WO2018230299A1 - 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.

Conventionally, asphalt compositions have been widely used for road pavement, waterproof sheets, sound insulation sheets, roofing and the like.
When the asphalt composition is used for various purposes, many attempts have been made to add various polymers to the asphalt to improve its properties.
Examples of 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.

On the other hand, in recent years, demands for improving the high-temperature physical properties of asphalt compositions are increasing from the viewpoint of increasing traffic and global warming.

Conventionally, in order to improve the high temperature physical properties of the asphalt composition, a technique for improving the high temperature physical properties of the asphalt composition by incorporating various additives has been proposed (see, for example, Patent Documents 1 to 3).
Specifically, polyphenylene ether is added as an additive to improve the softening point of an asphalt composition, or atactic polypropylene is added as an additive to improve the softening point of an asphalt composition, or styrene is used as an additive. A technique for adding a butadiene-styrene copolymer (SBS) to improve the softening point of an asphalt composition is known.

International Publication No. 2002/042377 JP-A-1-282235 JP-A-6-41439

However, even in the techniques disclosed in Patent Documents 1 to 3, sufficient characteristics have not yet been obtained with respect to the high temperature physical properties of the asphalt composition, and further improvement of the high temperature physical properties of the asphalt composition is desired. ing.
As a result of investigation by the present inventor, the technique described in 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.
Moreover, 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 that as the amount of the additive increases, the viscosity of the asphalt composition increases and the processability is inferior.

Therefore, 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.

As a result of intensive studies to solve the above-described problems of the prior art, 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.

[1]
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,
An asphalt composition.
[2]
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 asphalt composition according to the above [1], which has a modifying group.
[3]
The asphalt composition according to [1] or [2], wherein the polyphenylene ether (b) has a carboxyl group and / or a group derived from a carboxyl group.
[4]
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].
[5]
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].
[6]
Extruded molded product of copolymer (a) having vinyl aromatic monomer unit and conjugated diene monomer unit and polyphenylene ether (b) having reduced viscosity of 0.07 dL / g to 0.60 dL / g A thermoplastic resin composition (d),
Asphalt (c),
An asphalt composition comprising:
The content of (d) is 3 to 20% by mass,
The content of (c) is 80 to 97% by mass,
In the thermoplastic resin composition (d), the mass ratio between (a) and (b) is as follows:
(A) / (b) = 20 to 99/80 to 1,
Asphalt composition.
[7]
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 asphalt composition as described in [6] above, wherein an average dispersed particle diameter of the polyphenylene ether (b) in the thermoplastic resin composition (d) is less than 5 μm.
[8]
The content of (d) is 3 to 15% by mass,
The content of (c) is 85 to 97% by mass,
In (d), the mass ratio of (a) to (b) is (a) / (b) = 40 to 99/60 to 1.
Asphalt composition as described in said [6] or [7].
[9]
The asphalt composition according to any one of [6] to [8], wherein the thermoplastic resin composition (d) contains an antioxidant.
[10]
The asphalt composition according to any one of [6] to [9], wherein the copolymer (a) having the vinyl aromatic monomer unit and the conjugated diene monomer unit is hydrogenated. .
[11]
The asphalt composition according to any one of [6] to [10], further containing 1 to 10% by mass of a styrene-butadiene-styrene copolymer (SBS).
[12]
The copolymer (a) having the vinyl aromatic monomer unit and the conjugated diene monomer unit,
The asphalt composition according to any one of [1] to [11], which has a modifying group composed of a functional group.

According to the present invention, 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.

Hereinafter, 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]
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.

Here, 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”. .

(Copolymer (a))
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. Further, 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.
In the present specification, “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 | limiting in particular in an upper limit, It is preferable that it is 100 mass% or less, and it is preferable that it is 99 mass% or less.
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.

In this embodiment, 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).

(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- (S-R) _n (ix)
S- (RS) _n -X (x)
[(SR) _k ] _m -X (xi)
[(S−R) _k −S] _m −X (xii)

In the above 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, and 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, and 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.

When a plurality of blocks S, B, and R are present in the block copolymer (a), structures such as molecular weight and composition may be the same or different.

As described above, in the formulas (iv) to (vi) and (x) to (xii), 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.

From the viewpoint of the heat deterioration resistance of the block copolymer (a) during production of 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. preferable.

Examples of 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).

Examples of 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. A polymer block mainly comprising a body unit, B is a polymer block mainly comprising a conjugated diene monomer unit, and X is a residue of a coupling agent or a residue of a polymerization initiator). It is preferable to contain a block copolymer having a structure.
Further, from the viewpoint of the high temperature physical properties of the asphalt composition and the low viscosity of the asphalt composition, (SB) _n (n = 2 to 4 is an integer, and S is a heavy weight mainly composed of vinyl aromatic monomer units. It is preferable to contain a block copolymer having a structure of a combined block, and B is a polymer block mainly composed of a conjugated diene monomer unit.
Furthermore, from the viewpoint of the high temperature physical properties of the asphalt composition and the low temperature physical properties of the asphalt composition, S— (B—S) _n (n = 1 to 4 is an integer, and S is mainly composed of vinyl aromatic monomer units. It is preferable to contain a block copolymer having a structure of B), wherein B is a polymer block mainly composed of a conjugated diene monomer unit.
Furthermore, from the viewpoint of the high temperature physical properties of the asphalt composition and the solubility of the polyphenylene ether (b) and the copolymer (a) in asphalt, S— (RS) _n and [(S—R) _k ] _m— X (n = 1 to 4, integer of m = 2 to 4, k = 1 to 4, and S is a polymer block mainly composed of vinyl aromatic monomer units. Wherein R is a copolymer block composed 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). 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.

In addition, the weight average molecular weight of a copolymer (a) can be calculated | required by the method as described in the Example mentioned later.

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.

Here, 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).
In 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.

In addition, in this embodiment, content of the vinyl aromatic monomer unit in a copolymer (a) can be measured by the method as described in the Example mentioned later.

Content of the polymer block mainly composed of vinyl aromatic monomer units in the copolymer (a) used in the asphalt composition of the present embodiment (Here, as described above, “mainly” means heavy The vinyl aromatic monomer unit is included in the coalesced block in an amount of 80% by mass to 100% by mass.) 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, it is preferably 8% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, and further more preferably 20% by mass or more. preferable.
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 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.
However, 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 | required by the method as described in the Example mentioned later.

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.
In addition, 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. Further, from the viewpoint of a low polymer addition amount added to asphalt and recoverability after tension, 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.
Examples of 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. A method using a monomer having a modifying group consisting of these functional groups as a constituent monomer, a monomer unit constituting a block copolymer, and a polymerization initiator having a modifying group consisting of these functional groups , A coupling agent, or a method of binding to a terminating agent residue.

(Production method of copolymer (a))
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 polymerization step for obtaining a copolymer, a hydrogenation step for hydrogenating the double bond in the conjugated diene monomer unit of the obtained copolymer, and a solvent for the solution containing the copolymer as an optional step. A solvent removal step for removing the solvent can be sequentially performed for production.

<Polymerization process>
In the polymerization step, 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.

[Hydrocarbon solvent]
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.

[Polymerization initiator]
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.

[Monomer used for polymerization]
Examples of the conjugated diene monomer 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. Among these, 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.

Examples of the vinyl aromatic monomer include, but are not limited to, styrene, α-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.

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, randomizing agents]
In the polymerization process, adjustment of the polymerization rate, adjustment of the microstructure of the polymerized conjugated diene monomer units (ratio of cis, trans, and vinyl), reaction ratio of conjugated diene monomer and vinyl aromatic monomer A predetermined polar compound or a randomizing agent can be used for the purpose of adjusting the above.

Examples of 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 | polymerization process.
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.

<Hydrogenation process>
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 A homogeneous catalyst using organic Li, organic Al, organic Mg or the like as the reducing agent can be mentioned.
In particular, 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.
Specifically, hydrogenated block copolymer solution can be obtained by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent.

As the hydrogenation reaction, 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.

In the hydrogenation step, 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.
Moreover, 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. When the hydrogenation rate of the conjugated bond in the total vinyl aromatic monomer is within the above range, the amount of polymer added to the asphalt can be reduced, and the compatibility with the asphalt tends to increase. .

<Desolvation process>
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. Further, 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.

From the viewpoint of heat aging resistance of the copolymer (a) and suppression of gelation, it is preferable to add an antioxidant to the copolymer (a).
Examples of 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.

Among 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. Moreover, 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.

In addition, from the viewpoint of preventing coloring of the copolymer (a) and improving mechanical strength, 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.

(Polyphenylene ether (b) having a reduced viscosity of 0.07 dL / g to 0.60 dL / g)
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.
From the above viewpoint, 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. On the other hand, since a viscosity will become very high and workability will deteriorate when it puts in large quantities, 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). .
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 amino group, an amide group, a silanol group, and an alkoxysilane group.
Specific preferred embodiments of polyphenylene ether (b) include the following (1) to (3).
(1) includes polyphenylene ether (b-1) having no modifying group composed of a functional group.
(2) 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.
(3) A mixture of a polyphenylene ether (b-1) having no modifying group composed of the functional group and a polyphenylene ether (b-2) having a carboxyl group and / or a group derived from a carboxyl group.

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.
Further, from the viewpoint of low viscosity and flexibility of 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.

In addition, 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. For example, 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. .
In particular, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and maleic anhydride are preferable, and maleic acid and maleic anhydride are more preferable.
When 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.

In addition, 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). As a method to do, although it is not limited to the following, For example, the method etc. which couple | bond with the residue of a coupling agent or a terminator are mentioned.

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.

In the production of the asphalt composition of this embodiment, the copolymer (a) and the polyphenylene ether (b) may be added independently, or the copolymer (a) and the polyphenylene ether (b). You may add the thermoplastic resin composition (d) which is an extrusion molding body, for example, a pellet.
Moreover, you may add a copolymer (a) and the above-mentioned thermoplastic resin composition (d), respectively.
Further, two or more kinds of thermoplastic resin compositions (d) may be added in combination.
From the viewpoint of the solubility of polyphenylene ether (b) in asphalt, 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.
By pre-extrusion blending the copolymer (a) and the polyphenylene ether (b), the polyphenylene ether (b) can be finely dispersed in the pellets of the thermoplastic resin composition (d). When the pellet is dissolved in asphalt, the polyphenylene ether (b) is finely dispersed in advance, so that the solubility of the polyphenylene ether (b) tends to be improved.

In addition, as 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, and 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 (pressure) 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. on the downstream side when the double bond contained in the conjugated diene monomer unit of the copolymer (a) is hydrogenated. When the coalescence (a) is not hydrogenated, it is preferably set to 250 ° C. from the upstream side to 250 ° C.

By the above-mentioned method, 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).
In the present specification, the state in which polyphenylene ether is uniformly dispersed means a state in which polyphenylene ether aggregates having a particle diameter of 50 μm 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 μm.

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.
Next, as 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” Non-hydrogenated copolymer ”and / or“ non-hydrogenated copolymer block comprising at least one vinyl aromatic monomer and at least one conjugated diene monomer ”. If so, put the test piece for dyeing in a 2 mass% osmium tetrachloride aqueous solution in a heat-resistant container, pour it in a water bath at 80 ° C for 30 minutes, pull it up, cool it to room temperature, take it out from the heat-resistant container, wash it with water, Dry.
By the dyeing operation, 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.
Further, as 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”. In the case where the `` 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. Separately, 0.1 g of 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.
Hydrogenation of 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” Product "and / or" hydrogenated copolymer block comprising at least one vinyl aromatic monomer and at least one conjugated diene monomer "is dyed and observed black during TEM observation. The

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, 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 μm or more with respect to the total polyphenylene ether, and average dispersed particles of polyphenylene ether The diameter can be determined.
Here, the area fraction of the polyphenylene ether aggregate having a particle diameter of 50 μm 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 μm or more with respect to the total polyphenylene ether.
By the above operation, the state of “uniform dispersion” and “compatibility” of the polyphenylene ether (b) with respect to the copolymer (a) can be confirmed.

In the asphalt composition of the present embodiment, 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 μm, more preferably less than 4 μm, further preferably less than 3.5 μm, and still more preferably less than 3 μm.
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).
Examples of 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.
Examples of the antioxidant include, but are not limited to, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, amine antioxidants, and the like.
Specifically, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol (IRGANOX565 manufactured by BASF), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX 1010 manufactured by BASF, Adeka Stub AO-60 manufactured by ADEKA Corporation), 1,3,5-trimethyl-2,4 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330 manufactured by BASF), octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (( ADEKA ADK STAB AO-50), Tris (2,4-di-t-butylphenyl) phosphite (B SFGA IRGAFOS168, ADEKA ADK STAB 2112), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane (( ADEKA ADEKA STAB PEP-8), 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Undecane (ADEKA STAB PEP-36 manufactured by ADEKA Corporation), phosphoric acid = 2,2′-methylenebis (4,6-di-t-butylphenyl) = 2-ethylhexyl (ADEKA STAB manufactured by ADEKA Corporation) HP-10), dioctadecyl 3,3′-thiobispropanoate (IRGANOX PS802FD manufactured by BASF), N, N-dioctadecyl hydroxy Triethanolamine (BASF Corp. IRGASTAB FS042), and the like.
These may be used alone or in combination of two or more.
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))
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.
Examples of 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.
Moreover, you may add 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.

In the asphalt composition of the present embodiment, 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. Further, from the viewpoint of low viscosity of the asphalt composition, little 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 14% by mass. % Or less, more preferably 12% by mass or less.
Generally, when producing an asphalt composition, if 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.

(Mass ratio of (a) component and (b) component)
From the viewpoint of the high softening point of the asphalt composition, the mass ratio of the copolymer (a) and the polyphenylene ether (b) in the asphalt composition of the present embodiment was set to 100% by mass. 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.
From the viewpoint of low viscosity, good low-temperature physical properties, and solubility in asphalt, 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.

(Form of asphalt composition)
As a suitable form of the form of the asphalt composition of this embodiment,
Extruded molded product of copolymer (a) having vinyl aromatic monomer unit and conjugated diene monomer unit and polyphenylene ether (b) having reduced viscosity of 0.07 dL / g to 0.60 dL / g A thermoplastic resin composition (d),
Asphalt (c),
Asphalt compositions containing
The content of (d) is 3 to 20% by mass,
The content of (c) is 80 to 97% by mass,
In the thermoplastic resin composition (d), the mass ratio of the component (a) to the component (b) is (a) / (b) = 20 to 99/80 to 1.
Such an asphalt composition is produced by mixing an extruded product of a copolymer (a) and a polyphenylene ether (b), for example, a thermoplastic resin composition (d) which is a pellet and an asphalt (c). can do.

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

(Other materials)
The asphalt composition of this embodiment can mix | blend arbitrary petroleum resins as needed. Addition of petroleum resin tends to improve the adhesiveness between the asphalt composition and the aggregate when it is used as a mixture with the aggregate, and peeling can be suppressed.
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. Although 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 | blend arbitrary additives as needed.
The type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.
For example, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber 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 polysiloxanes, mineral oils; antioxidants such as hindered phenolic antioxidants and phosphorous heat stabilizers; hindered amine Mitsuan Agents, benzotriazole-based UV absorbers, flame retardants, antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers, metal whiskers; colorants, and other additives, mixtures thereof, etc. , “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Japan) and the like.
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).

In the asphalt composition of the present embodiment, 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.

In addition to the copolymer (a), the asphalt composition of the present embodiment may contain other polymers.
Examples of 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. 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.

[Method for producing asphalt composition]
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.
There are also no particular restrictions on the conditions for stirring the mixture of the copolymer (a), the polyphenylene ether (b), and / or the thermoplastic resin composition (d) that is a mixture thereof, and the asphalt (c). However, 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.

[Use]
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.

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.
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. In addition, asphalt-coated aggregates and recycled aggregates obtained by coating these aggregates with asphalt can also be used.
In addition, 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. In this embodiment, 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.

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 measuring method regarding the copolymer and asphalt composition in an Example and a comparative example is shown below.

〔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.

(Vinyl bond amount of block copolymer, hydrogenation rate of unsaturated group in conjugated diene monomer unit, content of vinyl aromatic monomer unit)
The amount of vinyl bonds in the block copolymer, the hydrogenation rate of unsaturated groups in the conjugated diene monomer unit, and the content of the vinyl aromatic monomer unit were analyzed by nuclear magnetic resonance spectrum analysis (NMR) as follows: It measured on condition of this.
The reaction solution after the hydrogenation reaction of the block copolymer was poured into a large amount of methanol and precipitated to precipitate and recover the block copolymer after hydrogenation.
Next, the hydrogenated block copolymer was extracted with acetone, and the extract was vacuum-dried and used as a sample for ¹ H-NMR measurement.
The conditions for ¹ H-NMR measurement are described below.
<Measurement conditions>
Measuring equipment: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Measurement sample: Extracted sample before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

(Weight average molecular weight)
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 (polystyrene equivalent 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, and the unit of measurement value was expressed in g / 10 minutes.

(Reduced viscosity of polyphenylene ether)
The reduced viscosity of polyphenylene ether was measured at 30 ° C. using an Ubbelohde viscometer by dissolving 0.5 g of polyphenylene ether (b) in 100 mL of chloroform.

[Method for producing copolymer]
(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.

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

<Second stage polymerization>
Seven minutes after reaching the maximum temperature (51 ° C.) due to the polymerization of styrene, the temperature decreased by 2 ° C. from the maximum temperature, and then 560 g of butadiene (1,3-butadiene) was added to the autoclave to continue the polymerization.
30 seconds after the butadiene was almost completely polymerized and reached the maximum temperature (90 ° C.), the autoclave was subjected to dichlorination of 2,2-bis (4-hydroxyphenyl) propane with epichlorohydrin as a coupling agent. 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.

10 minutes after the addition of the coupling agent, the autoclave was deactivated by adding water to obtain a block copolymer solution.

To the obtained block copolymer solution, 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 obtained block copolymer 1 is a mixture of block copolymers, and the ratio of the structure is
SB / (SB) ₂ —X = 20/80% by mass 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.
Moreover, 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.
In the above formula, S represents a polymer block mainly composed of vinyl aromatic monomer units, and 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 obtained block copolymer 2 is a mixture of block copolymers, and the structure ratio is
SB / (SB) ₄ —X = 20/80% by mass 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.
Moreover, 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.

(Block copolymer 3)
<Preparation of hydrogenation catalyst>
Into a reaction vessel purged with nitrogen, 1 L of dried and purified cyclohexane was added, 100 mmol of bis (cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. For about 3 days to obtain a hydrogenation catalyst.
<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>.
Then, after adding water and deactivating, 98 mol% of the double bond in the conjugated diene monomer unit in a block copolymer was hydrogenated with said hydrogenation catalyst, and the block copolymer solution was obtained.
Then, 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.
Moreover, 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.
Then, after deactivation by adding water, 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.
Moreover, content of the vinyl aromatic monomer unit was 50 mass%, and 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 obtained block copolymer 6 is a mixture of block copolymers, and the ratio of the structure is
SB / [(SB) ₂ -X + (SB) ₃ -X + (SB) ₄ -X] = 20/80 mass%
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.
Moreover, 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.

[Examples 1 to 23], [Comparative Examples 1 to 7]
(Manufacture of asphalt composition)
500 g of straight asphalt 60-80 [manufactured by Shin Nippon Oil Co., Ltd.] was put into a 750 mL metal can, and the metal can was sufficiently immersed in a 160 ° C. oil bath.
Next, while stirring the molten asphalt at a rotational speed of 4000 rpm, as shown in Tables 2 to 4 below, predetermined amounts of the block copolymer (a), polyphenylene ether (b), and a thermoplastic resin composition described later These were added to the asphalt using the product pellets (d), and stirred for 90 minutes after the addition to prepare an asphalt composition.

In addition, the following were used as polyphenylene ether (b).
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.

In Examples 7 to 13, 15, 16, 19, and 21, thermoplastic resin composition pellets (d) prepared by coextrusion blending of block copolymer (a) and polyphenylene ether (b). Was used.

Furthermore, in 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.

(Manufacture of asphalt mixture)
In a mixer having a capacity of 27 liters equipped with a heating device, 94.5 parts by mass of a fine-grained aggregate having the particle size shown in Table 1 below was charged and kneaded for 25 seconds.
Next, 5.5 parts by mass of the asphalt composition produced by the above-described method was put into the mixer and subjected to main kneading for 50 seconds to obtain asphalt mixtures of Examples 1 to 23 and Comparative Examples 1 to 7. .
The obtained asphalt mixture was a close-graded type asphalt mixture.
The total amount of the asphalt mixture was 10 kg, and the mixing temperature was adjusted to 177 ° C. for both the empty kneading and the main kneading.
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.

 

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

(Softening point of asphalt composition)
According to JIS-K2207, the softening point of the asphalt composition was measured by the ring and ball method.
When the sample is filled in the specified ring, supported horizontally in the glycerin liquid, a 3.5 g sphere is placed in the center of the sample, and the liquid temperature is increased at a rate of 5 ° C./min. Measured the temperature when touching the bottom plate of the ring base. The higher the softening point of the asphalt composition, the better the flow resistance, and the following criteria were evaluated as ○, ○, Δ, and × in order of goodness.
<Evaluation criteria>
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 .: Δ
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 ◎, ○, Δ, × in order from the following criteria.
<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: Δ
Melt viscosity is 1500 mPa · s or more: ×

(Asphalt compatibility in asphalt composition)
The average particle size of the polyphenylene ether during the production of the asphalt composition was measured. As a measuring method, observation was performed using transmitted light from a digital microscope.
The measurement apparatus and measurement conditions were as follows.
<Measurement device>
Digital microscope VHX-2000 made by KEYENCE
<Measurement conditions>
Measurement temperature: 25 ° C
Measurement magnification: 2000 times Measurement mode: transmitted light Measurement object: polyphenylene ether (clear color portion). Asphalt is a brown part and elastomer is a dark white part.

Sample preparation method: 10 mg of the asphalt composition being stirred is collected on a glass slide, allowed to stand for 20 seconds on a hot plate heated to 180 ° C. and melted. Thereafter, the cover glass is placed on a molten asphalt composition and thinly spread. After releasing at room temperature for 30 minutes, observation was performed with a digital microscope.
The smaller the average particle size of the polyphenylene ether in the asphalt composition, the better the high-temperature storage property and the low-temperature performance, and it was evaluated as ◎, ○, Δ, × in order from the following criteria.
<Evaluation criteria>
Average particle diameter is less than 10 μm: ◎
Average particle diameter of 10 μm or more and less than 25 μm: ○
Average particle diameter is 25 μm or more and less than 50 μm: Δ
Average particle diameter is 50 μm or more: ×

(Elongation of asphalt composition)
According to JIS-K2207, after pouring the sample into the form and making it into the specified shape, when the sample is kept at 15 ° C in a constant temperature water bath and then pulled at a rate of 5 cm / min, the sample stretches until it breaks. The measured distance (elongation) was measured. The asphalt composition having higher elongation had better resistance to cracking at low temperatures, and was evaluated as 、, ○, Δ, and × in order from the following criteria.
<Evaluation criteria>
Elongation is 80 cm or more: ◎
Elongation 65 cm or more and less than 80 cm: ○
Elongation is 50 cm or more and less than 65 cm: Δ
Elongation is less than 50 cm: ×

(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) 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. .
Then, after storing for 1 hour in a freezer, 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.
The smaller the softening point difference, the better the high-temperature storage stability and the low-temperature performance, and the following criteria were evaluated as ◎, ○, Δ, and × in order of goodness.
<Evaluation criteria>
Softening point difference is 2 ° C or less: ◎
Softening point difference is 6 ° C or less: ○
Softening point difference is 10 ° C. or less: Δ
Softening point difference exceeds 10 ° C: ×

(Rubber resistance of asphalt mixture)
The asphalt mixture produced according to the production example of the asphalt mixture described above was used as a test body, and the test was conducted in accordance with Test Method Manual B003.
A small rubber wheel loaded was repeatedly reciprocated at a specified temperature, a specified time, and a specified speed on a test body having a predetermined size, and the dynamic stability (times / mm) was determined from the amount of deformation per unit time.
The higher the dynamic stability, the better the rutting resistance.
The following criteria were evaluated as ◎, ○, △, × from the best order.
<Evaluation criteria>
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: Δ
Dynamic stability is less than 6000 times / mm: ×

 

 

 

This application is 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 Application No. 2017-243831), the contents of which are incorporated herein by reference.

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

Claims (12)

1. 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,
   An asphalt composition.
2. 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 asphalt composition of Claim 1 which has a modification group.
3. 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.
4. 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 claims 1 to 3, wherein
5. 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 claims 1 to 4, wherein
6. Extruded molded product of copolymer (a) having vinyl aromatic monomer unit and conjugated diene monomer unit and polyphenylene ether (b) having reduced viscosity of 0.07 dL / g to 0.60 dL / g A thermoplastic resin composition (d),
   Asphalt (c),
   An asphalt composition comprising:
   The content of (d) is 3 to 20% by mass,
   The content of (c) is 80 to 97% by mass,
   In the thermoplastic resin composition (d), the mass ratio between (a) and (b) is as follows:
   (A) / (b) = 20 to 99/80 to 1,
   Asphalt composition.
7. 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 asphalt composition of Claim 6 whose average dispersed particle diameter of the said polyphenylene ether (b) in the said thermoplastic resin composition (d) is less than 5 micrometers.
8. The content of (d) is 3 to 15% by mass,
   The content of (c) is 85 to 97% by mass,
   In (d), the mass ratio of (a) to (b) is (a) / (b) = 40 to 99/60 to 1.
   The asphalt composition according to claim 6 or 7.
9. The asphalt composition according to any one of claims 6 to 8, wherein the thermoplastic resin composition (d) contains an antioxidant.
10. The asphalt composition according to any one of claims 6 to 9, wherein the copolymer (a) having the vinyl aromatic monomer unit and the conjugated diene monomer unit is hydrogenated.
11. The asphalt composition according to any one of claims 6 to 10, further comprising 1 to 10% by mass of a styrene-butadiene-styrene copolymer (SBS).
12. The copolymer (a) having the vinyl aromatic monomer unit and the conjugated diene monomer unit,
    The asphalt composition according to any one of claims 1 to 11, which has a modifying group composed of a functional group.