TW201905077A - Asphalt composition - Google Patents

Abstract

This asphalt composition comprises: (a) a copolymer having vinyl aromatic monomer units and conjugated diene monomer units; (b) polyphenylene ether having a reduced viscosity of 0.07-0.60 dL/g; and (c) asphalt, wherein the content of (a) is 2.5-14 mass%, the content of (b) is 0.1-10 mass%, and the content of (c) is 80-97 mass%.

Description

Asphalt composition

The present invention relates to an asphalt composition.

Previously, asphalt compositions were widely used for road paving, waterproof sheets, soundproof sheets, roofing materials, and the like. When the above-mentioned asphalt composition is applied to various applications, many attempts have been made to improve the properties by adding various polymers to the asphalt. Examples of the polymer include an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a rubber latex, and a block copolymer containing a conjugated diene and a vinyl aromatic hydrocarbon.

On the other hand, in recent years, from the viewpoints of an increase in traffic volume and global warming, requirements such as improvement in high-temperature physical properties of the asphalt composition have been increasing.

In order to improve the high-temperature physical properties of the asphalt composition, a technique has been proposed that contains various additives to improve the high-temperature physical properties of the asphalt composition (for example, refer to Patent Documents 1 to 3). Specifically, it is known to add polyphenylene ether as an additive to increase the softening point of the asphalt composition, or to add heteropolypropylene as an additive to increase the softening point of the asphalt composition, or to add styrene-butadiene- A technique in which styrene copolymer (SBS) is used as an additive to increase the softening point of an asphalt composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2002/042377 [Patent Document 2] Japanese Patent Laid-Open No. 1-282235 [Patent Document 3] Japanese Patent Laid-Open No. 6-41439

[Problems to be solved by the invention]

However, even in the technologies disclosed in Patent Documents 1 to 3, sufficient properties have not been obtained regarding the high-temperature physical properties of the asphalt composition, and it is desired to further improve the high-temperature physical properties of the asphalt composition. The present inventors conducted research, and as a result, the technology described in the above-mentioned Patent Document 1 has the following problems: since the low-temperature physical properties are poor and the additives are not uniformly dissolved in the asphalt, there is a concern that the high-temperature storage properties are deteriorated. Further, the technique described in Patent Document 2 has a problem that the balance between low-temperature physical properties and various characteristics is poor. Furthermore, the technique described in Patent Document 3 has a problem in that the viscosity of the asphalt composition is increased due to an increase in the amount of the additive, and the processability is deteriorated.

Therefore, an object of the present invention is to provide an asphalt composition which has excellent viscosity, low temperature physical properties, copolymer and polyphenylene ether solubility in asphalt, and excellent high temperature physical properties. [Technical means to solve the problem]

The present inventors made earnest research in order to solve the problems of the prior art, and as a result, found that the copolymer contains a vinyl aromatic monomer unit and a conjugated diene monomer unit, and a polyphenylene ether having a specific specific viscosity. Asphalt compositions with specific amounts of asphalt, and asphalt can solve the above-mentioned problems of the prior art, thereby completing the present invention. That is, the present invention is as follows.

[1] An asphalt composition comprising a copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit, and a polyphenylene ether having a reduced viscosity of 0.07 dL / g to 0.60 dL / g (b) and bitumen (c), the content of (a) is 2.5 to 14% by mass, the content of (b) is 0.1 to 10% by mass, and the content of (c) is 80 to 97% by mass. [2] The asphalt composition according to the above [1], wherein the polyphenylene ether (b) has a modifying group, and the modifying group includes a group selected from a carboxyl group and / or a carboxyl group-derived group, a hydroxyl group, an acid anhydride group, and a ring. At least one functional group in the group consisting of oxy, amine, amido, silanol, and alkoxysilyl groups. [3] The asphalt composition according to the above [1] or [2], wherein the polyphenylene ether (b) has a carboxyl group and / or a group derived from a carboxyl group. [4] The asphalt composition according to any one of the above [1] to [3], wherein the content of the (a) is 4 to 14% by mass, and the content of the (b) is 0.1 to 8% by mass, the above The content of (c) is 80 to 97% by mass. [5] The asphalt composition according to any one of the above [1] to [4], wherein the content of the (a) is 4 to 12% by mass, and the content of the (b) is 0.1 to 5% by mass, and The content of the (c) is 85 to 97% by mass. [6] An asphalt composition comprising: a thermoplastic resin composition (d), which is a copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit and a reduced viscosity of 0.07 dL / g to 0.60 dL / g of an extruded body of polyphenylene ether (b); and bitumen (c); the content of (d) is 3 to 20% by mass, and the content of (c) is 80 to 97% by mass %, And the mass ratio of the (a) to the (b) in the thermoplastic resin composition (d) (a) / (b) = 20 to 99/80 to 1. [7] The asphalt composition according to the above [6], wherein the thermoplastic resin composition (d) has a sea-island structure, and the sea-island structure includes a marine phase composed of the copolymer (a), and the polyphenylene ether ( b) an island phase constituted, and the average dispersed particle diameter of the polyphenylene ether (b) in the thermoplastic resin composition (d) is less than 5 μm. [8] The asphalt composition according to the above [6] or [7], wherein the content of the (d) is 3 to 15% by mass, the content of the (c) is 85 to 97% by mass, in the (d) The mass ratio (a) / (b) of (a) to (b) above is 40 to 99/60 to 1. [9] The asphalt composition according to any one of the above [6] to [8], wherein the thermoplastic resin composition (d) contains an antioxidant. [10] The asphalt composition according to any one of the above [6] to [9], wherein the copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit is hydrogenated. [11] The asphalt composition according to any one of the above [6] to [10], further containing 1 to 10% by mass of a styrene-butadiene-styrene copolymer (SBS). [12] The asphalt composition according to any one of the above [1] to [11], wherein the copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit has a functional group Of modified groups. [Effect of the invention]

According to the present invention, an asphalt composition having excellent high-temperature physical properties and excellent viscosity, low-temperature physical properties, and copolymer and polyphenylene ether solubility in asphalt can be obtained.

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following. The present invention can be implemented with various changes within the scope of the gist thereof.

[Asphalt Composition] The asphalt composition of this embodiment contains a copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit, and has a specific viscosity of 0.07 dL / g to 0.60 dL / g. Polyphenylene ether (b) and asphalt (c), and the content of (a) is 2.5 to 14% by mass, the content of (b) is 0.1 to 10% by mass, and the content of (c) is 80 to 97 quality%.

Here, the structural unit constituting the copolymer is referred to as "~ monomer unit", and when it is described as a material of the polymer, "unit" is omitted, and only "~ monomer" is described.

(Copolymer (a)) The asphalt composition according to the present embodiment contains a copolymer (a) (hereinafter referred to as a copolymer (a), (a)) having a vinyl aromatic monomer unit and a conjugated diene monomer unit. a) case of ingredients). The copolymer (a) may be any of a random copolymer and a block copolymer, and both are in a preferred form. In addition, it is a preferable form. Examples thereof include block copolymers having a polymer block having a vinyl aromatic monomer unit as a main body and a polymer block having a conjugated diene monomer unit as a main body. Other monomer units may be contained in the range which does not inhibit the objective of this embodiment. In the present specification, the "main body" means that the content of a specific monomer unit in a block is 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The upper limit is not particularly limited, but is preferably 100% by mass or less, and more preferably 99% by mass or less. The asphalt composition according to this embodiment contains 2.5 to 14% by mass of the copolymer (a), which is excellent in high-temperature physical properties, and has viscosity, low-temperature performance, and solubility of the copolymer (a) to the asphalt. Those who are excellent in each characteristic become those who are excellent in balance of these characteristics. The content of the copolymer (a) in the asphalt composition of the present embodiment is preferably from 4 to 14% by mass, and more preferably from 4 to 12% by mass from the viewpoint described above.

In the present embodiment, the copolymer (a) can be exemplified by a polymer block having a polymer block having a vinyl aromatic monomer unit as a main body and a polymer block having a conjugated diene monomer unit as a main body as described above. A segment copolymer (hereinafter, described as a block copolymer (a)) is a preferred embodiment. Furthermore, in addition to this, it may have a copolymer block containing a vinyl aromatic monomer unit and a conjugated diene monomer unit. The block copolymer (a) preferably contains at least one block copolymer selected from the group consisting of the following formulae (i) to (xii).

(SB) _n (i) S- (BS) _n (ii) B- (SB) _n (iii) S- (BS) _n -X (iv) [(SB) _k ] _m -X (v) [( SB) _k -S] _m -X (vi) (SR) _n (vii) S- (RS) _n (viii) R- (SR) _n (ix) S- (RS) _n -X (x) (( SR) _k ] _m -X (xi) [(SR) _k -S] _m -X (xii)

In the above formulae (i) to (xii), S represents a polymer block having a vinyl aromatic monomer unit as a main body, B represents a polymer block having a conjugated diene monomer unit as a main body, and R represents a polymer block containing A copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit, X represents a residue of a coupling agent or a residue of a polymerization initiator such as a polyfunctional organolithium, and m is an integer of 2 to 6, n and k are each independently an integer of 1 to 4. The values of m, n, and k in the above (i) to (vi) may be the same or different.

When there are a plurality of blocks S, B, and R in the block copolymer (a), the respective structures such as molecular weights and compositions may be the same or different.

As described above, in the above formulae (iv) to (vi) and (x) to (xii), X represents a residue of a coupling agent or a residue of a polymerization initiator such as a polyfunctional organolithium, and the From the viewpoint of molecular weight, X is preferably a residue of a coupling agent.

The coupling agent is not limited to the following, and examples thereof include silicon tetrachloride, tin tetrachloride, epoxy compounds, polyhalogenated hydrocarbon compounds, carboxylic acid ester compounds, polyethylene compounds, alkoxysilane compounds, and halogenated silane compounds. , Ester compounds and so on.

From the viewpoint of heat resistance deterioration of the block copolymer (a) when producing the asphalt composition of the present embodiment, the coupling agent is preferably an alkoxysilane compound or an epoxy compound, and more preferably an epoxy compound.

The alkoxysilane compound is not limited to the following, and examples thereof include tetramethoxysilane and tetraalkoxysilane compounds such as the same; tetraphenoxysilane and tetraaryloxysilane compounds such as the same ; Methyltriethoxysilane and its alkoxyalkane compounds having 2 or 3 or more alkoxy groups and the like; methyltriethoxysilane and its equivalents having 2 or more aryl groups and the like Alkyl aryloxy silane compounds; vinyl trimethoxy silanes and their likes, alkenyl alkoxy silane compounds having 2 or more alkoxy groups; and trimethoxychlorosilanes and their likes And other halogenated alkoxysilane compounds. Among these, an alkylalkoxysilane having 2 to 4 alkoxy groups is preferred from the viewpoint of heat resistance deterioration or the manufacturability of the block copolymer (a).

The epoxy compound is not limited to the following, and examples thereof include polyepoxidized vegetable oils such as epoxidized soybean oil or epoxidized linseed oil; epoxidized polybutadiene, epoxidized tetraallyl ether pentaerythritol, Epoxy compounds such as phenyl. Among these, the epoxy compound which has a phenyl group is preferable from a viewpoint of heat resistance deterioration or the manufacturability of a block copolymer.

Regarding the amount of the alkoxysilane group or epoxy group in the alkoxysilane compound or epoxy compound, the lower mixing temperature of the asphalt composition of the present embodiment, the lower viscosity of the asphalt composition, and the asphalt composition From the viewpoint of less deterioration of the copolymer (a) and high peel resistance of the aggregate when the mixture of the asphalt composition and the aggregate is made, preferably 2 to 5 per molecule, more preferably Two to four.

The copolymer (a) used in the asphalt composition of this embodiment is the high temperature physical properties of the asphalt composition, the low viscosity of the asphalt composition, the low temperature physical properties of the asphalt composition, and the polyphenylene ether (b) and the copolymer (a ) From the viewpoint of the solubility of the pitch, it is preferable to include a compound having [(SB) _k ] _m -X (m = an integer of 2 to 4, k = an integer of 1 to 4, and S is a vinyl aromatic monomer. Polymer block with body unit as main body, B is polymer block with conjugated diene monomer unit as main body, X is block copolymerization of the structure of the coupling agent residue or the polymerization initiator residue) Thing. From the viewpoint of the high-temperature physical properties of the asphalt composition and the relatively low viscosity of the asphalt composition, it is preferable to contain an integer having (SB) _n (n = 2 to 4), and S is a vinyl aromatic monomer unit. As the main polymer block, B is a block copolymer having a structure of a conjugated diene monomer unit as the main polymer block). Furthermore, from the viewpoint of the high-temperature physical properties of the asphalt composition and the low-temperature physical properties of the asphalt composition, it is preferable to contain an integer having S- (BS) _n (n = 1 to 4), and S is a vinyl aromatic monomer. A block copolymer having a polymer block having a unit as a host, and a block B having a polymer block having a conjugated diene monomer unit as a host. Furthermore, from the viewpoints of the high-temperature physical properties of the asphalt composition and the solubility of the polyphenylene ether (b) and the copolymer (a) with respect to the asphalt, it is preferable to contain the compounds having S- (RS) _n and [(SR) _k ] _m -X (n = 1 to 4 integers, m = 2 to 4 integers, k = 1 to 4 integers, S is a polymer block having a vinyl aromatic monomer unit as a main body, and R is a polymer block containing A block copolymer of a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit, and X is a residue of a coupling agent or a residue of a polymerization initiator).

Regarding the weight average molecular weight (Mw) of the copolymer (a) used in the asphalt composition of this embodiment, the higher the softening point of the asphalt composition and the comparison of the aggregate when the asphalt composition and the aggregate are made into a mixture From the viewpoint of high peel resistance, it is preferably 40,000 or more, more preferably 60,000 or more, and even more preferably 100,000 or more. From the viewpoint of lower viscosity of the asphalt composition and less deterioration of the copolymer (a) in the asphalt composition, it is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000. the following.

The weight average molecular weight of the copolymer (a) can be determined by the method described in the following examples.

Regarding the content of the vinyl aromatic monomer unit in the copolymer (a) used in the asphalt composition of the present embodiment, the higher the softening point of the asphalt composition, and the ratio when the asphalt composition and the aggregate are made into From the viewpoint of high peel resistance of the aggregate, it is preferably 10% by mass or more, more preferably 14% by mass or more, still more preferably 20% by mass or more, and even more preferably 25% by mass or more. From the viewpoints of lower viscosity of the asphalt composition, less deterioration of the copolymer (a), and softness of the asphalt composition, it is preferably 60% by mass or less, more preferably 55% by mass or less, and more preferably It is preferably 52% by mass or less, and even more preferably 45% by mass or less.

Here, the content of the vinyl aromatic monomer unit in the copolymer (a) refers to the content of the vinyl aromatic monomer unit in the entire copolymer (a). In the case where a plurality of components are present in the copolymer (a), that is, the copolymer (a) is a mixture of a plurality of copolymers, when the content of the vinyl aromatic monomer unit of each copolymer is different, it is each ethylene The average value of the content of the base aromatic monomer unit.

In this embodiment, the content of the vinyl aromatic monomer unit in the copolymer (a) can be measured by the method described in the following examples.

The content of the polymer block having a vinyl aromatic monomer unit as a main component in the copolymer (a) used in the asphalt composition of the present embodiment (here, as described above, the so-called "main component" is a Refers to a polymer block containing more than 80% by mass and less than 100% by mass of a vinyl aromatic monomer unit), compared to the higher softening point of the asphalt composition and the comparison of the asphalt composition and the aggregate From the viewpoint of high peel resistance, it is preferably 8% by mass or more, more preferably 12% by mass or more, still more preferably 15% by mass or more, and still more preferably 20% by mass or more. From the viewpoints of lower viscosity of the asphalt composition, less deterioration of the copolymer (a), and softness of the asphalt composition, it is preferably 50% by mass or less, more preferably 45% by mass or less, It is preferably 40% by mass or less, and even more preferably 35% by mass or less.

In addition, the content of the polymer block having the vinyl aromatic monomer unit as the main component in the copolymer (a) can be determined by the vinyl aromatic monomer in the block copolymer described in the following examples. The measurement method of the block content was measured.

The copolymer (a) used in the asphalt composition of the present embodiment is the higher softening point of the asphalt composition, the higher thermal deterioration resistance of the copolymer (a), and the following extrusion molding with polyphenylene ether (b) From the viewpoint of less thermal degradation during blending, it is preferred that the double bond contained in the conjugated diene monomer unit in the copolymer (a) is hydrogenated. The conjugated diene monomer is from the viewpoints of a higher softening point of the asphalt composition, higher thermal degradation resistance during storage, and less thermal degradation when blended with extrusion molding of polyphenylene ether (b). The hydrogenation rate of the double bond contained in the unit is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. However, the hydrogenation rate of the amount of double bonds contained in the conjugated diene monomer unit is preferably 90 mol% or less, more preferably 75 mol% or less, and more preferably from the viewpoint of higher compatibility with asphalt. It is 60 mol% or less.

In addition, a conjugated diene monomer unit does not have a conjugated diene due to hydrogenation, but in this specification, it is called "conjugated diene monomer unit" before and after hydrogenation.

The hydrogenation rate of the amount of double bonds can be adjusted by controlling the amount of hydrogenation or the reaction time in the hydrogenation step. In this embodiment, the hydrogenation rate can be determined by the method described in the following examples.

Regarding the amount of ethylene bonds in the conjugated diene monomer unit of the copolymer (a) used in the asphalt composition of the present embodiment before hydrogenation, from the viewpoint of higher compatibility with the asphalt and lower viscosity of the asphalt composition In particular, it is preferably 8 mol% or more, more preferably 10 mol% or more, and still more preferably 12 mol% or more. The amount of ethylene bonds in the conjugated diene monomer unit before the hydrogenation of the copolymer (a) is preferably 45 mol from the viewpoint that the degradation of the copolymer (a) in the asphalt composition is small. % Or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, even more preferably 25 mol% or less.

Regarding the melt flow rate (MFR, 200 ° C, 5 kgf) of the copolymer (a) used in the asphalt composition of this embodiment, regarding the manufacturability of the copolymer (a) and the extrusion of the polyphenylene ether (b) From the viewpoint of less thermal degradation during molding blending, it is preferably 0.01 g / 10 min or more, more preferably 0.2 g / 10 min or more, still more preferably 1.0 g / 10 min or more, and even more preferably 3 g / 10 min or more. From the viewpoint of low addition amount of the polymer added to the asphalt or recoverability after stretching, it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and even more preferably 30 g / 10 min or less.

The copolymer (a) is preferably a functional group-containing modified group (a functional group-containing modified group containing a functional group-containing modified group) from the standpoint of excellent separability of the asphalt composition and interaction with asphalt and / or aggregate. Modified copolymer). The functional group is not limited to the following, and examples include, for example, at least one selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, an amido group, a silanol group, and an alkoxysilyl group. Functional groups. It is preferable to add a modified group containing these functional groups to the copolymer (a), and the addition method of the modified group containing functional groups is not limited to the following, and examples include: A method for using a monomer having a modifying group containing these functional groups as a monomer; a monomer unit constituting a block copolymer, a polymerization initiator having a modifying group containing these functional groups, and a coupling agent Or a method for bonding residues of a terminator.

(Manufacturing method of copolymer (a)) The copolymer (a) used in the asphalt composition of this embodiment can be produced, for example, by sequentially performing the following steps: a polymerization step, which is a polymerization of a lithium compound in a hydrocarbon solvent An initiator, at least polymerizing a conjugated diene monomer and a vinyl aromatic monomer to obtain a copolymer; as an optional hydrogenation step, the conjugated diene monomer unit of the obtained copolymer is The double bond undergoes hydrogenation; and a solvent removal step, which is a solvent removal of the solvent of the solution containing the copolymer.

<Polymerization Step> In the polymerization step, a lithium compound is used as a polymerization initiator in a hydrocarbon solvent, and at least a monomer including a conjugated diene monomer and a vinyl aromatic monomer is polymerized to obtain a polymer.

[Hydrocarbon solvent] The hydrocarbon solvent used in the polymerization step is not limited to the following, and examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; cyclopentane , Cycloaliphatic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and the like. These may be used alone or in combination of two or more.

[Polymerization initiator] The lithium compound used as the polymerization initiator in the polymerization step is not limited to the following, and examples thereof include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds. Compounds of more than one lithium atom. The organic lithium compound is not limited to the following, and examples thereof include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, second butyl lithium, third butyl lithium, and hexamethylene. Methyl dilithium, butadienyl dilithium, isoprenyl dilithium, and the like. These may be used alone or in combination of two or more.

[Monomer used for polymerization] The conjugated diene monomer is not limited to the following, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene Ene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. have 1 Diene to conjugated double bonds. Among these, 1,3-butadiene and isoprene are preferable from a viewpoint of economy. From the viewpoint of mechanical strength, 1,3-butadiene is more preferred. These may be used individually by 1 type, and may use 2 or more types together.

The vinyl aromatic monomer is not limited to the following, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-stilbene, and N, N- Vinyl aromatic compounds such as dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene. Among these, styrene is preferable from a viewpoint of economy. These may be used individually by 1 type, and may use 2 or more types together.

In addition to the above-mentioned conjugated diene monomer and vinyl aromatic monomer, other monomers that can be copolymerized with the conjugated diene monomer and vinyl aromatic monomer may be used.

[Polar compound, randomizer] In the polymerization step, adjust the polymerization speed, adjust the microstructure of the polymerized conjugated diene monomer unit (the ratio of cis, trans, and vinyl), and adjust the conjugate For the purpose of the reaction ratio of a diene monomer to a vinyl aromatic monomer, a specific polar compound or a randomizer can be used.

The polar compound or randomizer is not limited to the following, and examples include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; triethylamine and tetramethylethylenediamine And other amines; thioethers, phosphines, phosphatidamines, alkylbenzene sulfonates, potassium or sodium alkoxides, etc.

The polymerization method is not particularly limited, and a known method can be applied. Examples of known methods include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, and Japan Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 56-28925, Japanese Patent Publication No. 59-166518, and Japanese Patent Publication No. 60-186577 And so on.

<Deactivation step> In the production method of the copolymer (a), it is preferable to deactivate the active end of the copolymer by performing a deactivation step after the polymerization step. The method of deactivating the active end of the copolymer includes a method of reacting the active end with a compound having active hydrogen. Although it does not specifically limit as a compound which has active hydrogen, From an economic viewpoint, alcohol or water is preferable.

<Hydrogenation step> The hydrogenation step is a step of performing a hydrogenation reaction 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 specific catalyst. The catalyst used in the hydrogenation reaction is not limited to the following, and examples thereof include a metal such as Ni, Pt, Pd, and Ru supported on a carrier such as carbon, silica, alumina, and diatomaceous earth. Supported heterogeneous catalysts; so-called Ziegler-type catalysts using organic salts of Ni, Co, Fe, Cr, etc., or acetamidine and organic Al, and reducing agents such as organic Al; organometallic compounds such as Ru, Rh, etc. A so-called organic complex catalyst or a homogeneous catalyst using organic Li, organic Al, organic Mg, or the like as a reducing agent for a titanocene compound. In particular, from the viewpoints of economic efficiency, heat aging resistance of a polymer, and weather resistance, a homogeneous catalyst system using organic Li, organic Al, organic Mg, or the like as a reducing agent for the titanocene compound is preferred.

The hydrogenation method is not limited to the following, and examples thereof include the methods described in Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43-6636, or preferably Japanese Patent Publication No. 63-4841. The method described in the Gazette and Japanese Patent Publication No. 63-5401. Specifically, the hydrogenated block copolymer solution can be obtained by performing hydrogenation in an inactive solvent in the presence of a hydrogenation catalyst.

The hydrogenation reaction may use any of a batch process, a continuous process, or a combination thereof.

From the viewpoint of higher hydrogenation activity, the hydrogenation reaction is preferably performed after the above-mentioned step of deactivating the active end of the copolymer, but it is not particularly limited.

In the hydrogenation step, the conjugate bond of the vinyl aromatic monomer unit may also be hydrogenated. The hydrogenation rate of the conjugate bond in all vinyl aromatic monomer units is preferably 30 mol% or less, more preferably 10 mol% or less, and even more preferably 3 mol% or less. In addition, the lower limit of the hydrogenation rate of the conjugate bond in all vinyl aromatic monomers is not particularly limited, but it is preferably a value higher than 0 mol%, and more preferably 1 mol% or more. When the hydrogenation rate of the conjugate bond in all the vinyl aromatic monomers is within the above range, the amount of the polymer added to the asphalt can be reduced, and the compatibility with the asphalt tends to be high.

<Solvent Removal Step> The solvent removal step is a step of solvent removal of a solvent containing a solution of 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 desolvation 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, still more preferably 0.05% by mass or less, further It is more preferably 0.01% by mass or less. In addition, the lower limit of the amount of the residual solvent in the copolymer is not particularly limited, and it is preferably smaller, preferably 0% by mass. From the viewpoint of economical efficiency at the time of solvent removal, it is usually 0.01% by mass or more and 0.1% by mass. The range is less than%.

From the viewpoint of heat aging resistance of the copolymer (a) or suppression of gelation, it is preferable to add an antioxidant to the copolymer (a). The antioxidant is not limited to the following, and examples thereof include a phenol-based antioxidant such as a radical scavenger, a phosphorus-based antioxidant such as a peroxide decomposer, or a sulfur-based antioxidant. It is also possible to use an antioxidant having both properties. These may be used individually by 1 type, and may use 2 or more types together.

Among the above-mentioned antioxidants, it is preferable to add at least a phenol-based antioxidant from the viewpoint of the heat-resistant aging resistance of the copolymer (a) or the asphalt composition of the present embodiment or the inhibition of gelation. Regarding the addition amount of the phenol-based antioxidant, from the viewpoint of higher low-temperature manufacturability or less deterioration of the copolymer during mixing, it is preferably 0.05 parts by mass or more relative to 100 parts by mass of the copolymer (a). It is more preferably 0.10 parts by mass or more, and still more preferably 0.20 parts by mass or more. In addition, the added amount of the phenol-based antioxidant is preferably 1 part by mass or less, more preferably 100 parts by mass, more preferably 100 parts by mass of the copolymer (a), and more preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and even more preferably 0.3 parts by mass or less.

In addition, from the viewpoint of preventing the coloring of the copolymer (a) or improving the mechanical strength, it is also possible to perform an ash removal step to remove the metal in the copolymer (a) or to adjust the pH of the polymer before the solvent removal step. Neutralization steps, such as adding acid or carbon dioxide.

(Polyphenylene ether (b) with a reduced viscosity of 0.07 dL / g to 0.60 dL / g) The asphalt composition of this embodiment becomes the high-temperature physical properties of the asphalt composition, and the viscosity, low-temperature performance, and copolymer of the asphalt composition. (a) From the viewpoint of excellent solubility of asphalt and balance of these properties, it includes polyphenylene ether having a reduced viscosity of 0.1 to 10% by mass and a 0.07 dL / g to 0.60 dL / g (b) (Hereinafter, it may be described as the polyphenylene ether (b), (b) component). From the viewpoint described above, the content of the polyphenylene ether (b) is preferably 0.1 to 8% by mass, and more preferably 0.1 to 5% by mass. Regarding polyphenylene ether (b), it is considered that generally, the glass transition point is high, and even if it is small, it is of great help to performance, and even if the addition amount is 0.1% by mass, it has an improvement effect. On the other hand, if it is added in a large amount, the viscosity becomes very high and the processability is deteriorated. Therefore, the upper limit is set to 10% by mass. The polyphenylene ether (b) may be one having a functional group (having a modifying group containing a functional group) or one having no functional group (having no modifying group containing a functional group). Examples of the functional group include a carboxyl group and / or a group derived from a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, an amido group, a silanol group, and an alkoxysilyl group. Specific preferable aspects of the polyphenylene ether (b) include the following (1) to (3). (1) Polyphenylene ether (b-1) containing no modified group containing a functional group. (2) Polyphenylene ether (b-2) containing a carboxyl group and / or a group derived from a carboxyl group as a modified group containing a functional group. (3) A mixture containing the above-mentioned polyphenylene ether (b-1) which does not have a functional group-containing modified group, and a polyphenylene ether (b-2) which has a carboxyl group and / or a group derived from a carboxyl group.

The polyphenylene ether (b) used in the asphalt composition of this embodiment has a specific viscosity of 0.07 dL / g to 0.60 dL / g, and from the viewpoint of a higher softening point of the asphalt composition, 0.07 dL / g The above is preferably 0.15 dL / g or more, more preferably 0.20 dL / g or more, and even more preferably 0.30 dL / g or more. From the viewpoint of the relatively low viscosity, softness of the asphalt composition, and the solubility of the polyphenylene ether (b) to the asphalt, it is 0.60 dL / g or less, preferably 0.55 dL / g or less, and more preferably 0.50 dL / g or less, more preferably 0.40 dL / g or less.

The reduced viscosity of the polyphenylene ether (b) can be measured by the method described in the following examples. The reduced viscosity of the polyphenylene ether (b) can be controlled to the above-mentioned 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 is obtained by combining polyphenylene ether (b-1) which does not have a functional group-containing modified group with unsaturated It is obtained by reacting a carboxylic acid or its derivative (F). The addition amount of the unsaturated carboxylic acid or its derivative (F) to the polyphenylene ether (b-1) which does not have a modifying group containing a functional group is preferably relative to the polyphenylene ether (b-1) 100% by mass, 0.01 to 10% by mass. The reaction conditions are not limited to the following. For example, addition can be performed in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. due to the presence or absence of a radical generator. . The addition amount may be appropriately set depending on the purpose, and if the addition amount is small, a mixture of a polyphenylene ether having a functional group-containing modified group and a polyphenylene ether not having a functional group-containing modified group is obtained.

The unsaturated carboxylic acid or its derivative (F) is not limited to the following, and examples thereof include maleic acid, fumaric acid, citraconic acid, mesaconic acid, aconitic acid, itaconic acid, and cis-4- Unsaturated carboxylic acids such as cyclohexene-1,2-dicarboxylic acid and chloromaleic acid; maleic anhydride, citraconic anhydride, aconitic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-di Carboxylic anhydride, chloromaleic anhydride and other anhydrides; monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate Ester compounds such as esters, monoethyl fumarate and diethyl fumarate. Especially preferred are maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and maleic anhydride, and more preferred are maleic acid and maleic anhydride. When maleic acid or maleic anhydride is selected as the unsaturated carboxylic acid or its derivative (F), it is considered that the polyphenylene ether (b-2) having a modified group containing a functional group is equivalent to this embodiment The interaction of other polar ingredients contained in the asphalt composition improves the compatibility as a composition. The unsaturated carboxylic acid or its derivative (F) may be used singly or in combination of two or more kinds.

In addition, as the introduction to the polyphenylene ether (b), at least one function selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, a fluorenamine group, a silanol group, and an alkoxysilyl group is introduced. The method of modifying the group is not limited to the following, and examples thereof include a method of bonding with a residue of a coupling agent or a terminator.

Regarding the polyphenylene ether (b) used in the asphalt composition of the present embodiment, it is more preferable to have a functional group-containing modification from the viewpoints of the separability of the asphalt composition, the low-temperature performance, and the rut resistance of the asphalt mixture. Polyphenylene ether. As a reason for improving the rut resistance by using a polyphenylene ether having a functional group-containing modified group as the polyphenylene ether (b), it is considered that an aggregate (stone), which is a polar material, and polyphenylene ether are used. The interaction of the functional group-containing modified group and the position of the aggregate in the asphalt composition are fixed, whereby rut formation becomes difficult to occur.

In the production of the asphalt composition of this embodiment, the copolymer (a) and the polyphenylene ether (b) can be added independently, and the copolymer (a) and the polyphenylene ether (b) can also be added by extrusion molding. A thermoplastic resin composition (d), such as a pellet. The copolymer (a) and the above-mentioned thermoplastic resin composition (d) may be added separately. Furthermore, two or more thermoplastic resin compositions (d) may be added in combination. From the viewpoint of the solubility of polyphenylene ether (b) to asphalt, it is preferable to prepare a thermoplastic resin composition (d) by extrusion-blending the copolymer (a) and polyphenylene ether (b). It is preferable to add the copolymer (a) and the thermoplastic resin composition (d) from the viewpoint of the solubility of the polyphenylene ether (b) to the asphalt and the low-temperature physical properties of the asphalt composition. ) Particles. By extruding the copolymer (a) and the polyphenylene ether (b) in advance, the polyphenylene ether (b) can be finely dispersed in the particles of the thermoplastic resin composition (d). As a result, in When the particles are dissolved in the asphalt, the polyphenylene ether (b) is slightly dispersed in advance, so that the solubility of the polyphenylene ether (b) tends to be improved.

In addition, as a method of extruding and blending the copolymer (a) and the polyphenylene ether (b), a biaxial extruder (manufactured by Ikegai Co., Ltd., "PCM-30") is used for melting. Method of mixing. The cylinder temperature is preferably appropriately set according to the type of the copolymer (a), and the rotation speed of the screw can be set to 150 rpm, for example, and the ejection amount can be set to 7 kg / h. Residual volatiles can be removed by providing an opening (exhaust hole) in the cylinder block and performing vacuum suction. The degree of pressure reduction (pressure) is preferably -0.05 MPa-G or less, more preferably -0.07 MPa-G or less, still more preferably -0.08 MPa-G or less, and even more preferably -0.09 MPa-G or less. The "G" means a gauge pressure when the atmospheric pressure is set to 0. The strand extruded from the die mouth is cooled and continuously cut with a cutter to obtain pellets. The size of the particles also depends on the specific application, for example, it can be set to about 3 mm length × 3 mm diameter. Regarding the cylinder temperature, when the double bond included in the conjugated diene monomer unit of the copolymer (a) is hydrogenated, it is preferably set to 250 ° C on the upstream side to 300 ° C on the downstream side. When it is not hydrogenated, it is preferably set to 250 ° C on the upstream side to 250 ° C on the downstream side.

According to the method described above, the thermoplastic resin composition (d) may have an island structure including an ocean phase composed of the copolymer (a) and an island phase composed of the polyphenylene ether (b). The polyphenylene ether (b) is uniformly dispersed and / or compatible with the copolymer (a). In addition, in the present specification, the state in which the polyphenylene ether is uniformly dispersed means a state in which polyphenylene ether aggregates having a particle size of 50 μm or more are included in a volume of less than 5% by volume of the entire polyphenylene ether. In addition, the state in which the polyphenylene ether is compatible means a state in which the average dispersed particle diameter of the polyphenylene ether is less than 5 μm.

The state in which the polyphenylene ether (b) is uniformly dispersed and compatible with the copolymer (a) can be easily confirmed using a transmission electron microscope (TEM) or the like. Specifically, a dyeing test piece having a length of 10 mm × width 5 mm × thickness of 3 to 4 mm was cut out from a molded piece of the thermoplastic resin composition (d), and an ultra-thin microtome was used to prepare an end portion of the dyeing test piece. Cut out the plane for cutting. Then, in a non-hydrogenated product of a block copolymer containing "a polymer block containing at least one vinyl aromatic monomer as a host and at least one polymer block containing a conjugated diene monomer as a host "And / or" non-hydrogenated product comprising a copolymer block of at least one vinyl aromatic monomer and at least one conjugated diene monomer "as the copolymer (a), the above-mentioned dyeing is used The test piece was immersed in a 2% by mass aqueous solution of osmium tetrachloride in a heat-resistant container, heated at 80 ° C for 30 minutes in a water bath, and then pulled and cooled to normal temperature, and then taken out of the heat-resistant container and carried out Wash and dry. By the above-mentioned dyeing operation, the above-mentioned "block copolymer comprising at least one polymer block having a vinyl aromatic monomer as a main body and at least one polymer block having a conjugated diene monomer as a main body "Non-hydride" and / or the above-mentioned "Non-hydride containing a copolymer block of at least one vinyl aromatic monomer and at least one conjugated diene monomer" were stained, and black was observed upon TEM observation . Furthermore, in a hydride containing a "block copolymer comprising at least one polymer block mainly composed of a vinyl aromatic monomer and at least one polymer block mainly composed of a conjugated diene monomer" And / or "Hydride of a copolymer block containing at least one vinyl aromatic monomer and at least one conjugated diene monomer" as the copolymer (a), a diamond with water will be added A knife was installed on the ultra-thin microtome, and for the above-mentioned dyeing test piece, a film with a thickness of 85 nm was cut from the plane used for slicing and cutting on water, and was cut with a Cu sieve for TEM observation. The Cu sieve on which the film was carried was previously arranged on a stainless steel net. In addition, 0.1 g of ruthenium trichloride n hydrate and 1 mL of purified water were added to a petri dish in a glass drier, and after dissolving, 5 mL of sodium hypochlorite solution was added, and a stainless steel net carrying a Cu mesh was immediately placed. The Cu sieve was loaded with a film. After the glass dryer was covered and left for 4 minutes, the Cu sieve was taken out. With the above dyeing operation, "the hydrogenation of a block copolymer comprising at least one polymer block having a vinyl aromatic monomer as a main body and at least one polymer block having a conjugated diene monomer as a main body. ”And / or“ Hydride of a copolymer block containing at least one vinyl aromatic monomer and at least one conjugated diene monomer ”was stained, and black was observed upon TEM observation.

By using the dyeing method described above, TEM observation can be performed using the copolymer (a) as a black phase and the polyphenylene ether (b) as a white phase. Furthermore, image analysis of this TEM image photograph was performed using commercially available image analysis software, whereby the area fraction of polyphenylene ether aggregates with a particle size of 50 μm or more with respect to all polyphenylene ethers, And the average dispersed particle size of polyphenylene ether. Here, the area fraction of polyphenylene ether aggregates having a particle size of 50 μm or more with respect to all polyphenylene ethers is considered to be the same as that of polyphenylene ether aggregates having a particle size of 50 μm or more with respect to all polyphenylene ethers. The phenyl ether has the same volume fraction. By the above operation, the state of "uniform dispersion" and "compatible" of the polyphenylene ether (b) with respect to the copolymer (a) can be confirmed.

In the asphalt composition of the present embodiment, regarding the average dispersion particle diameter of the polyphenylene ether (b) and the copolymer (a) constituting the thermoplastic resin composition (d), in terms of the high ductility of the asphalt composition, the pitch From the standpoint of the separability of the composition, it is preferably less than 5 μm, more preferably less than 4 μm, still more preferably less than 3.5 μm, and even more preferably less than 3 μm. The average dispersion particle diameter of the polyphenylene ether (b) can be controlled to the above-mentioned numerical range by adjusting the temperature during melt-kneading or adjusting the number of stirring revolutions during melt-kneading.

The pellets of the thermoplastic resin composition (d) used in the pitch composition of the present embodiment preferably contain a lubricant from the viewpoint of the moldability of the pellets of the thermoplastic resin composition (d). The lubricant is not limited to the following, and examples thereof include hydrocarbon-based lubricants such as paraffin wax, microwax, and polyethylene wax; butyl stearate, monoglyceryl stearate, pentaerythritol distearate, and pentaerythritol tetra Fatty acid ester lubricants such as stearates, stearate stearate, and ammonium distearate; magnesium distearate, calcium distearate, zinc distearate, calcium montanate And other fatty acid metal salt lubricants. The added amount of the lubricant is preferably 0 parts 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 of the total of the copolymer (a) and the polyphenylene ether (b). It is more preferably 5 parts by mass or more and 20 parts by mass or less.

The thermoplastic resin composition (d) used in the asphalt composition of the present embodiment preferably contains an antioxidant from the viewpoint of improving heat resistance deterioration. The antioxidant is not limited to the following, and examples include hindered phenol antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like. Specific examples include 2,6-di-third-butyl-4- (4,6-bis (octylthio) -1,3,5-tri-2-ylamino) phenol (BASF Corporation). IRGANOX565 manufactured), pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (IRGANOX1010 manufactured by BASF Corporation, Adekastab AO-60 manufactured by ADEKA Corporation) 1,3,5-trimethyl-2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330 manufactured by BASF), 3- (3, 5-Di-Third-butyl-4-hydroxyphenyl) propanoic stearyl ester (Adekastab AO-50 manufactured by ADEKA), Tris (2,4-di-tert-butylbenzene) Ester) ester (IRGAFOS168 manufactured by BASF, Adekastab 2112 manufactured by ADEKA), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-di Phosphospiro [5,5] undecane (Adekastab PEP-8 manufactured by ADEKA), 3,9-bis (2,6-di-third-butyl-4-methylphenoxy) -2 , 4,8,10-tetraoxa-3,9-diphosphospiro [5,5] undecane (Adekastab PEP-36 manufactured by ADEKA Corporation), phosphoric acid = 2,2'-methylenebis (4,6-di-tert-butylphenyl) = 2-ethylhexyl ester (Adekastab HP-10 manufactured by ADEKA), 3,3'-thiodipropionate di-octadecyl Esters (IRGANOX PS manufactured by BASF) 802FD), N, N-di-octadecylhydroxylamine (IRGASTAB FS042 manufactured by BASF) and the like. These can be used alone or in combination of two or more. The amount of the antioxidant to be added is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass based on 100 parts by mass of the total of the copolymer (a) and the polyphenylene ether (b). It is preferably 0.5 parts by mass or more and 4 parts by mass or less.

(Asphalt (c)) The asphalt composition of the present embodiment contains asphalt (c) (hereinafter, it may be described as the component (c)). The pitch (c) used as the pitch composition of the present embodiment is not limited to the following, and examples thereof include those obtained as a by-product (petroleum pitch) during petroleum refining or a natural product (natural pitch). Or by mixing petroleum with these. Its main component is called bitumen. The bitumen is not limited to the following, and examples thereof include straight run asphalt, semi-blown bitumen, blown bitumen, solvent deasphalt, tar, bitumen, cutback asphalt with oil, bitumen emulsion, and the like. These can be used alone or in combination of two or more. In addition, aromatic heavy mineral oils such as petroleum-based solvent extraction oils, aromatic hydrocarbon-based processing oils, and extracts may be added to various asphalts.

Asphalt (c) used in the asphalt composition of the present embodiment, from the viewpoints of high-temperature physical properties, low-temperature physical properties, and economy, the penetration degree (measured in accordance with JIS-K2207) is preferably 30 or more and 300 or less It is more preferably 40 or more and 200 or less, and even more preferably 45 or more and 150 or less straight run asphalt.

In the asphalt composition of the present embodiment, the content of the asphalt (c) is 80 to 97% by mass, preferably 85 to 97% by mass, and more preferably 87 to 97% in terms of economy and viscosity. 97% by mass.

(Total content of copolymer (a) and polyphenylene ether (b)) Regarding the total content of copolymer (a) and polyphenylene ether (b) in the asphalt composition of this embodiment, the bituminous composition has a higher content. From the viewpoint of the softening point, the higher ductility of the asphalt composition, and the higher peel resistance of the aggregate when the mixture of the asphalt composition and the aggregate is made, it is 2.6% by mass or more, and preferably 3.5% by mass or more , More preferably 5 mass% or more, and even more preferably 6 mass% or more. From the viewpoints of lower viscosity of the asphalt composition, less deterioration of the copolymer (a) in the asphalt composition, and economical efficiency, it is 20% by mass or less, more preferably 16% by mass or less, and more preferably It is 14% by mass or less, and more preferably 12% by mass or less. Generally speaking, in the case of making an asphalt composition, if the addition amount of the copolymer (a) is small, the interaction with the components of the asphalt is insufficient, so the effect on the performance of the asphalt composition is small.

(mass ratio of (a) component and (b) component) Regarding the mass ratio of the copolymer (a) and the polyphenylene ether (b) in the asphalt composition of the present embodiment, the higher the softening point of the asphalt composition From a viewpoint, when (a) + (b) is 100% by mass, the ratio of (b) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and It is more preferably 15% by mass or more. From the viewpoints of low viscosity of the asphalt composition, good low-temperature physical properties, and solubility in asphalt, when (a) + (b) is set to 100% by mass, the ratio of (b) is preferably 80. Mass% or less, more preferably 70 mass% or less, still more preferably 50 mass% or less, and still more preferably 30 mass% or less.

(Form of Asphalt Composition) As a preferred form of the aspect of the asphalt composition of the present embodiment, the following bituminous composition may be mentioned, which contains: as a unit having a vinyl aromatic monomer unit and a conjugated diene monomer unit A thermoplastic resin composition (d) of an extruded body of the copolymer (a) and polyphenylene ether (b) having a reduced viscosity of 0.07 dL / g to 0.60 dL / g, and asphalt (c). The content of the (d) is 3 to 20% by mass, the content of the (c) is 80 to 97% by mass, and the mass ratio of the component (a) to the component (b) in the thermoplastic resin composition (d) (a) / (b) = 20 to 99/80 to 1. The asphalt composition can be produced by mixing an extruded body of the copolymer (a) and the polyphenylene ether (b), for example, a thermoplastic resin composition (d) as a pellet, and the asphalt (c).

In the asphalt composition of the present embodiment described above, from the viewpoints of viscosity and low-temperature elongation, the content of the component (d) is preferably 3 to 15% by mass, and the content of the component (c) is 85 to 97. % By mass, and the mass ratio of the component (a) to the component (b) in the component (d) (a) / (b) = 40 to 99/60 to 1.

(Other materials) The asphalt composition of this embodiment can be blended with any petroleum resin as required. The addition of petroleum resin tends to improve the adhesion between the asphalt composition and the aggregate when it is made into a mixture with the aggregate, and can suppress peeling. The type of petroleum resin is not limited to the following, and examples thereof include aliphatic petroleum resins such as C5 petroleum resin, aromatic petroleum resins such as C9 petroleum resin, and cycloaliphatic resins such as dicyclopentadiene petroleum resin. Petroleum resins such as petroleum resins, C5 / C9 copolymerized petroleum resins, and hydrogenated petroleum resins obtained by hydrogenating these petroleum resins. The blending amount of the petroleum resin is not particularly limited, but it is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 2 parts by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the asphalt (c).

The asphalt composition of this embodiment can be blended with any additives as needed. The type of the additive is not particularly limited as long as it is generally used for blending thermoplastic resins or rubber-like polymers. Examples include: calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, oxidation Non-polar fillers such as zinc, slag wool, and glass fiber; pigments such as carbon black and iron oxide; stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and diethylstearate Lubricants such as amines; release agents, paraffin-based processing oils, naphthenic-based processing oils, aromatic-based processing oils, paraffin, organic polysiloxanes, mineral oils and other softeners and plasticizers; hindered phenol Antioxidants, phosphorus-based thermal stabilizers and other antioxidants; hindered amine-based light stabilizers, benzotriazole-based ultraviolet absorbers, flame retardants, antistatic agents; organic fibers, glass fibers, carbon fibers, metal whiskers and other reinforcing agents; Examples of the colorant include additives other than these, or mixtures thereof, and those described in "Rubber and Plastic Blended Drugs" (edited by Japan Rubber Digest). The blending amount of the additives is not particularly limited, but it is usually 50 parts by mass or less based on 100 parts by mass of the asphalt (c).

An anti-stripping agent may be added to the asphalt composition of the present embodiment in order to prevent the asphalt composition from being peeled from the aggregate when it is made into a mixture with the aggregate.

As the anti-stripping agent, a resin acid is preferable, and examples thereof include polycyclic terpenes having a carboxyl group of 20 carbon atoms, and containing abietic acid, dehydroabietic acid, neo-rosin acid, pisaric acid, isopimaric acid, long Any one or more of rosin acids. In addition, in order to function as an anti-stripping agent and a lubricant, a fatty acid or fatty acid ammonium may be added.

The asphalt composition of this embodiment may contain other polymers in addition to the copolymer (a). Other polymers are not limited to the following, and examples thereof include olefin-based elastomers such as natural rubber, polyisoprene rubber, polybutadiene rubber, styrene butadiene rubber, and ethylene-propylene copolymers; neoprene Diene rubber, acrylic rubber, ethylene-vinyl acetate copolymer, etc.

From the viewpoints of softening point, melt viscosity, and low-temperature elongation, the asphalt composition of the present embodiment preferably contains 1 to 10% by mass of a styrene-butadiene-styrene copolymer (SBS). It is more preferably 3 to 10% by mass, and even more preferably 5 to 10% by mass.

[Production Method of Asphalt Composition] The method for producing the asphalt composition of the present embodiment is not particularly limited, and it can be produced by appropriately mixing the components (a) to (d). The conditions for stirring the copolymer (a), the polyphenylene ether (b), and / or the mixture of the thermoplastic resin composition (d) and the asphalt (c) are not particularly limited. The limitation 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, and from the viewpoint of economy, a shorter stirring time is preferable. The stirring speed can be selected in a timely manner according to the device used, and is usually 100 ppm or more and 8,000 rpm or less.

[Application] The asphalt composition of this embodiment can be applied to the fields of road paving, roofing materials, waterproof sheets, and sealants, and can be compared to the fields of road paving, roofing materials, and waterproof sheets. Good application.

For road paving, an example in which a large amount of aggregate is mixed with the asphalt composition of the present embodiment is used. Hereinafter, those containing an asphalt composition and aggregate are referred to as an asphalt mixture. There is no limitation on the aggregate material. For example, as long as it is the aggregate for paving described in the "Asphalt Paving Outline" issued by the Japan Road Association, it is not limited to the following, and examples include gravel, pebble, Gravel, steel slag, etc. In addition, it can also be used in asphalt-coated aggregates and recycled aggregates made of such aggregate-coated asphalt. In addition, similar granular materials such as artificial calcined aggregate, calcined foamed aggregate, artificial lightweight aggregate, ceramic granules, roxbyite, aluminum granules, plastic granules, ceramics, Emery, construction waste, fiber, etc. Aggregates are generally roughly divided into coarse aggregates, fine aggregates, and fillers. The so-called coarse aggregate is an aggregate that ends in a 2.36 mm sieve. Generally speaking, there are No. 7 crushed stones with a particle size range of 2.5 to 5 mm, No. 6 crushed stones with a particle size range of 5 to 13 mm, and a particle size range of 13 No. 5 crushed stone with a size of 20 to 20 mm, and no. 4 crushed stone with a particle size range of 20 to 30 mm. In this embodiment, one or two types of coarse aggregates with various particle sizes can be used. Aggregate made from the above, or synthetic aggregate. About these coarse aggregates, it is also possible to coat the aggregates with about 0.3 to 1% by mass of straight run asphalt. The so-called fine aggregate refers to the aggregate passing through a 2.36 mm sieve and ending with a 0.075 mm sieve, and is not limited to the following. , Silica sand, artificial sand, glass shavings, casting sand, recycled aggregate crushed sand, etc. The so-called fillers are those that pass through the 0.075 mm sieve, and are not limited to the following. For example, the fillers are sieve dust, stone powder, slaked lime, cement, incinerator ash, clay, talc, fly ash, carbon black, etc. It is rubber powder, cork powder, wood powder, resin powder, fiber powder, pulp, artificial aggregate, etc., as long as it passes through 0.075 mm sieve, it can be used as filler. The coarse aggregate, the fine aggregate, and the filler may be used singly alone, but generally, two or more kinds are used in combination. The content of the aggregate in the asphalt mixture containing the asphalt composition and the aggregate is preferably 85% by mass or more from the viewpoint of obtaining a mixture having higher resistance to mass loss or higher reduction in strength when oil is adhered. The range of 98% by mass or less is more preferably 90% by mass or more and 97% by mass or less. The method for producing an asphalt mixture containing an asphalt composition and an aggregate is not particularly limited, and examples thereof include a method in which the mixing temperature of the asphalt composition and the aggregate is generally within a range of 120 ° C to 200 ° C and mixed . In addition, if necessary, it can be emulsified and used in water of asphalt composition. [Example]

Hereinafter, the present invention will be described in detail with specific examples and comparative examples, but the present invention is not limited to the following examples. The measurement methods of the copolymer and the asphalt composition in Examples and Comparative Examples are shown below.

[Measurement method] (Block content of vinyl aromatic monomer in block copolymer) The copolymer before hydrogenation was used as the measurement object, and IM Kolthoff, et. Al, J. Polym. Sci. 1, p. 429 The osmium tetroxide method according to (1946) measures the vinyl aromatic monomer block content of the copolymer. In the decomposition of the copolymer, a 0.1 g / 125 mL tertiary butanol solution of osmic acid was used.

(The ethylene bond amount of the block copolymer, the hydrogenation rate of the unsaturated group in the conjugated diene monomer unit, and the content of the vinyl aromatic monomer unit) According to nuclear magnetic resonance spectrum analysis (NMR), The amount of ethylene bonds in the block copolymer, the hydrogenation rate of the unsaturated group in the conjugated diene monomer unit, and the content of the vinyl aromatic monomer unit were measured under the conditions. The reaction solution after the hydrogenation of the block copolymer is put into a large amount of methanol and precipitated, whereby the hydrogenated block copolymer is precipitated and recovered. Then, the hydrogenated block copolymer was extracted with acetone, and the extract was vacuum-dried to be used as a sample for ¹ H-NMR measurement. The conditions for ¹ H-NMR measurement are described below. <Measurement conditions> Measurement equipment: JNM-LA400 (manufactured by JEOL) Solvent: Deuterium chloroform Measurement sample: Sample before and after hydrogenation of polymer Sample concentration: 50 mg / mL Observation frequency: 400 MHz Chemical shift standard: TMS (tetramethyl Silane) Pulse delay: 2.904 seconds Scans: 64 pulses: 45 ° Measurement temperature: 26 ° C

(Weight-average molecular weight) The weight-average molecular weight is measured by GPC [manufactured by Device Waters]. Tetrahydrofuran was used as the solvent, and the temperature was set to 35 ° C. For the peak molecular weight of the chromatogram, a weight average molecular weight (polystyrene-equivalent molecular weight) was obtained by using a calibration curve (produced using the peak molecular weight of standard polystyrene) obtained by measurement of commercially available standard polystyrene.

(MFR) MFR is calculated by a method based on JIS K7210 using a melt index tester (L247; manufactured by TECHNOLSEVEN CO., LTD). The test temperature is 200 ° C, the test load is 5.00 kgf, and the unit of the measured value is expressed in g / 10 min.

(Reduced viscosity of polyphenylene ether) The reduced viscosity of polyphenylene ether was obtained by dissolving 0.5 g of polyphenylene ether (b) in 100 mL of chloroform to make a solution, and measuring it at 30 ° C using a Ubbelohde viscometer.

[Manufacturing method of copolymer] (Block copolymer 1) <First-stage polymerization> A stainless steel autoclave with a content of 10 L with a stirrer and a sleeve was washed, dried, and replaced with nitrogen. To this autoclave was added 5,720 g of cyclohexane and 240 g of styrene that had been purified in advance, and warm water was passed through the sleeve to set the content to about 40 ° C.

Then, an n-butyllithium cyclohexane solution (0.70 g in pure amount) was added to the autoclave to start polymerization of styrene.

<Second-stage polymerization> After the styrene has been polymerized, 7 minutes after reaching the maximum temperature (51 ° C), the maximum temperature is decreased by 2 ° C, and then butadiene (1,3 -Butadiene) 560 g, and the polymerization was continued. Butadiene was almost completely polymerized. Thirty seconds after reaching the maximum temperature (90 ° C), in the above-mentioned autoclave, the dichloromethane of 2,2-bis (4-hydroxyphenyl) propane was shrunk using epichlorohydrin. A mixture of glycerol etherification modified product and phenol / formaldehyde polycondensate with a mass ratio of 1/1 of diglycidyl etherification modified product of epichlorohydrin is added to be 0.4 mol / Li as a coupling agent, Thereby, coupling is performed.

Ten minutes after the addition of the coupling agent, water was added to the autoclave and deactivated to obtain a block copolymer solution.

To the solution of the obtained block copolymer, 3- (3,5-dibutyl-third butyl-4-hydroxyphenyl) was added in an amount of 0.25 part by mass based on 100 parts by mass of the above-mentioned block copolymer. Octadecyl propionate was used as a stabilizer, and the block copolymer 1 was obtained by sufficiently mixing. The obtained block copolymer 1 is a mixture of block copolymers, the ratio of the structure is SB / (SB) ₂ -X = 20/80% by mass, and the weight average molecular weight of the block copolymer of the SB structure is 90,000. The weight average molecular weight of the (SB) _2- X block copolymer is twice the weight average molecular weight of the SB structure. The content of the vinyl aromatic monomer unit was 30% by mass, and the MFR (200 ° C, 5 kgf) was 0.2 g / 10 min. The vinyl aromatic monomer block content was 30% by mass, and the amount of ethylene bonds was 11% by mass. In the above formula, S represents a polymer block having a vinyl aromatic monomer unit as a main body, and B represents a polymer block having a conjugated diene monomer unit as a main body. X represents a residue of a coupling agent or a residue of a polymerization initiator such as a polyfunctional organolithium.

(Block copolymer 2) In the above-mentioned "second-stage polymerization", the coupling agent was changed to silicon tetrachloride and added so as to become 0.2 mol / Li. The other conditions are that the block copolymer 2 is obtained by the same method as the above (block copolymer 1). The obtained block copolymer 2 is a mixture of block copolymers, the ratio of the structure is SB / (SB) ₄ -X = 20/80% by mass, and the weight average molecular weight of the block copolymer of the SB structure is 90,000. The weight average molecular weight of the (SB) _4- X block copolymer is 4 times the weight average molecular weight of the SB structure. The content of the vinyl aromatic monomer unit was 30% by mass, and the MFR (200 ° C, 5 kgf) was 0.01 g / 10 min. The vinyl aromatic monomer block content was 30% by mass, and the amount of ethylene bonds was 11% by mass.

(Block copolymer 3) <Preparation of hydrogenation catalyst> Add 1 L of dried and refined cyclohexane to a reaction vessel substituted with nitrogen, and add 100 mmol of bis (cyclopentadienyl) titanium dichloride. While stirring well, a n-hexane solution containing 200 mmol of trimethylaluminum was added and reacted at room temperature for about 3 days to obtain a hydrogenation catalyst. <Polymerization> In the <First-stage polymerization> of the above (block copolymer 1), the amount of n-butyllithium cyclohexane solution and the amount of styrene were changed, and tetramethylenediamine was added. In the second-stage polymerization>, the amount of butadiene was changed, without using a coupling agent, and as the "third-stage polymerization", styrene was polymerized with the same amount of styrene as the first-stage polymerization. Thereafter, water was added and deactivated, and then 98 mol% of the double bond in the conjugated diene monomer unit in the block copolymer was hydrogenated using the hydrogenation catalyst to obtain a block copolymer solution. Thereafter, a block copolymer 3 was obtained by the same method as (block copolymer 1). The obtained block copolymer had a S-B-S structure of 3 and a weight average molecular weight of 70,000. The content of the vinyl aromatic monomer unit was 40% by mass, and the MFR (200 ° C, 5 kgf) was 0.5 g / 10 min. The vinyl aromatic monomer block content was 29% by mass, and the amount of ethylene bonds was 40% by mass.

(Block copolymer 4) In the <First-stage polymerization> of (block copolymer 1) above, change the amount of n-butyllithium cyclohexane solution and the amount of styrene, and add tetramethylene di For amine, styrene and butadiene were continuously added in the second-stage polymerization without using a coupling agent. Finally, as the third-stage polymerization, benzene was used in the same amount of styrene as in the first stage. Polymerization of ethylene. Thereafter, water was added and deactivated, and then the hydrogenation catalyst prepared in the above-mentioned (block copolymer 3) production method was used to make 98% of the double bonds in the conjugated diene monomer unit in the block copolymer. The mol% was hydrogenated to obtain a block copolymer solution. Thereafter, a block copolymer 4 was obtained by the same method as (block copolymer 1). The obtained block copolymer 4 had an S-R-S structure and a weight average molecular weight of 150,000. R represents a copolymer block including a vinyl aromatic monomer unit and a conjugated diene monomer unit. The content of the vinyl aromatic monomer unit was 50% by mass, and the MFR (200 ° C, 5 kgf) was 3 g / 10 min. The vinyl aromatic monomer block content was 15% by mass, and the amount of ethylene bonds was 20% by mass.

(Block copolymer 5) In the first-stage polymerization of (block copolymer 1), styrene was changed to butadiene, and in the second-stage polymerization, styrene and butadiene were changed. Diene was added at a certain ratio, and then styrene was further added as <polymerization in the third stage>. Styrene and butadiene were added in a certain ratio as <polymerization in the fourth stage>. Polymerization of styrene was carried out at the same amount of styrene at each stage. Thereafter, water was added and deactivated, and then a block copolymer 5 was obtained by the same method as (block copolymer 1). The block copolymer 5 has a B-S-B-S structure and a weight average molecular weight of 100,000. The content of the vinyl aromatic monomer unit was 40%, and the MFR (200 ° C, 5 kgf) was 13 g / 10 min. The vinyl aromatic monomer block content was 35% by mass, and the amount of ethylene bonds was 11% by mass.

(Block copolymer 6) In the above-mentioned (block copolymer 1), the second-stage polymerization, the coupling agent was changed to a 1,3-bis (N, N'-diglycidylamine methyl) ring. Hexane was added so as to be 0.23 mol / Li. The other conditions are that a block copolymer 6 is obtained by the same method as the above (block copolymer 1). The mixture of the obtained block copolymer 6-series block copolymer has a structure ratio of SB / [(SB) ₂ -X + (SB) ₃ -X ＋ (SB) ₄ -X] = 20/80% by mass, SB The weight average molecular weight of the structured block copolymer is 90,000, and the weight average molecular weight of (SB) ₂ -X + (SB) ₃ -X + (SB) ₄ -X is 3.7 times the weight average molecular weight of the SB structure. The content of the vinyl aromatic monomer unit was 30% by mass, and the MFR (200 ° C, 5 kgf) was 0.01 g / 10 min. The vinyl aromatic monomer block content was 30% by mass, and the amount of ethylene bonds was 12% by mass.

[Examples 1 to 23], [Comparative Examples 1 to 7] (Production of Asphalt Composition) 500 g of straight run asphalt (made by Shin Nippon Oil Co., Ltd.) was put into a 750 mL metal tank, and the metal The tank was fully immersed in an oil bath at 160 ° C. Next, while stirring the molten asphalt at a speed of 4000 rpm, the specific amounts of the block copolymer (a), polyphenylene ether (b), and the following thermoplastics are used as shown in Tables 2 to 4 below. The resin composition particles (d) are added to the above-mentioned asphalt, and the mixture is stirred for 90 minutes after the addition to prepare an asphalt composition.

As the polyphenylene ether (b), the following was used. The reduced viscosity of polyphenylene ether 1 was 0.33 dL / g. The reduced viscosity of polyphenylene ether 2 was 0.07 dL / g. The reduced viscosity of polyphenylene ether 3 was 0.60 dL / g. The reduced viscosity of polyphenylene ether 4 was 0.70 dL / g. The reduced viscosity of polyphenylene ether 5 was 0.39 dL / g.

Polyphenylene ether 5 is prepared by melting 100 parts by mass of polyphenylene ether having a reduced viscosity of 0.40 dL / g and 2 parts by mass of maleic anhydride (Crystal Man, manufactured by Nippon Oil & Fats Co., Ltd.) using a biaxial extruder. Obtained by mixing. At this time, the addition amount of maleic anhydride was measured by IR and calculated to be 0.5% by mass based on 100% by mass of the polyphenylene ether.

In addition, in Examples 7 to 13, 15, 16, 19, and 21, a thermoplastic resin combination produced by coextrusion molding of the block copolymer (a) and the polyphenylene ether (b) was used.物 粒 (d).

Furthermore, in Example 14, the block copolymer 1 and the thermoplastic resin composition particle (d) containing the block copolymer 4 and the polyphenylene ether 1 were used, respectively.

(Production of Asphalt Mixture) In a 27-liter capacity mixer equipped with a heating device, 94.5 parts by mass of the dense-grain type aggregate having the particle size shown in Table 1 below was put, and dry stirring was performed for 25 seconds. Then, 5.5 parts by mass of the asphalt composition produced by the above-mentioned method was put into the above-mentioned mixer, and the mixture was officially stirred for 50 seconds to obtain the asphalt mixtures of Examples 1 to 23 and Comparative Examples 1 to 7. The obtained asphalt mixture is a dense-grain type asphalt mixture. In addition, the total amount of the asphalt mixture was set to 10 kg, and the mixing temperature was adjusted to 177 ° C with dry stirring and formal stirring. The aggregates used are crushed stone and sand from Iwaku-cho, Shimotoga-gun, Tochigi Prefecture, fine sand from Sakae-machi, Inba-gun, Chiba Prefecture, and stone powder from Yamato-cho, Sano, Tochigi. Of a mixture. The particle size distribution of the aggregate used in the asphalt mixture is shown in Table 1 below.

[Table 1]

[Evaluation of Asphalt Composition and Asphalt Mixture] The physical properties of the asphalt composition and the asphalt mixture produced as described above were measured by the following methods. The measurement results are shown in Tables 2 to 4.

(Softening Point of Asphalt Composition) The softening point of the asphalt composition was measured by a ring and ball method in accordance with JIS-K2207. Fill the specified ring with the sample, support it horizontally in the glycerol solution, and place a 3.5 g ball in the center of the sample to increase the liquid temperature at a rate of 5 ° C / min. Temperature when contacting the bottom plate of the ring platform. The bituminous composition has a higher softening point, and the fluidity resistance is good, and it is evaluated as 良好, ○, △, and × from good to poor based on the following criteria. <Evaluation criteria> The softening point is 112 ° C or higher: ◎ The softening point is 105 ° C or higher and less than 112 ° C: ○ The softening point is 98 ° C or higher and less than 105 ° C: △ The softening point is lower than 98 ° C: ×

(Melting Viscosity of Asphalt Composition) The melt viscosity of the asphalt composition at 160 ° C was measured with a Brookfield viscometer. The bituminous composition has good manufacturability with a lower melt viscosity, and is evaluated as ◎, ○, △, and × based on the following criteria and in the order of good. <Evaluation 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 1500 mPa · s or more: ×

(Asphalt Compatibility in Asphalt Composition) The average particle diameter of the polyphenylene ether in the production of the asphalt composition was measured. As a measuring method, observation was performed using transmitted light using a digital microscope. The measurement apparatus and measurement conditions are as follows. <Measuring device> Digital microscope VHX-2000 manufactured by KEYENCE Corporation <Measuring conditions> Measuring temperature: 25 ° C Measuring magnification: 2000 times Measuring mode: transmitted light Measuring object: polyphenylene ether (bright white portion). The asphalt is brown, and the elastic system is dark white. Sample preparation method: Take 10 mg of the asphalt composition under stirring onto a glass slide, and leave it on a heating plate heated to 180 ° C for 20 seconds to melt it. Thereafter, the cover glass is placed on the molten asphalt composition to make it thin and stretched. After leaving at room temperature for 30 minutes, observation was performed with a digital microscope. The smaller average particle diameter of the polyphenylene ether in the asphalt composition was high-temperature storage properties and low-temperature properties, and was evaluated as ◎, ○, △, and × based on the following criteria and in the order of good. <Evaluation criteria> The average particle diameter is less than 10 μm: ◎ The average particle diameter is 10 μm or more and less than 25 μm: ○ The average particle diameter is 25 μm or more and less than 50 μm: △ The average particle size is 50 μm or more: ×

(Elongation of Asphalt Composition) According to JIS-K2207, the sample was flowed into the frame to form a predetermined shape, and then maintained at 15 ° C in a constant temperature water bath, and then the sample was pulled at a speed of 5 cm / min. At the time of stretching, the distance (elongation) at which the sample extends until it breaks is measured. The bituminous composition had a higher elongation resistance at low temperature cracking resistance, and was evaluated as ○, ○, △, × based on the following criteria and in the order of good. <Evaluation Criteria> Elongation of 80 cm or more: ◎ Elongation of 65 cm or more and less than 80 cm: ○ Elongation of 50 cm or more and less than 65 cm: △ Elongation of 50 cm or less: ×

(Asphalt Separability of Asphalt Composition) The separability of the asphalt composition after high-temperature storage was evaluated. As a measuring method, a sample was poured into a Teflon (registered trademark) pipe body having a diameter of 2.5 cm and a length of 15 cm, and was covered with an aluminum sheet, and then subjected to 175 ° C for 72 hours in an oven. Let stand. After that, after being stored in a freezer for one hour, the asphalt composition was divided into three equal parts in the longitudinal direction. The softening points of the upper layer and the lower layer were measured separately, and the softening point difference was obtained. Those with a small softening point had good high-temperature storage stability and low-temperature performance, and were evaluated as ◎, ○, △, and × based on the following criteria and in the order of excellence. <Evaluation criteria> The softening point is below 2 ° C: ◎ The softening point is below 6 ° C: ○ The softening point is below 10 ° C: △ The softening point exceeds 10 ° C: ×

(Rutting Resistance of Asphalt Mixtures) The asphalt mixtures produced according to the above-mentioned examples of the production of asphalt mixtures were used as test bodies in accordance with the test method manual B003. On a test body of a specific size, a small rubber wheel with a load is repeatedly moved back and forth at a specified temperature, a specified time, and a specified speed, and the dynamic stability (times / mm) is obtained based on the amount of deformation per unit time. The higher the dynamic stability, the better the rut resistance. Based on the following criteria and in the order of good, they were evaluated as ◎, ◯, △, and ×. <Evaluation criteria> Dynamic stability is 13,000 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: ×

[Table 2]

[table 3]

[Table 4]

This application is based on a Japanese patent application filed with the Japan Patent Office on June 14, 2017 (Japanese Patent Application No. 2017-116680), and a Japanese patent application filed with the Japan Patent Office on December 20, 2017 (Japanese Patent The contents of this article are hereby incorporated by reference. [Industrial availability]

The asphalt composition of the present invention has industrial applicability in the fields of road paving, roofing materials, waterproof sheets, and sealants.

Claims (13)

An asphalt composition comprising: a copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit, and a polyphenylene ether (b) having a specific viscosity of 0.07 dL / g to 0.60 dL / g And asphalt (c), the content of (a) is 2.5 to 14% by mass, the content of (b) is 0.1 to 10% by mass, and the content of (c) is 80 to 97% by mass. The asphalt composition according to claim 1, wherein the polyphenylene ether (b) has a modifying group, and the modifying group includes a group selected from a carboxyl group and / or derived from a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, and an amine group. At least one functional group in the group consisting of sulfonylamino, silanol, and alkoxysilyl. The asphalt composition according to claim 1 or 2, wherein the polyphenylene ether (b) has a carboxyl group and / or a group derived from a carboxyl group. For example, the asphalt composition of claim 1 or 2, wherein the content of (a) is 4 to 14% by mass, the content of (b) is 0.1 to 8% by mass, and the content of (c) is 80 to 97% %. For example, the asphalt composition of claim 1 or 2, wherein the content of (a) is 4 to 12% by mass, the content of (b) is 0.1 to 5% by mass, and the content of (c) is 85 to 97% %. The asphalt composition according to claim 3, wherein the content of (a) is 4 to 12% by mass, the content of (b) is 0.1 to 5% by mass, and the content of (c) is 85 to 97% by mass. An asphalt composition comprising: a thermoplastic resin composition (d), which is a copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit and a reduced viscosity of 0.07 dL / g to 0.60 dL / g extruded body of polyphenylene ether (b); and bitumen (c); the content of (d) is 3 to 20% by mass, the content of (c) is 80 to 97% by mass, and the above The mass ratio (a) / (b) of the above-mentioned (a) and (b) in the thermoplastic resin composition (d) is 20 to 99/80 to 1. The asphalt composition according to claim 7, wherein the thermoplastic resin composition (d) has a sea-island structure, and the sea-island structure includes a marine phase composed of the copolymer (a) and an island composed of the polyphenylene ether (b). Phase, and the average dispersed particle diameter of the polyphenylene ether (b) in the thermoplastic resin composition (d) is less than 5 μm. For example, the asphalt composition of claim 7 or 8, wherein the content of (d) is 3 to 15% by mass, the content of (c) is 85 to 97% by mass, and (a) and (a) above The mass ratio (a) / (b) of (b) above is 40 to 99/60 to 1. The asphalt composition according to claim 7 or 8, wherein the thermoplastic resin composition (d) contains an antioxidant. The asphalt composition according to claim 7 or 8, wherein the above-mentioned copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit is hydrogenated. The asphalt composition according to claim 7 or 8, further comprising 1 to 10% by mass of a styrene-butadiene-styrene copolymer (SBS). The asphalt composition of 2, 7 or 8, wherein the above-mentioned copolymer (a) having a vinyl aromatic monomer unit and a conjugated diene monomer unit has a modifying group containing a functional group.