewpoint of thermal deterioration with little, it is preferable that the double bond contained in the conjugated diene monomer unit in the copolymer (a) is hydrogenated.
  • Double bond water contained in the conjugated diene monomer unit from the viewpoint of high softening point of asphalt composition, high heat deterioration resistance during storage, and low thermal deterioration during extrusion blending with polyphenylene ether (b)
  • the addition rate is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more.
  • the hydrogenation rate of the double bond amount contained in the conjugated diene monomer unit is preferably 90 mol% or less, more preferably 75 mol% or less, and more preferably 60 mol% or less from the viewpoint of high compatibility with asphalt. Further preferred.
  • the conjugated diene monomer unit does not have the conjugated diene by hydrogenation, but is referred to as “conjugated diene monomer unit” in the present specification regardless of before and after hydrogenation.
  • the hydrogenation rate of the double bond amount can be adjusted by controlling the hydrogenation amount and the hydrogenation reaction time in the hydrogenation step. Moreover, in this embodiment, a hydrogenation rate can be calculated
  • the amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation of the copolymer (a) used in the asphalt composition of the present embodiment is from the viewpoint of high compatibility with asphalt and low viscosity of the asphalt composition. 8 mol% or more, preferably 10 mol% or more, more preferably 12 mol% or more.
  • the vinyl bond amount in the conjugated diene monomer unit before hydrogenation of the copolymer (a) is preferably 45 mol% or less from the viewpoint of less deterioration of the copolymer (a) in the asphalt composition, 40 mol% or less is more preferable, 30 mol% or less is more preferable, and 25 mol% or less is even more preferable.
  • the melt flow rate (MFR, 200 ° C., 5 kgf) of the copolymer (a) used in the asphalt composition of the present embodiment is the productivity of the copolymer (a), during extrusion blending with the polyphenylene ether (b) From the viewpoint of low thermal deterioration, it is preferably 0.01 g / 10 min or more, more preferably 0.2 g / 10 min or more, further preferably 1.0 g / 10 min or more, and further preferably 3 g / 10 min or more. More preferred.
  • 100 g / 10 min or less is preferable, 50 g / 10 min or less is more preferable, and 30 g / 10 min or less is more preferable.
  • the copolymer (a) contains a modifying group composed of a functional group (a modified copolymer having a modifying group composed of a functional group) from the viewpoint of excellent separability of the asphalt composition and interaction with asphalt and / or aggregate. It is preferably a polymer.
  • the functional group include, but are not limited to, at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group. It is done. It is preferable that a modifying group comprising these functional groups is added to the copolymer (a).
  • the method for adding a modifying group comprising a functional group is not limited to the following, but for example, a block copolymer may be used.
  • the copolymer (a) used in the asphalt composition of the present embodiment is obtained by polymerizing at least a conjugated diene monomer and a vinyl aromatic monomer using, for example, a lithium compound as a polymerization initiator in a hydrocarbon solvent.
  • a solvent removal step for removing the solvent can be sequentially performed for production.
  • a polymer is obtained by polymerizing a monomer containing at least a conjugated diene monomer and a vinyl aromatic monomer in a hydrocarbon solvent using a lithium compound as a polymerization initiator.
  • the hydrocarbon solvent used in the polymerization step is not limited to the following, but examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. And alicyclic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. These may be used alone or in combination of two or more.
  • Examples of the lithium compound used as a polymerization initiator in the polymerization step include, but are not limited to, for example, a compound in which one or more lithium atoms are bonded in a molecule such as an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound. It is done.
  • Examples of such an organic lithium compound include, but are not limited to, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadiene
  • Examples include enildilithium and isoprenyldilithium. These may be used alone or in combination of two or more.
  • conjugated diene monomer examples include, but are not limited to, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3 -Diolefins having a pair of conjugated double bonds such as pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc.
  • 1,3-butadiene and isoprene are preferable from the viewpoint of economy. From the viewpoint of mechanical strength, 1,3-butadiene is more preferable. These may be used individually by 1 type and may use 2 or more types together.
  • vinyl aromatic monomer examples include, but are not limited to, styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene. And vinyl aromatic compounds such as N, N-diethyl-p-aminoethylstyrene. Among these, styrene is preferable from the viewpoint of economy. These may be used alone or in combination of two or more.
  • conjugated diene monomer and vinyl aromatic monomer In addition to the conjugated diene monomer and vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and vinyl aromatic monomer can also be used.
  • polar compounds and randomizing agents include, but are not limited to, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; amines such as triethylamine and tetramethylethylenediamine; thioethers, phosphines, phosphoramides, alkylbenzenes Examples thereof include sulfonates, potassium and sodium alkoxides, and the like.
  • the polymerization method is not particularly limited, and a known method can be applied.
  • Known methods include, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, and Japanese Patent Publication No. Sho. Examples thereof include the methods described in JP-A-48-4106, JP-B-56-28925, JP-A-59-166518, JP-A-60-186777, and the like.
  • ⁇ Deactivation process> In the manufacturing method of a copolymer (a), it is preferable to deactivate the active terminal of a copolymer by performing a deactivation process after a superposition
  • Examples of the method of deactivating the active terminal of the copolymer include a method of reacting with a compound having an active terminal and active hydrogen. Although it does not specifically limit as a compound which has active hydrogen, From an economical viewpoint, alcohol and water are preferable.
  • the hydrogenation step is a step in which a hydrogenation reaction is performed on a part of the double bond in the conjugated diene monomer unit of the copolymer obtained in the polymerization step in the presence of a predetermined catalyst.
  • the catalyst used in the hydrogenation reaction is not limited to the following, but, for example, a supported heterogeneous system in which a metal such as Ni, Pt, Pd, or Ru is supported on a support such as carbon, silica, alumina, or diatomaceous earth.
  • Catalyst So-called Ziegler type catalyst using organic salt such as Ni, Co, Fe, Cr or the like and acetylacetone salt and reducing agent such as organic Al; so-called organic complex catalyst such as organometallic compound such as Ru and Rh, or titanocene compound
  • organic complex catalyst such as organometallic compound such as Ru and Rh, or titanocene compound
  • a homogeneous catalyst using organic Li, organic Al, organic Mg or the like as the reducing agent can be mentioned.
  • a homogeneous catalyst system using organic Li, organic Al, organic Mg or the like as a reducing agent in a titanocene compound is preferable from the viewpoints of economy, heat aging resistance of the polymer, or weather resistance.
  • the hydrogenation method is not limited to the following, but for example, the method described in JP-B-42-8704 and JP-B-43-6636, preferably JP-B-63-4841 and JP-B-63- The method described in 5401 gazette is mentioned.
  • hydrogenated block copolymer solution can be obtained by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent.
  • any of a batch process, a continuous process, or a combination thereof can be used.
  • the hydrogenation reaction is not particularly limited, but is preferably performed after the above-described step of deactivating the active terminal of the copolymer from the viewpoint of high hydrogenation activity.
  • the conjugated bond of the vinyl aromatic monomer unit may be hydrogenated.
  • the hydrogenation rate of the conjugated bond in all vinyl aromatic monomer units is preferably 30 mol% or less, more preferably 10 mol% or less, and further preferably 3 mol% or less.
  • the lower limit of the hydrogenation rate of the conjugated bond in the all vinyl aromatic monomer is not particularly limited, but is preferably a value higher than 0 mol%, more preferably 1 mol% or more.
  • the solvent removal step is a step of removing the solvent of the solution containing the copolymer (a).
  • the solvent removal method is not particularly limited, and examples thereof include a steam stripping method and a direct solvent removal method.
  • the amount of residual solvent in the copolymer obtained by the solvent removal step is preferably 2% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.01 mass% or less.
  • the lower limit of the residual solvent amount in the copolymer is not particularly limited, but it is preferably less, and preferably 0% by mass, but is usually 0.01% by mass from the viewpoint of economy at the time of solvent removal. It is the range of 0.1 mass% or less.
  • an antioxidant to the copolymer (a).
  • the antioxidant include, but are not limited to, phenolic antioxidants such as radical scavengers, phosphorus antioxidants such as peroxide decomposers, and sulfur antioxidants. Moreover, you may use the antioxidant which has both performances together. These may be used alone or in combination of two or more.
  • the antioxidants it is preferable to add at least a phenolic antioxidant from the viewpoint of heat aging resistance and suppression of gelation of the copolymer (a) and the asphalt composition of the present embodiment.
  • the addition amount of the phenolic antioxidant is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the copolymer (a), from the viewpoint of high low-temperature productivity and less deterioration of the copolymer during mixing. 0.10 parts by mass or more is more preferable, and 0.20 parts by mass or more is more preferable.
  • the addition amount of the phenolic antioxidant is preferably 1 part by mass or less with respect to 100 parts by mass of the copolymer (a), from the viewpoint of high peeling resistance and economic efficiency of the aggregate, and 0.5 mass. Part or less is more preferable, 0.4 part by weight or less is more preferable, and 0.3 part by weight or less is even more preferable.
  • a deashing step for removing the metal in the copolymer (a) and adjusting the pH of the polymer before the solvent removal step For example, an acid addition or carbon dioxide addition may be performed.
  • the asphalt composition of the present embodiment is excellent in the high temperature physical properties of the asphalt composition, the viscosity of the asphalt composition, the low temperature performance, the solubility of the copolymer (a) in asphalt, and the balance of these properties. From this point of view, 0.1 to 0.1 of polyphenylene ether (b) having a reduced viscosity of 0.07 dL / g to 0.60 dL / g (hereinafter sometimes referred to as polyphenylene ether (b) or (b) component). Contains 10% by mass.
  • the content of the polyphenylene ether (b) is preferably 0.1 to 8% by mass, and more preferably 0.1 to 5% by mass.
  • the polyphenylene ether (b) generally has a high glass transition point, greatly contributes to performance even in a small amount, and is considered to have an improving effect even when the addition amount is 0.1% by mass.
  • 10 mass% is set as the upper limit.
  • the polyphenylene ether (b) may be either one having a functional group (having a modified group comprising a functional group) or one having no functional group (having no modified group comprising a functional group). .
  • polyphenylene ether (b) examples include the following (1) to (3).
  • Polycarboxyl ether (b-2) having a carboxyl group and / or a group derived from a carboxyl group as a modifying group comprising a functional group is included.
  • the polyphenylene ether (b) used in the asphalt composition of the present embodiment has a reduced viscosity of 0.07 dL / g to 0.60 dL / g, and from the viewpoint of a high softening point of the asphalt composition, 0.07 dL / g or more. 0.15 dL / g or more is preferable, 0.20 dL / g or more is more preferable, and 0.30 dL / g or more is more preferable.
  • the asphalt composition and solubility of the polyphenylene ether (b) in asphalt it is 0.60 dL / g or less, preferably 0.55 dL / g or less, and 0.50 dL / g. The following is more preferable, and 0.40 dL / g or less is more preferable.
  • the reduced viscosity of polyphenylene ether (b) can be measured by the method as described in the Example mentioned later. Further, the reduced viscosity of the polyphenylene ether (b) can be controlled within the above numerical range by adjusting the molecular weight.
  • the functional group-modified polyphenylene ether (b-2) having a carboxyl group and / or a group derived from a carboxyl group includes a polyphenylene ether (b-1) having no modified group consisting of a functional group and an unsaturated carboxylic acid. It can be obtained by reacting an acid or its derivative (F).
  • the amount of the unsaturated carboxylic acid or derivative (F) added to the polyphenylene ether (b-1) having no functional group-modified group is 100% by mass of the polyphenylene ether (b-1). 0.01 to 10% by mass is preferable.
  • the reaction conditions are not limited to the following.
  • the reaction is carried out in the molten state, in the solution state or in the slurry state in the presence or absence of a radical generator, at a temperature of 80 to 350 ° C. can do.
  • the addition amount may be appropriately set according to the purpose. If the addition amount is small, a mixture of a polyphenylene ether having a modifying group made of a functional group and a polyphenylene ether not having the functional group can be obtained.
  • the unsaturated carboxylic acid or derivative (F) is not limited to the following, and examples thereof include maleic acid, fumaric acid, citraconic acid, mesaconic acid, aconitic acid, itaconic acid, cis-4-cyclohexene-1 , 2-dicarboxylic acid, chloromaleic acid, etc., unsaturated carboxylic acid, maleic anhydride, citraconic anhydride, aconitic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, chloro Acid anhydrides such as maleic anhydride, ester compounds such as monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, etc.
  • maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and maleic anhydride are preferable, and maleic acid and maleic anhydride are more preferable.
  • maleic acid or maleic anhydride is selected as the unsaturated carboxylic acid or derivative thereof (F), it is contained in the polyphenylene ether (b-2) having a modifying group consisting of a functional group and the asphalt composition of this embodiment. It is thought that the compatibility as a composition increases by interaction with other polar components.
  • Unsaturated carboxylic acid or its derivative (F) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a modified group comprising at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group is introduced into the polyphenylene ether (b).
  • a method to do although it is not limited to the following, For example, the method etc. which couple
  • the polyphenylene ether (b) used in the asphalt composition of the present embodiment is more preferably a polyphenylene ether having a modifying group composed of a functional group from the viewpoint of separability of the asphalt composition, low temperature performance, and resistance to digging of the asphalt mixture. .
  • the reason why the resistance to digging is improved by adopting a polyphenylene ether having a modifying group consisting of a functional group as the polyphenylene ether (b) is composed of aggregate (stone) which is a polar material and a functional group of polyphenylene ether. It is considered that the position of the aggregate is fixed in the asphalt composition due to the interaction with the modifying group, so that digging is less likely to occur.
  • the copolymer (a) and the polyphenylene ether (b) may be added independently, or the copolymer (a) and the polyphenylene ether (b).
  • a pellet of the thermoplastic resin composition (d) is prepared by extrusion molding blending the copolymer (a) and the polyphenylene ether (b), and added. Further, from the viewpoint of the solubility of polyphenylene ether (b) in asphalt and the low-temperature properties of the asphalt composition, the copolymer (a) and the pellets of the thermoplastic resin composition (d) described above are respectively provided. It is preferable to add.
  • the polyphenylene ether (b) can be finely dispersed in the pellets of the thermoplastic resin composition (d).
  • the polyphenylene ether (b) is finely dispersed in advance, so that the solubility of the polyphenylene ether (b) tends to be improved.
  • a method of extrusion molding blending the copolymer (a) and the polyphenylene ether (b) a method of melt kneading using a twin screw extruder (“PCM-30” manufactured by Ikekai Co., Ltd.) can be mentioned.
  • the cylinder temperature is preferably set as appropriate depending on the type of the copolymer (a)
  • the screw rotation speed can be set to 150 rotations / minute
  • the discharge rate can be set to 7 kg / h, for example.
  • Residual volatilization can be removed by providing an opening (vent) in the cylinder block and suctioning under reduced pressure.
  • the degree of pressure reduction is preferably ⁇ 0.05 MPa-G or less, more preferably ⁇ 0.07 MPa-G or less, further preferably ⁇ 0.08 MPa-G or less, and further preferably ⁇ 0.09 MPa-G or less.
  • “G” indicates the gauge pressure when the atmospheric pressure is zero.
  • the strand extruded from the die can be cooled and continuously cut with a cutter to obtain pellets. Although the size of the pellet depends on the specific application, it can be, for example, about 3 mm long ⁇ 3 mm diameter.
  • the cylinder temperature is preferably set to 250 ° C. on the upstream side to 300 ° C.
  • coalescence (a) is not hydrogenated, it is preferably set to 250 ° C. from the upstream side to 250 ° C.
  • the thermoplastic resin composition (d) has a sea-island structure composed of a sea phase composed of the copolymer (a) and an island phase composed of the polyphenylene ether (b).
  • the polyphenylene ether (b) can be uniformly dispersed and / or compatible with the copolymer (a).
  • the state in which polyphenylene ether is uniformly dispersed means a state in which polyphenylene ether aggregates having a particle diameter of 50 ⁇ m or more are contained in less than 5% by volume of the total polyphenylene ether.
  • the state in which polyphenylene ether is compatible means a state in which the average dispersed particle size of polyphenylene ether is less than 5 ⁇ m.
  • the state of uniform dispersion and compatibility of the polyphenylene ether (b) with respect to the copolymer (a) can be easily confirmed using a transmission electron microscope (TEM) or the like. Specifically, from a molded piece of the thermoplastic resin composition (d), a test piece for length 10 mm ⁇ width 5 mm ⁇ thickness 3 to 4 mm is cut out, and a slice is cut out at the end of the test piece for dyeing with an ultramicrotome. Create a flat surface.
  • TEM transmission electron microscope
  • the copolymer (a) “a block containing a polymer block mainly composed of at least one vinyl aromatic monomer and a polymer block mainly composed of at least one conjugated diene monomer”
  • a non-block copolymer comprising “a polymer block mainly composed of at least one vinyl aromatic monomer and a polymer block mainly composed of at least one conjugated diene monomer”.
  • "Hydrogenated product” and / or “Non-hydrogenated product of copolymer block comprising at least one vinyl aromatic monomer and at least one conjugated diene monomer” are dyed and observed during TEM observation. Observed in black.
  • the copolymer (a) “a block copolymer comprising a polymer block mainly composed of at least one vinyl aromatic monomer and a polymer block mainly composed of at least one conjugated diene monomer”.
  • ⁇ polymer hydrogenated product '' and / or “the hydrogenated product of a copolymer block comprising at least one vinyl aromatic monomer and at least one conjugated diene monomer” are included,
  • a diamond knife containing water in an ultramicrotome is attached to the test specimen for staining, and a thin film having a thickness of 85 nm is cut out from the plane for sectioning on the water, and then rinsed with Cu mesh for TEM observation.
  • Cu mesh on which this thin film is placed is arranged on a stainless steel net.
  • ruthenium trichloride nhydrate and 1 mL of purified water were dissolved in a petri dish in a glass desiccator, and after adding 5 mL of sodium hypochlorite solution, a Cu mesh on which the thin film was placed was placed. A stainless steel net is placed, the glass desiccator is covered and left to stand for 4 minutes, and then the Cu mesh is taken out.
  • TEM observation can be performed using the copolymer (a) as a black phase and the polyphenylene ether (b) as a white phase. Furthermore, by analyzing this TEM image photograph using commercially available image analysis software, the area fraction of polyphenylene ether aggregates having a particle diameter of 50 ⁇ m or more with respect to the total polyphenylene ether, and average dispersed particles of polyphenylene ether The diameter can be determined.
  • the area fraction of the polyphenylene ether aggregate having a particle diameter of 50 ⁇ m or more with respect to the total polyphenylene ether is regarded as being equivalent to the volume fraction of the polyphenylene ether aggregate having a particle diameter of 50 ⁇ m or more with respect to the total polyphenylene ether.
  • the average dispersed particle size of the polyphenylene ether (b) with respect to the copolymer (a) constituting the thermoplastic resin composition (d) described above is high ductility of the asphalt composition, asphalt composition From the viewpoint of separation of objects, it is preferably less than 5 ⁇ m, more preferably less than 4 ⁇ m, further preferably less than 3.5 ⁇ m, and still more preferably less than 3 ⁇ m.
  • the average dispersed particle size of the polyphenylene ether (b) can be controlled within the above numerical range by adjusting the temperature at the time of melt-kneading or adjusting the number of stirring revolutions at the time of melt-kneading.
  • the above-mentioned pellets of the thermoplastic resin composition (d) used in the asphalt composition of the present embodiment preferably contain a lubricant from the viewpoint of the moldability of the thermoplastic resin composition (d).
  • the lubricant include, but are not limited to, hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; butyl stearate, monoglyceride stearate, pentaerythritol distearate, pentaerythritol tetrastearate, stearyl stearate And fatty acid ester lubricants such as ethylene bis stearamide; fatty acid metal salt lubricants such as magnesium distearate, calcium distearate, zinc distearate and calcium montanate.
  • the addition amount of the lubricant is preferably 0 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 25 parts by mass or less, with respect to 100 parts by mass in total of the copolymer (a) and the polyphenylene ether (b). 5 parts by mass or more and 20 parts by mass or less are more preferable.
  • the thermoplastic resin composition (d) used for the asphalt composition of the present embodiment preferably contains an antioxidant from the viewpoint of improving the heat deterioration resistance.
  • the antioxidant include, but are not limited to, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, amine antioxidants, and the like.
  • the addition amount of the antioxidant is preferably 0 part by mass or more and 10 parts by mass or less, and 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass in total of the copolymer (a) and the polyphenylene ether (b). Is more preferably 0.5 parts by mass or more and 4 parts by mass or less.
  • Asphalt (c) used in the asphalt composition of the present embodiment contains asphalt (c) (hereinafter may be referred to as component (c)).
  • Asphalt (c) used in the asphalt composition of the present embodiment is not limited to the following, for example, one obtained as a by-product during petroleum refining (petroleum asphalt), or a natural product (natural asphalt), or The thing etc. which mixed these and petroleum are mentioned. Its main component is called bitumen.
  • the asphalt include, but are not limited to, straight asphalt, semi-blown asphalt, blown asphalt, solvent deasphalted asphalt, tar, pitch, cutback asphalt to which oil is added, asphalt emulsion, and the like. These may be used alone or in combination of two or more.
  • aromatic heavy mineral oils such as petroleum-type solvent extraction oil, aroma-type hydrocarbon process oil, and extract, to various asphalts.
  • the asphalt (c) used in the asphalt composition of the present embodiment preferably has a penetration (measured according to JIS-K2207) of 30 or more and 300 or less, more preferably from the viewpoint of high temperature physical properties, low temperature physical properties, and economic efficiency.
  • Straight asphalt that is 40 or more and 200 or less, and more preferably 45 or more and 150 or less.
  • the content of asphalt (c) is 80 to 97% by mass, preferably 85 to 97% by mass, and 87 to 97% by mass from the viewpoint of economy and viscosity. More preferred.
  • Total content of copolymer (a) and polyphenylene ether (b) The total content of the copolymer (a) and the polyphenylene ether (b) in the asphalt composition of the present embodiment is such that the high softening point of the asphalt composition, the high ductility of the asphalt composition, the asphalt composition and the aggregate. From the viewpoint of high peeling resistance of the aggregate when it is used as a mixture, it is 2.6% by mass or more, preferably 3.5% by mass or more, more preferably 5% by mass or more, and further preferably 6% by mass or more.
  • the copolymer (a) in the asphalt composition is 20% by mass or less, more preferably 16% by mass or less, and 14% by mass. % Or less, more preferably 12% by mass or less.
  • the addition amount of the copolymer (a) is small, the interaction with the asphalt component is insufficient, and therefore the influence on the performance of the asphalt composition is small.
  • the ratio of (b) is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and further more preferably 15% by mass or more. preferable.
  • the ratio of (b) is 80% by mass or less when (a) + (b) is 100% by mass. Is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • the content of the component (d) is 3 to 15% by mass, and the content of the component (c) is 85 to 97.
  • the asphalt composition of this embodiment can mix
  • the types of petroleum resins are not limited to the following, but include, for example, aliphatic petroleum resins such as C5 petroleum resins, aromatic petroleum resins such as C9 petroleum resins, dicyclopentadiene petroleum resins, and the like. And alicyclic petroleum resins, C5 / C9 copolymer petroleum resins and the like, and hydrogenated petroleum resins obtained by hydrogenating these petroleum resins.
  • the compounding quantity of petroleum resin is not specifically limited, Preferably it is 1 mass part or more and 10 mass parts or less with respect to 100 mass parts of asphalt (c), More preferably, it is 2 mass parts or more and 6 mass parts or less. It is.
  • the asphalt composition of this embodiment can mix
  • the type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.
  • the type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.
  • Inorganic fillers such as carbon black, iron oxide and other pigments;
  • Lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide; release agents, paraffinic process oils, Softeners and plasticizers such as naphthenic process oils, aromatic process oils, paraffins, organic poly
  • the compounding quantity of an additive is not specifically limited, Usually, it is 50 mass parts or less with respect to 100 mass parts of asphalt (c).
  • an anti-peeling agent may be added to prevent the asphalt composition and the aggregate from being peeled when mixed with the aggregate.
  • Resin acid is suitable as the anti-peeling agent, and is a polycyclic diterpene having 20 carbon atoms having a carboxyl group, and any one of abietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, and parastrinic acid Or rosin containing one or more of them. Moreover, you may add a fatty acid or fatty acid amide in order to function as a peeling prevention agent and a lubricant.
  • the asphalt composition of the present embodiment may contain other polymers.
  • other polymers include, but are not limited to, olefin elastomers such as natural rubber, polyisoprene rubber, polybutadiene rubber, styrene butadiene rubber, and ethylene propylene copolymer; chloroprene rubber, acrylic rubber, and ethylene.
  • olefin elastomers such as natural rubber, polyisoprene rubber, polybutadiene rubber, styrene butadiene rubber, and ethylene propylene copolymer
  • chloroprene rubber acrylic rubber
  • ethylene ethylene
  • a vinyl acetate copolymer etc. are mentioned.
  • the asphalt composition of the present embodiment preferably contains 1 to 10% by mass of a styrene-butadiene-styrene copolymer (SBS) from the viewpoints of softening point, melt viscosity, and low temperature elongation. More preferably, it is 3 to 10% by mass, and further preferably 5 to 10% by mass.
  • SBS styrene-butadiene-styrene copolymer
  • the method for producing the asphalt composition of the present embodiment is not particularly limited, and can be produced by appropriately mixing the components (a) to (d) described above.
  • it is preferably performed at a temperature of 120 ° C. or higher and 200 ° C. or lower.
  • the stirring time is usually 30 minutes to 6 hours, but a shorter one is preferable from the viewpoint of economy.
  • the stirring speed may be appropriately selected depending on the apparatus to be used, but is usually 100 ppm or more and 8,000 rpm or less.
  • the asphalt composition of the present embodiment can be used in the fields of road pavement, roofing / waterproof sheet, and sealant, and can be suitably used particularly in the field of road pavement, roofing / waterproof sheet.
  • asphalt mixture For road paving, an example in which a large amount of aggregate is mixed with the asphalt composition of the present embodiment and used can be given. What contains an asphalt composition and an aggregate is hereafter called an asphalt mixture.
  • an asphalt mixture There is no limitation on the aggregate, for example, any aggregate can be used as long as it is described in “Asphalt Pavement Summary” published by the Japan Road Association, and is not limited to the following. However, for example, crushed stone, cobblestone, gravel, steel slag and the like can be mentioned.
  • asphalt-coated aggregates and recycled aggregates obtained by coating these aggregates with asphalt can also be used.
  • granular materials similar to these can be used such as artificial sintered aggregate, sintered foam aggregate, artificial lightweight aggregate, ceramic grains, loxobite, aluminum grains, plastic grains, ceramics, emery, construction waste, fibers, and the like.
  • Aggregates are generally classified into coarse aggregates, fine aggregates, and fillers.
  • Coarse aggregate is an aggregate that remains on a 2.36 mm sieve, and is generally No. 7 crushed stone with a particle size range of 2.5-5 mm, No. 6 crushed stone with a particle size range of 5-13 mm, and a particle size range of 13-20 mm No. 5 crushed stone, and also No. 4 crushed stone having a particle size range of 20 to 30 mm.
  • one or more kinds of coarse aggregates having various particle size ranges are mixed.
  • Aggregates or synthesized aggregates can be used. These coarse aggregates may be coated with about 0.3 to 1% by mass of straight asphalt with respect to the aggregates.
  • Fine aggregate means an aggregate that passes through a 2.36 mm sieve and stops at a 0.075 mm sieve, and is not limited to the following, but is not limited to, for example, river sand, hill sand, mountain sand, sea sand, Screening, crushed stone dust, silica sand, artificial sand, glass cullet, foundry sand, recycled aggregate crushed sand and the like.
  • Fillers pass through a 0.075 mm sieve and are not limited to the following, but include, for example, screenings filler, stone powder, slaked lime, cement, incinerator ash, clay, talc, fly ash Carbon black, etc., but also rubber particles, cork particles, wood particles, resin particles, fiber particles, pulp, artificial aggregates, etc. that pass through a 0.075 mm sieve If so, it can be used as a filler.
  • Coarse aggregates, fine aggregates, and fillers may be used alone or in combination of two or more.
  • the aggregate content in the asphalt mixture containing the asphalt composition and the aggregate is 85% by mass or more and 98% by mass or less from the viewpoint of obtaining a mixture having a high mass loss resistance and a high strength reduction at the time of oil adhesion.
  • the range is preferably 90% by mass or more and 97% by mass or less.
  • the method for producing the asphalt mixture containing the asphalt composition and the aggregate is not particularly limited, but the mixing temperature of the asphalt composition and the aggregate is usually within a range of 120 ° C. or more and 200 ° C. or less. Is mentioned. Moreover, you may emulsify the asphalt composition in water as needed.
  • ⁇ Measuring method ⁇ (Vinyl aromatic monomer block content in the block copolymer) As a measurement object, a copolymer before hydrogenation was used. M. Kolthoff, etal. , J .; Polym. Sci. 1, p. 429 (1946), the vinyl aromatic monomer block content of the copolymer was measured by the osmium tetroxide method. An osmic acid 0.1 g / 125 mL tertiary butanol solution was used for the decomposition of the copolymer.
  • the weight average molecular weight was measured by GPC (apparatus manufactured by Waters). Tetrahydrofuran was used as the solvent, and the temperature was set to 35 ° C.
  • the weight average molecular weight was determined using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene for the molecular weight of the peak of the chromatogram.
  • MFR MFR was calculated by a method according to JIS K7210 using a melt indexer (L247; manufactured by TECHNOLSEVEN CO., LTD).
  • the test temperature was 200 ° C.
  • the test load was 5.00 kgf
  • the unit of measurement value was expressed in g / 10 minutes.
  • Block copolymer 1 (Block copolymer 1) ⁇ First stage polymerization> A stainless steel autoclave with a stirrer and a jacket with an internal volume of 10 L was washed, dried, and purged with nitrogen. The autoclave was charged with 5720 g of cyclohexane and 240 g of pre-purified styrene, and warm water was passed through the jacket to set the contents at about 40 ° C.
  • n-butyllithium cyclohexane solution (0.70 g in pure content) was added to the autoclave to start polymerization of styrene.
  • a mixture of a glycidyl etherified modified product and a phenol-formaldehyde polycondensate diglycidyl etherified modified product with epichlorohydrin at a mass ratio of 1/1 was added so as to be 0.4 mol / Li, and a cup was added. I let it ring.
  • octadecyl-3- (3,5-dibutyl-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added in an amount of 0. 1 to 100 parts by mass of the block copolymer. 25 parts by mass was added and mixed well to obtain block copolymer 1.
  • the block copolymer having the SB structure has a weight average molecular weight of 90,000, and (SB) 2 —X structure
  • the weight average molecular weight of the block copolymer was twice the weight average molecular weight of the SB structure.
  • content of the vinyl aromatic monomer unit was 30 mass%, and MFR (200 degreeC, 5 kgf) was 0.2 g / 10min.
  • the vinyl aromatic monomer block content was 30% by mass, and the vinyl bond content was 11% by mass.
  • S represents a polymer block mainly composed of vinyl aromatic monomer units
  • B represents a polymer block mainly composed of conjugated diene monomer units
  • X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium.
  • Block copolymer 2 In the above ⁇ second stage polymerization>, the coupling agent was changed to silicon tetrachloride and added so as to be 0.2 mol / Li. Other conditions were obtained block copolymer 2 by the same method as the above (block copolymer 1).
  • the block copolymer having the SB structure has a weight average molecular weight of 90,000, and (SB) 4 —X structure
  • the weight average molecular weight of the block copolymer was 4 times the weight average molecular weight of the SB structure.
  • content of the vinyl aromatic monomer unit was 30 mass%, and MFR (200 degreeC, 5 kgf) was 0.01 g / 10min.
  • the vinyl aromatic monomer block content was 30% by mass, and the vinyl bond content was 11% by mass.
  • ⁇ Polymerization> In the ⁇ first stage polymerization> of the (block copolymer 1), the amount of n-butyllithium cyclohexane solution and the amount of styrene were changed, tetramethylenediamine was added, and in the ⁇ second stage polymerization> The amount of butadiene was changed, and without using a coupling agent, the polymerization of styrene was carried out in the same amount of styrene as that of the first stage polymerization as ⁇ third stage polymerization>.
  • the block copolymer 3 was obtained by the method similar to the (block copolymer 1).
  • the obtained block copolymer 3 had an SBS structure and a weight average molecular weight of 70,000.
  • content of the vinyl aromatic monomer unit was 40 mass%, and MFR (200 degreeC, 5 kgf) was 0.5 g / 10min.
  • the vinyl aromatic monomer block content was 29% by mass, and the vinyl bond content was 40% by mass.
  • Block copolymer 4 In the ⁇ first stage polymerization> of the (block copolymer 1), the amount of n-butyllithium cyclohexane solution and the amount of styrene were changed, tetramethylenediamine was added, and in the ⁇ second stage polymerization> Styrene and butadiene were continuously added, and a styrene polymerization was carried out at the same styrene amount as in the first stage as a ⁇ third stage polymerization> without using a coupling agent.
  • Block Copolymer 3 98 mol% of the double bond in the conjugated diene monomer unit in the block copolymer was hydrogenated with the hydrogenation catalyst prepared by the production method of the above (Block Copolymer 3). This was added to obtain a block copolymer solution. Then, the block copolymer 4 was obtained by the method similar to the (block copolymer 1).
  • the obtained block copolymer 4 had an S—R—S structure and had a weight average molecular weight of 150,000.
  • R represents a copolymer block composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit.
  • content of the vinyl aromatic monomer unit was 50 mass%
  • MFR (200 degreeC, 5 kgf) was 3 g / 10min.
  • the vinyl aromatic monomer block content was 15% by mass, and the vinyl bond content was 20% by mass.
  • Block copolymer 5 In ⁇ First Stage Polymerization> of (Block Copolymer 1), styrene is changed to butadiene, and in ⁇ Second Stage Polymerization>, styrene and butadiene are added at a constant ratio, and then styrene is further added. Then, styrene and butadiene were added at a fixed ratio as ⁇ third stage polymerization>, and styrene polymerization was performed with the same styrene amount as in the second stage as ⁇ fourth stage polymerization>. Then, after adding water and deactivating, the block copolymer 5 was obtained by the method similar to the (block copolymer 1).
  • the block copolymer 5 had a BSSBS structure, and the weight average molecular weight was 100,000. Moreover, content of the vinyl aromatic monomer unit was 40%, and MFR (200 ° C., 5 kgf) was 13 g / 10 min. The vinyl aromatic monomer block content was 35% by mass, and the vinyl bond content was 11% by mass.
  • Block copolymer 6 In ⁇ Second Stage Polymerization> of the (Block Copolymer 1), the coupling agent was changed to 1,3-bis (N, N′-diurisidylaminomethyl) cyclohexane to 0.23 mol / Li. It added so that it might become. In other conditions, the block copolymer 6 was obtained in the same manner as in the above (Block copolymer 1).
  • the weight average molecular weight of the SB structure block copolymer is 90,000, and the weight average molecular weight of (SB) 2 -X + (SB) 3 -X + (SB) 4 -X was 3.7 times the weight average molecular weight of the SB structure.
  • content of the vinyl aromatic monomer unit was 30 mass%, and MFR (200 degreeC, 5 kgf) was 0.01 g / 10min.
  • the vinyl aromatic monomer block content was 30% by mass, and the vinyl bond content was 12% by mass.
  • Polyphenylene ether 1 has a reduced viscosity of 0.33 dL / g.
  • Polyphenylene ether 2 has a reduced viscosity of 0.07 dL / g.
  • Polyphenylene ether 3 has a reduced viscosity of 0.60 dL / g.
  • Polyphenylene ether 4 has a reduced viscosity of 0.70 dL / g.
  • Polyphenylene ether 5 has a reduced viscosity of 0.39 dL / g.
  • Polyphenylene ether 5 is obtained by melt-kneading 100 parts by mass of polyphenylene ether having a reduced viscosity of 0.40 dL / g and 2 parts by mass of maleic anhydride (manufactured by NOF Corporation, Crystal MAN) using a twin screw extruder. Was obtained. At this time, the maleic anhydride addition amount was calculated to be 0.5% by mass with respect to 100% by mass of polyphenylene ether by IR measurement.
  • thermoplastic resin composition pellets (d) prepared by coextrusion blending of block copolymer (a) and polyphenylene ether (b). was used.
  • Example 14 the block copolymer 1, and the thermoplastic resin composition pellet (d) composed of the block copolymer 4 and the polyphenylene ether 1 were used.
  • the aggregate used was a mixture of crushed stone and crushed sand produced from Iwafune-cho, Shimotsuga-gun, Tochigi Prefecture, fine sand produced from Sakae-machi, Inba-gun, Chiba Prefecture, and stone powder produced from Yamagata-machi, Sano City, Tochigi Prefecture.
  • the particle size distribution of the aggregate used in the asphalt mixture is shown in Table 1 below.
  • Softening point is 112 ° C or higher: ⁇ Softening point 105 ° C or higher and lower than 112 ° C: ⁇ Softening point is 98 ° C. or higher and lower than 105 ° C .: ⁇ Softening point less than 98 ° C: ⁇
  • melt viscosity of asphalt composition The melt viscosity of the asphalt composition at 160 ° C. was measured with a Brookfield viscometer. The lower the melt viscosity of the asphalt composition, the better the manufacturability, and it was evaluated as ⁇ , ⁇ , ⁇ , ⁇ in order from the following criteria.
  • Melt viscosity is less than 900 mPa ⁇ s: ⁇ Melt viscosity is 900 mPa ⁇ s or more and less than 1200 mPa ⁇ s: ⁇ Melt viscosity is 1200 mPa ⁇ s or more and less than 1500 mPa ⁇ s: ⁇ Melt viscosity is 1500 mPa ⁇ s or more: ⁇
  • Average particle diameter is less than 10 ⁇ m: ⁇ Average particle diameter of 10 ⁇ m or more and less than 25 ⁇ m: ⁇ Average particle diameter is 25 ⁇ m or more and less than 50 ⁇ m: ⁇ Average particle diameter is 50 ⁇ m or more: ⁇
  • Asphaltt separability of asphalt composition The separability of the asphalt composition after high temperature storage was evaluated.
  • a sample was poured into a Teflon (registered trademark) tube whose bottom was 2.5 cm in diameter and 15 cm long and was sealed with a rubber stopper, covered with an aluminum sheet, and then left in an oven at 175 ° C. for 72 hours. .
  • the asphalt composition was divided into three equal parts in the length direction. The softening points of the upper layer and the lower layer were measured, and the difference between the softening points was determined.
  • Softening point difference is 2 ° C or less: ⁇ Softening point difference is 6 ° C or less: ⁇ Softening point difference is 10 ° C. or less: ⁇ Softening point difference exceeds 10 ° C: ⁇
  • Dynamic stability is 13000 times / mm or more: ⁇ Dynamic stability is 10,000 times / mm or more: ⁇ Dynamic stability is 6000 times / mm or more: ⁇ Dynamic stability is less than 6000 times / mm: ⁇
  • the asphalt composition of the present invention has industrial applicability in the fields of road paving, roofing / waterproof sheets, and sealants.

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Abstract

L'invention concerne une composition d'asphalte comprenant : (a) un copolymère contenant des unités monomères aromatiques vinyliques et des unités monomères diènes conjuguées ; (b) un éther de polyphénylène présentant une viscosité réduite de 0,07 à 0,60 dL/g ; et (c) de l'asphalte, la teneur en (a) étant de 2,5 à 14% en masse, la teneur en (b) étant de 0,1 à 10% en masse et la teneur en (c) étant de 80 à 97% en masse.
PCT/JP2018/020039 2017-06-14 2018-05-24 Composition d'asphalte WO2018230299A1 (fr)

Priority Applications (1)

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WO2020194702A1 (fr) * 2019-03-28 2020-10-01 出光興産株式会社 Composition d'asphalte, mélange d'asphalte, appareil de production de composition d'asphalte, système de production de composition d'asphalte, et procédé de production de composition d'asphalte
WO2022023531A1 (fr) * 2020-07-31 2022-02-03 Shell Internationale Research Maatschappij B.V. Additifs anti-vieillissement pour bitume
CN114350150A (zh) * 2019-04-18 2022-04-15 重庆市智翔铺道技术工程有限公司 基于聚合物合金的高强轻质钢桥面铺装材料及其制备方法
WO2024034294A1 (fr) * 2022-08-08 2024-02-15 旭化成株式会社 Composition d'asphalte

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WO2020194702A1 (fr) * 2019-03-28 2020-10-01 出光興産株式会社 Composition d'asphalte, mélange d'asphalte, appareil de production de composition d'asphalte, système de production de composition d'asphalte, et procédé de production de composition d'asphalte
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CN114350150A (zh) * 2019-04-18 2022-04-15 重庆市智翔铺道技术工程有限公司 基于聚合物合金的高强轻质钢桥面铺装材料及其制备方法
WO2022023531A1 (fr) * 2020-07-31 2022-02-03 Shell Internationale Research Maatschappij B.V. Additifs anti-vieillissement pour bitume
WO2024034294A1 (fr) * 2022-08-08 2024-02-15 旭化成株式会社 Composition d'asphalte

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