JP2016210874A - Modified asphalt composition for adhesion and mixture, and laminate thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified asphalt composition for adhesion which exhibits a high adhesive force with an adjacent layer during drying and water adhesion and has excellent workability and weather resistance and a mixture therefor, and to provide a laminate thereof.SOLUTION: There is provided a modified asphalt composition for adhesion to at least one adherend selected from the group consisting of a polar resin, metal, an inorganic oxide, asphalt, an asphalt mixture and their composite body which contains 20 mass% or more and 99.5 mass% or less of asphalt (A) and 0.5 mass% or more and 80 mass% or less of a block copolymer (B), where the block copolymer (B) contains at least a conjugated diene monomer unit and a vinyl aromatic monomer unit, the vinyl aromatic monomer unit in the block copolymer (B) is 15 mass% or more and 60 mass% or less, and a peak temperature of a loss tangent (tanδ) by dynamic viscoelasticity measurement of the block copolymer (B) is -50°C or higher and -5°C or lower.SELECTED DRAWING: None

Description

  The present invention relates to a modified asphalt composition and mixture for adhesion, and a laminate thereof.

  A modified asphalt composition obtained by adding a polymer to asphalt is widely used as a laminate used in road paving applications, asphalt tarpaulin applications, concrete applications, pipelines, and iron parts applications.

  The modified asphalt composition is required to have not only properties such as processability, mechanical properties and thermal stability as various layers, but also adhesion to adjacent layers. In recent years, from the viewpoint of energy saving, environmental load reduction, work environment improvement, etc., adding an adhesive to the modified asphalt composition, or adhering a layer of the modified asphalt composition to the substrate by a self-adhesive layer, Construction that incorporates a so-called cold method has been carried out in many applications including road paving and asphalt tarpaulin applications.

  Patent Document 1 describes a laminate of a surface layer containing a polyolefin resin containing inorganic particles, a modified asphalt layer modified with APP or SBS, and a base material layer made of nylon, glass, or the like. .

Patent Document 2 describes a laminate composed of a gypsum board layer, a modified asphalt layer modified with butyl rubber, and a gypsum board layer.
Patent Document 3 includes an asphalt layer modified with a styrene-butadiene copolymer (SBR), a coating-type floor slab waterproofing layer, an ultrahigh strength fiber reinforced concrete layer, an adhesive layer, and a floor slab. A layered pavement structure has been proposed.

JP 2009-138486 A Japanese Utility Model Publication No. 06-014314 JP 2013-007188 A

  As a result of the intensive studies by the inventors, the conventional modified asphalt composition layer as described in Patent Documents 1, 2, and 3 does not necessarily have a satisfactory adhesive force with an adjacent layer. It turns out that there is room for further improvement.

  The problem to be solved by the present invention is to provide a modified asphalt composition and mixture for adhesion, which exhibits high adhesion to an adjacent layer at the time of drying and water adhesion, and has excellent processability and weather resistance, and its It is to provide a laminate.

  As a result of intensive studies, the present inventors have found that an asphalt composition containing a block copolymer having a specific molecular structure has high adhesion to an adherend, and completed the present invention.

That is, the present invention is as follows.
[1]
A modified asphalt composition for adhesion to at least one adherend selected from the group consisting of polar resin, metal, inorganic oxide, asphalt, asphalt mixture, and composites thereof,
20% to 99.5% by weight of asphalt (A),
Including 0.5% by mass or more and 80% by mass or less of the block copolymer (B),
The block copolymer (B) includes at least a conjugated diene monomer unit and a vinyl aromatic monomer unit,
The vinyl aromatic monomer unit in the block copolymer (B) is 15% by mass or more and 60% by mass or less,
The modified asphalt composition for adhesion, wherein the peak temperature of loss tangent (tan δ) measured by dynamic viscoelasticity of the block copolymer (B) is −50 ° C. or more and −5 ° C. or less.
[2]
The block copolymer (B) is mainly composed of at least a polymer block (a) mainly composed of a vinyl aromatic monomer unit, a conjugated diene monomer unit and a vinyl aromatic monomer unit. Item 2. The modified asphalt composition for bonding according to Item 1, comprising a copolymer block (b).
[3]
Item 3. The modified asphalt composition for bonding according to Item 1 or 2, wherein the hydrogenation rate of the double bond in the conjugated diene monomer unit in the block copolymer (B) is 95 mol% or less.
[4]
The modified asphalt composition for bonding according to any one of Items 1 to 3, wherein the content of the polymer block (a) in the block copolymer (B) is 10% by mass or more and 50% by mass or less. .
[5]
The modified asphalt composition for adhesion according to any one of Items 1 to 4, wherein the block copolymer (B) includes a modified block copolymer having a modifying group.
[6]
Item 6. The adhesive according to Item 5, wherein the modifying group is at least one modifying 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. Modified asphalt composition.
[7]
For a total of 100 parts by mass of the asphalt (A) and the block copolymer (B), the tackifier contains 0 part by mass to 300 parts by mass or less, or the softener contains 0 part by mass and 50 parts by mass or less. Or the modified asphalt composition for bonding according to any one of Items 1 to 6, comprising both of them.
[8]
The modified asphalt mixture for adhesion containing the modified asphalt composition for adhesion according to any one of items 1 to 7 and an aggregate.
[9]
The first layer of at least one adherend selected from the group consisting of a polar resin, a metal, an inorganic oxide, asphalt, an asphalt mixture, and a composite thereof, and the adhesion according to any one of items 1 to 7 A laminated body obtained by laminating a second layer of the modified asphalt composition for use.
[10]
The first layer of at least one adherend selected from the group consisting of a polar resin, a metal, an inorganic oxide, asphalt, an asphalt mixture, and a composite thereof, and the first modified asphalt mixture for bonding according to Item 8 A laminated body in which two layers are laminated.

  According to the present invention, there are provided a modified asphalt composition and mixture for adhesion, and a laminate thereof, which exhibit high adhesive strength with adjacent layers at the time of drying and adhesion of water, and have excellent processability and weather resistance. can do. Furthermore, the modified asphalt composition for adhering and the mixture of the present invention have high adhesion to the adherend, thereby simplifying the paving structure, reducing the weight, improving the strength and waterproofing, and shortening the paving work time. Etc. can be expected.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

≪Adhesive modified asphalt composition≫
The modified asphalt composition for adhesion of the present embodiment is a modified asphalt composition for adhesion to at least one adherend selected from the group consisting of polar resins, metals, inorganic oxides, asphalt, asphalt mixtures, and composites thereof. Asphalt composition comprising:
20% to 99.5% by weight of asphalt (A),
0.5% by mass or more and 80% by mass or less of the block copolymer (B), and the block copolymer (B) comprises at least a conjugated diene monomer unit and a vinyl aromatic monomer unit. Including
The vinyl aromatic monomer unit in the block copolymer (B) is 15% by mass or more and 60% by mass or less,
The peak temperature of loss tangent (tan δ) by dynamic viscoelasticity measurement of the block copolymer (B) is −50 ° C. or more and −5 ° C. or less.
Here, the constitutional unit constituting the polymer is referred to as “˜monomer unit”, and when described as a polymer material, “unit” is omitted and simply “˜monomer”.

<Adherent>
In the present embodiment, the adherend is at least one adherend selected from the group consisting of a polar resin, a metal, an inorganic oxide, asphalt, an asphalt mixture, and a composite thereof.

  Examples of the polar resin to be an adherend include polyolefin, polyester, polyether, polyurethane, poly (meth) acrylate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyamide, and polyvinyl acetate. As the polar resin to be the adherend, polyester and polyurethane are preferable from the viewpoint of initial peel strength.

  Examples of the metal serving as the adherend include stainless steel (SUS), iron, aluminum, copper, zinc, silver, gold, titanium, nickel, and brass.

  Examples of the inorganic oxide to be adhered include iron oxide, copper oxide, alumina, zinc oxide, lead oxide, titanium oxide, magnesium oxide, calcium oxide, silver oxide, manganese oxide, vanadium oxide, cobalt oxide, nickel oxide, Examples include silica, clay, talc, mica, wollastonite, montmorillonite, and zeolite.

  As the asphalt to be the adherend, the same asphalt (A) described later can be used.

  The asphalt mixture to be an adherend refers to a mixture containing at least asphalt and aggregate. The asphalt mixture to be an adherend may contain any additive in addition to asphalt and aggregate. As an additive, the additive similar to the additive which can be used for the adhesion modified asphalt mixture of this embodiment mentioned later can be used, For example, inorganic carbonates, such as a calcium carbonate, are mentioned. As the aggregate, an aggregate similar to the aggregate that can be used in the modified asphalt mixture for bonding according to the present embodiment described later can be used. As a specific example of the asphalt mixture to be an adherend, an asphalt road pavement can be mentioned.

<Asphalt (A)>
The modified asphalt composition for adhesion according to the present embodiment contains 20% by mass or more and 99.5% by mass or less of asphalt (A).
The lower limit of the content of asphalt (A) may be 20% by mass or more, and may be 50% by mass or more, or 80% by mass or more from the viewpoint of a short production time of the modified asphalt composition for adhesion. preferable. The upper limit of the content of asphalt (A) may be 99.5% by mass or less, and is preferably 98% by mass or less, or 97% by mass or less from the viewpoint of initial peel strength.

  Asphalt (A) is not particularly limited. For example, asphalt (A) can be obtained as a by-product during petroleum refining (petroleum asphalt), a natural product (natural asphalt), or a mixture of these with petroleum. Can be mentioned. The main component is generally called bitumen.

  Specific examples of the asphalt (A) include, but are not limited to, straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch, cutback asphalt added with oil, asphalt emulsion, and the like. Asphalt (A) is preferably straight asphalt. These may be used alone or in combination. Moreover, you may add aromatic heavy mineral oils, such as petroleum-type solvent extraction oil, aroma-type hydrocarbon process oil, or an extract, to various asphalts.

    As the asphalt (A), straight asphalt having a penetration (measured according to JIS-K2207) of 30 to 300 is preferable, straight asphalt having a penetration of 40 to 200 is more preferable, and a penetration of 45 to 150 is preferable. The following straight asphalt is more preferable.

<Block copolymer (B)>
The modified asphalt composition for adhesion according to the present embodiment contains the block copolymer (B) in an amount of 0.5% by mass to 80% by mass, and the block copolymer (B) contains at least a conjugated diene monomer. The vinyl aromatic monomer unit in the block copolymer (B) is 15% by mass or more and 60% by mass or less, and the block copolymer (B ) Of the loss tangent (tan δ) measured by dynamic viscoelasticity is −50 ° C. or higher and −5 ° C. or lower.

  Since the block copolymer (B) of the embodiment of the present application has the above-described configuration, the modified asphalt composition for adhering and the mixture of the embodiment of the present invention are the above-described adherend when dried and when adhering to water. It is considered that it has excellent workability and weather resistance.

  The lower limit of content of a block copolymer (B) should just be 0.5 mass% or more, and it is preferable that it is 2 mass% or more or 3 mass% or more from a viewpoint of initial stage peeling strength. The upper limit of content of a block copolymer (B) should just be 80 mass% or less, and it is preferable that it is 20 mass% or less or 15 mass% or less from the point of economical efficiency.

  In this embodiment, the block copolymer (B) is at least a vinyl aromatic monomer unit in terms of processability of the modified asphalt composition for adhesion, short production time, and adhesiveness to the adherend. It is preferable to contain a polymer block (a) mainly comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit (b).

  In the present specification, “mainly composed of a vinyl aromatic monomer unit” means that the content of a predetermined monomer unit in the block is preferably 60% by mass or more, more preferably 80% by mass. It means mass% or more, more preferably 90 mass% or more, and still more preferably 95 mol% or more.

[Polymer structure]
In this embodiment, the block copolymer (B) is
It is preferable to contain at least one block copolymer selected from the group consisting of (i) to (vi).

(Ab) _n (i)
b- (ab) _n (ii)
a- (b-a) _n (iii)
a- (ba) _n -X (iv)
[(A−b) _k ] _m −X (v)
[(A−b) _k −a] _m −X (vi)
In the above formulas (i) to (vi), (a) represents a block mainly composed of a vinyl aromatic monomer unit, and (b) represents a conjugated diene monomer unit and a vinyl aromatic monomer unit. And X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium, and m, n, and k represent an integer of 1 or more. , Preferably an integer of 1 to 5. When a plurality of polymer blocks a and b are present in the block copolymer, the structures such as molecular weight and composition may be the same or different. The block copolymer may be a mixture of a coupling body in which X is a residue of a coupling agent and a non-coupling body having no X or X being a residue of a polymerization initiator. The boundary and the end of each block need not necessarily be clearly distinguished.

  The double bond of the conjugated diene monomer unit may or may not be hydrogenated. In the block copolymer (B), the upper limit value of the hydrogenation rate of the double bond in the conjugated diene monomer unit is 95 mol% or less in terms of the short production time of the modified asphalt composition for adhesion. From the viewpoint of viscosity, 94 mol% or less is preferable, 93 mol% or less is more preferable, and 92 mol% or less is more preferable. The lower limit of the hydrogenation rate of the double bond in the conjugated diene monomer unit is not particularly limited, but is preferably more than 0 mol%, for example, 1 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more. It can be. The range of the hydrogenation rate of the double bond in the conjugated diene monomer unit is, for example, more than 0 mol% to 95 mol%, 1 mol% to 90 mol%, 10 mol% to 90 mol%, 30 mol% to 80 mol%, 30 mol% to 70 mol%. , 45 mol% to 80 mol%, or 45 mol% to 70 mol%.

  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 described later. Moreover, a hydrogenation rate can be calculated | required by the method as described in the Example mentioned later.

  Vinyl aroma in a polymer block (a) mainly composed of a vinyl aromatic monomer unit and in a copolymer block (b) mainly composed of a conjugated diene monomer unit and a vinyl aromatic monomer alone. The distribution of the group monomer unit is not particularly limited, and may be uniformly distributed, or may be distributed in a tapered shape, a stepped shape, a convex shape, or a concave shape. In addition, a crystal part may be present in the polymer block.

  In this embodiment, content of the vinyl aromatic monomer unit contained in (B) in a block copolymer is 15-60 mass%. The lower limit of the content of the vinyl aromatic monomer unit in the block copolymer (B) may be 15% by mass or more from the viewpoint of the aggregate peel resistance of the modified asphalt composition for adhesion, and 33 More preferably, it is more preferably 35% by mass or more, and even more preferably 38% by mass or more. Moreover, the upper limit of content of the vinyl aromatic monomer unit in a block copolymer (B) should just be 60 mass% or less at the point of the solubility of a polymer, and 50 mass% or less is preferable, 45 mass% or less is more preferable, and 44 mass% or less is further more preferable.

  In this embodiment, in the case where the block copolymer (B) contains a copolymer block (b) mainly composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit, the copolymer block (b The vinyl aromatic monomer unit content is preferably 5% by mass or more, more preferably 20% by mass or more from the viewpoint of separation stability, heat aging resistance, and recoverability after tension of the modified asphalt composition for adhesion. Is more preferable, and more preferably 25% by mass or more. Further, the amount of addition of the block copolymer (B) to the asphalt (A) is reduced, the separation stability of the modified asphalt composition for adhesion, the flexibility of the modified asphalt composition for adhesion and the block copolymer, weather resistance, The vinyl aromatic monomer unit content in the copolymer block (b) is preferably 50% by mass or less, more preferably 40% by mass or less, and further 35% by mass or less in terms of the anti-aggregate resistance. Preferably, 30 mass% or less is the most preferable.

The vinyl aromatic monomer unit content (RS) in the copolymer block (b) is calculated from the content (TS) of the vinyl aromatic monomer unit in the block copolymer (B). It is obtained by dividing the content (BS) of the polymer block (a) mainly composed of vinyl aromatic monomer units.
Specifically, RS (%) = (TS−BS) / (100−BS) × 100.

  The lower limit of the content of the block (a) mainly composed of the vinyl aromatic monomer unit in the block copolymer (B) is 10 in terms of the anti-aggregation resistance of the modified asphalt composition for adhesion. % By mass or more is preferable, 13% by mass or more is more preferable, 16% by mass or more is more preferable, and 17% by mass or more is most preferable. The upper limit of the content of the block (a) mainly composed of vinyl aromatic monomer units in the block copolymer is 50% by mass or less in terms of a short production time of the modified asphalt composition for adhesion. Is preferably 35% by mass or less, more preferably 29% by mass or less, and most preferably 22% by mass or less. In addition, content of the block (a) which has a vinyl aromatic monomer unit as a main body can be measured by the method as described in the Example mentioned later.

  In this embodiment, the lower limit of the peak temperature of loss tangent (tan δ) by dynamic viscoelasticity measurement of the block copolymer (B) is high compatibility with asphalt, short production time of the modified asphalt composition In this respect, it may be −50 ° C. or higher, preferably −40 ° C. or higher, and more preferably −35 ° C. or higher. In addition, the peak temperature upper limit of loss tangent (tan δ) is −5 ° C. or less in terms of the short production time of the modified asphalt composition for bonding and the low-temperature aggregate peel resistance of the modified asphalt composition for bonding. What is necessary is just -10 degrees C or less, more preferably -15 degrees C or less, and most preferably -25 degrees C or less.

  The peak height of loss tangent (tan δ) in the range of −50 ° C. or more and −5 ° C. or less as measured by dynamic viscoelasticity of the block copolymer (B) is short production time of the modified asphalt composition for bonding, In view of the low-temperature aggregate peeling resistance of the modified asphalt composition, 0.5 or more and 1.8 or less are preferable, 0.6 or more and 1.7 or less are more preferable, and 0.7 or more and 1.5 or less are further included. preferable. The peak temperature and peak height of the loss tangent (tan δ) by the dynamic viscoelasticity measurement can be determined by the method described in the examples described later.

    The block copolymer (B) used in the present embodiment has a short production time for the modified asphalt composition for adhesion, separation stability during storage of the modified asphalt composition for adhesion, and the modified asphalt composition for adhesion. It is preferable that the block copolymer (B) has a modifying group in terms of mechanical properties and adhesion to an adherend. More preferably, the modifying group has at least one modifying 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. Among these, from the viewpoint of adhesion to an adherend, the block copolymer preferably has at least one modifying group selected from the group consisting of an amino group and an amide group, and has an amino group. Is more preferable. More preferably, the block copolymer contains 2 mol or more of at least one modifying group selected from the group consisting of an amino group and an amide group with respect to 1 mol of the molecule.

  In the present embodiment, the block copolymer (B) comprises at least a polymer block (a) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer in terms of adhesion to an adherend. More preferably, it contains a copolymer block (b) mainly composed of a body unit and a vinyl aromatic monomer unit and has a modifying group.

<Other ingredients>
The modified asphalt composition for adhesion of this embodiment may contain other components other than the asphalt (A) and the block copolymer (B). However, in the case of containing other components, in terms of adhesiveness and short-time manufacturability of the modified asphalt composition for adhesion, with respect to a total of 100 parts by mass of the asphalt (A) and the block copolymer (B), The total content of other components is preferably more than 0 parts by mass to 350 parts by mass, more preferably 1 part by mass to 100 parts by mass, and still more preferably 1 part by mass to 30 parts by mass.

  For example, the modified asphalt composition for adhesion of the present embodiment has a tackifier of 0 to 300 parts by mass or softening with respect to a total of 100 parts by mass of the asphalt (A) and the block copolymer (B). It can contain more than 0 parts by weight and less than 50 parts by weight of the agent, or both. More preferably, they are 1 mass part or more and 20 mass parts or less of tackifiers, or 0.2 mass part or more and 10 mass parts or less of a softening agent, or both.

  There are no particular restrictions on the type of tackifier, but aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, alicyclic petroleum resins such as dicyclopentadiene petroleum resins, C5 and Petroleum resins such as C5 / C9 copolymerized petroleum resins used in combination with C9 series, and hydrogenated petroleum resins obtained by hydrogenating these petroleum resins can be used.

  Specifically, as a tackifier, coumarone resin, aromatic hydrocarbon resin, rosin resin, terpene resin, polyterpene resin, petroleum resin, phenol resin, terpene-phenol resin, aliphatic cyclic Examples thereof include tackifier resins such as hydrocarbon resins, alicyclic hydrocarbon resins, hydrogenated terpene resins, and hydrogenated rosin resins.

  The kind of the softening agent is not particularly limited, and either a mineral oil softener or a synthetic resin softener can be used. The mineral oil softener generally includes aromatic hydrocarbons, naphthenic hydrocarbons, paraffinic hydrocarbons, and mixtures thereof.

  Paraffinic hydrocarbons with 50% or more carbon atoms in all carbon atoms are called paraffinic oils, naphthenic hydrocarbons with 30 to 45% carbon atoms are called naphthenic oils, An aromatic hydrocarbon having 35% or more carbon atoms is called an aromatic oil. Examples of the synthetic resin softener include polybutene and low molecular weight polybutadiene.

  The modified asphalt composition for adhesion according to this embodiment can contain other additives. 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, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, lubricants, mold release agents, hindered phenolic oxidation Reinforcing agents such as antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, metal whiskers, Colorant, other additives or Those described in such as a mixture of these, such as "rubber-Plastics Additives" (Japan ed. Rubber Digest Co.) can be mentioned. There is no restriction | limiting in particular regarding the quantity of an additive, Although it can select suitably, Usually, it is 50 mass parts or less with respect to 100 mass parts of asphalt.

  When improving oil resistance or flexibility, other polymers other than the block copolymer (B) may be added to the modified asphalt composition for adhesion. 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, ethylene vinyl acetate copolymer Olefin polymers such as polymers, ethylene-ethyl acrylate copolymers, atactic polypropylene, amorphous polyalphaolefins, blends of polypropylene and ethylene / propylene copolymers, polypropylene / ethylene / propylene / diene terpolymers An olefinic thermoplastic elastomer which is a copolymer such as a blend or ethylene may be used in combination. These polymers may have a functional group.

  In order to improve the high softening point, separation stability during storage, and oil resistance of the modified asphalt composition for adhesion, a crosslinking agent may be added to the modified asphalt composition for adhesion.

  Examples of the crosslinking agent include sulfur / sulfur compound series, phosphorus series, organic peroxide series, epoxy series, isocyanate series, resin series, amine series, metal chelate series, and thiuram. These crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type. Two or more of the same systems may be used.

  The sulfur / sulfur compound-based crosslinking agents include elemental sulfur, sulfur chloride, morpholine disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4′-morpholinodithio) benzothiazole, 4,4′-dithio. Dimorpholine, thioacetamide and the like can be used.

Examples of the phosphorus-based crosslinking agent include phosphoric anhydride (P ₂ O ₅ ), polyphosphoric acid, phosphorus oxytrichloride (POCl ₃ ), phosphorus trichloride (PCl ₃ ), and phosphorus pentasulfide (P ₂ S ₅ ). Can be used.

  Examples of the organic peroxide-based crosslinking agent include tert-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl- 2,5-di (benzoylperoxy) hexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl Peroxide, tert-butyl peroxyisobutyrate and the like can be used.

  Epoxy-based crosslinking agents include ethylene, normal butyl acrylate, glycidyl methacrylate (glycidyl methacrylate), neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, etc. Can be used.

  As the isocyanate-based crosslinking agent, triallyl isocyanurate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, or the like can be used.

  As the resin-based crosslinking agent, alkylphenol / formaldehyde resin, hexamethoxymethyl / melamine resin and the like can be used.

  Examples of amine-based crosslinking agents include hexamethylene diamine, triethylene tetramine, tetraethylene pentamine, hexamethylene diamine carbamate, N, N-dicinnamylidene-1,6-hexane diamine, 4,4-methylene bis (cyclohexylamine). ) Carbamate, 4,4-methylenebis (2-chloroaniline) and the like can be used.

  As the metal chelate-based crosslinking agent, zinc methacrylate, magnesium methacrylate, zinc dimethacrylate, magnesium dimethacrylate, or the like can be used.

  Among these crosslinking agents, the effects of the modified asphalt composition for adhesion, such as the high softening point, the separation stability during storage, and the oil resistance, are great, and in terms of economy, sulfur / sulfur compounds or polyphosphoric acid Is preferred.

  The content of the cross-linking agent in the modified asphalt composition for bonding is high in compatibility between the polymer and asphalt, and high mass loss resistance and high strength reduction at the time of oil adhesion of the modified asphalt composition for bonding. Therefore, 0.02 parts by mass or more is preferable, 0.04 parts by mass or more is more preferable, and 0.06 parts by mass or more is more preferable with respect to 100 parts by mass of asphalt. Further, the content of the crosslinking agent in the modified asphalt composition for adhesion is described in the specification of JP 2013-520543 A, from the viewpoint of obtaining a modified asphalt composition for adhesion with a high penetration. Moreover, you may use about 20-60 mass% in the modified asphalt composition for adhesion | attachment. The content of the crosslinking agent in the modified asphalt composition for adhesion is 1.0 mass relative to 100 parts by mass of asphalt in terms of obtaining an improved modified asphalt composition for adhesion and economical efficiency. Part or less, preferably 0.4 part by weight or less, and more preferably 0.2 part by weight or less.

  From the viewpoint of sufficiently reacting the crosslinking agent, the mixing time after adding the crosslinking agent to the modified asphalt master batch or the modified asphalt composition for adhesion is preferably 20 minutes or more, more preferably 40 minutes or more, More preferably 60 minutes or more. In addition, the mixing time after the addition of the crosslinking agent to the modified asphalt master batch or the modified asphalt composition for adhesion is preferably 5 hours or less and more preferably 3 hours or less from the viewpoint of suppressing thermal degradation of the polymer.

≪Method for producing modified asphalt composition for adhesion≫
<Method for producing block copolymer (B)>
The block copolymer (B) is, for example, a polymerization step in which a polymer is obtained by polymerizing at least a conjugated diene monomer and a vinyl aromatic monomer using a lithium compound as a polymerization initiator in a hydrocarbon solvent, It can manufacture by performing the solvent removal process of removing the solvent of the solution containing the obtained block copolymer. When hydrogenating the block copolymer, after the polymerization step, a hydrogenation step of hydrogenating the double bond in the conjugated diene monomer unit of the obtained polymer, the solvent of the solution containing the polymer is removed. By performing the solvent removal step, a hydrogenated block copolymer can be produced. When the block copolymer is partially hydrogenated, after the polymerization step, a hydrogenation step is performed in which hydrogen is added to a part of the double bond in the conjugated diene monomer unit of the obtained block copolymer. The partially hydrogenated block copolymer can be produced by performing a solvent removal step of removing the solvent of the solution containing the obtained partially hydrogenated block copolymer.
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.

  The hydrocarbon solvent used in the polymerization step is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. And aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. These may be used alone or in combination of two or more.

  Although it does not specifically limit as a lithium compound used as a polymerization initiator in a superposition | polymerization process, For example, the compound which combined one or more lithium atoms in molecules, such as an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound, is mentioned. . Such an organic lithium compound is not particularly limited. For example, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyl Examples include dilithium, isoprenyl dilithium, lithium piperidide and the like. These may be used alone or in combination of two or more.

  The conjugated diene monomer is not particularly limited. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3- Examples thereof include diolefins having a pair of conjugated double bonds such as pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are preferable. 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.

Although it does not specifically limit as a vinyl aromatic monomer, For example, styrene, (alpha) -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethyl styrene, And vinyl aromatic compounds such as N, N-diethyl-p-aminoethylstyrene. Of these, styrene is preferred 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 the vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer can also be used.

  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.

  Although it does not specifically limit as a polar compound or a randomizing agent, For example, ethers, such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether; Triethylamine, N, N, N ', N'-tetramethylethylenediamine (henceforth "TMEDA") Amines such as thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, and alkoxides of potassium and sodium.

  It does not specifically limit as a polymerization method implemented at the superposition | polymerization process of a block copolymer, A well-known method is applicable. Known methods include, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17799, 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 methods described in Japanese Patent No. 48-4106, Japanese Patent Publication No. 56-28925, Japanese Patent Application Laid-Open No. 59-166518, Japanese Patent Application Laid-Open No. 60-186777, and the like.

  The block copolymer may be coupled using a coupling agent. Although it does not specifically limit as a coupling agent, Bifunctional or more arbitrary coupling agents can be used. Although it does not specifically limit as a bifunctional coupling agent, For example, Bifunctional halogenated silanes, such as dichlorosilane, monomethyldichlorosilane, dimethyldichlorosilane; Diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldi Bifunctional alkoxysilanes such as ethoxysilane; Bifunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, dibromomethane; dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyl Bifunctional tin halides such as dichlorotin and dibutyldichlorotin; dibromobenzene, benzoic acid, CO, 2-chloropropene and the like.

  The trifunctional coupling agent is not particularly limited, and examples thereof include trifunctional halogenated alkanes such as trichloroethane and trichloropropane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; methyltrimethoxysilane; And trifunctional alkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane.

  The tetrafunctional coupling agent is not particularly limited, and examples thereof include tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; tetrafunctional halogenated silanes such as tetrachlorosilane and tetrabromosilane. Tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; tetrafunctional tin halides such as tetrachlorotin and tetrabromotin;

  The pentafunctional or higher functional coupling agent is not particularly limited. For example, polyhalogen such as 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, decabromodiphenyl ether, and the like. And hydrocarbon compounds.

  In addition, polyvinyl compounds such as epoxidized soybean oil, 2- to 6-functional epoxy group-containing compounds, bisphenol-type epoxy compounds, carboxylic acid esters, and divinylbenzene can also be used. A coupling agent may be used individually by 1 type, and can also be used in combination of 2 or more type.

  After the polymerization step, it is preferable to perform a deactivation step of deactivating the active end of the block copolymer. The active terminal of the polymer can be deactivated by reacting the active hydrogen-containing compound with the active terminal. Although it does not specifically limit as a compound which has active hydrogen, From an economical point, alcohol, water, etc. can be mentioned.

  When performing a hydrogenation process, you may add hydrogen to a part of double bond in the conjugated diene monomer unit of the block copolymer obtained at the superposition | polymerization process. The catalyst used in the hydrogenation reaction is not particularly limited. For example, a supported heterogeneous material in which a metal such as Ni, Pt, Pd, or Ru is supported on a support such as carbon, silica, alumina, or diatomaceous earth. System catalysts; so-called Ziegler type catalysts using organic salts such as Ni, Co, Fe, Cr or the like and acetylacetone salts and reducing agents such as organic Al; so-called organic complex catalysts such as organometallic compounds such as Ru and Rh; and titanocene Examples of the compound include a homogeneous catalyst using organic Li, organic Al, organic Mg, or the like as a reducing agent. Among these, a homogeneous catalyst system using organic Li, organic Al, organic Mg, or the like as a reducing agent for the titanocene compound is preferable from the viewpoint of economy, colorability of the polymer, or adhesive strength.

  The method for the hydrogenation reaction is not particularly limited. For example, the method described in JP-B-42-8704 and JP-B-43-6636, preferably JP-B-63-4841 and JP-B-63. And the method described in Japanese Patent No. 5401. Specifically, a hydrogenation reaction can be performed in an inert solvent in the presence of a hydrogenation catalyst to obtain a partially hydrogenated block copolymer solution. The hydrogenation reaction is preferably performed after the deactivation step from the viewpoint of high hydrogenation activity.

  In the hydrogenation step, the conjugated bond of the vinyl aromatic monomer unit may be hydrogenated. The upper limit of the hydrogenation rate of the conjugated bond in all vinyl aromatic monomer units may be, for example, 30 mol% or less, 10 mol% or less, or 3 mol% or less, based on the total amount of unsaturated groups in the aromatic. The lower limit can be, for example, 0.1 mol% or more, or 0 mol%.

  It is preferable to add a modifying group to the resulting block copolymer using a compound having a modifying group as a polymerization initiator, a monomer, a coupling agent, or a terminator.

  As the polymerization initiator containing a modifying group, a polymerization initiator containing a nitrogen-containing group is preferable, dioctylaminolithium, di-2-ethylhexylaminolithium, ethylbenzylaminolithium, (3- (dibutylamino) -propyl) lithium. And piperidinolithium.

  The monomer containing the modifying group is 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 in the monomer used for the above-described polymerization. And monomers having at least one modifying group. Among these, a monomer containing a nitrogen-containing group is preferable, for example, N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-dibutylvinylbenzyl. Amine, N, N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis (trimethylsilyl) aminoethylstyrene, 1- (4-N, N-dimethylaminophenyl) -1- Phenylethylene, N, N-dimethyl-2- (4-vinylbenzyloxy) ethylamine, 4- (2-pyrrolidinoethyl) styrene, 4- (2-piperidinoethyl) styrene, 4- (2-hexamethyleneiminoethyl) Styrene, 4- (2-morpholinoethyl) styrene, 4- (2- Ajinoechiru) styrene, 4- (2-N-methyl-piperazino-ethyl) styrene, 1 - ((4-vinyl) methyl) pyrrolidine, and 1- (4-vinyl benzyloxycarbonyl) pyrrolidine, and the like.

  As the coupling agent and terminator containing a modifying group, among the aforementioned coupling agents and terminators, a 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 And coupling agents having at least one modifying group selected from:

  Among these, coupling agents and terminators containing nitrogen-containing groups or oxygen-containing groups are preferred, for example, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyl. Diaminodiphenylmethane, diglycidylaniline, γ-caprolactone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane Γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl Dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β -(3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, 1,3 -Dimethyl-2-imidazolidinone, 1, - diethyl-2-imidazolidinone, N, N'-dimethyl propylene urea, N- methylpyrrolidone, and 1-methyl-4- (3- (triethoxysilyl) propyl) piperazine.

  In the solvent removal step, the solvent of the solution containing the block copolymer is removed. 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 block copolymer obtained by the solvent removal step is preferably as small as possible. For example, 2% by mass or less, 0.5% by mass or less, 0.2% by mass or less, 0.05% by mass or less, Or it can be 0.01 mass% or less, More preferably, it is 0 mass%. From the economical viewpoint, the amount of residual solvent in the block copolymer is usually in the range of 0.01% by mass to 0.1% by mass.

  From the viewpoint of heat aging resistance and gelation suppression of the block copolymer, it is preferable to add an antioxidant to the block copolymer. Examples of the antioxidant include 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 these, a phenolic antioxidant is preferable from the viewpoint of heat aging resistance and gelation suppression of the block copolymer.

  From the viewpoint of preventing coloration of block copolymer and improving mechanical strength, deashing process to remove metal in solution containing block copolymer, pH of solution containing block copolymer is adjusted before solvent removal process. For example, an acid and / or carbon dioxide gas may be added.

<Method for producing modified asphalt composition for adhesion>
There is no particular limitation regarding the method for producing the modified asphalt composition for adhesion of the present embodiment. For example, the modified asphalt composition for bonding according to the present embodiment comprises 20% by mass or more and 99.5% by mass or less of asphalt (A), and 0.5% by mass or more and 80% by mass or less of the block copolymer (B). It can manufacture by mixing with.

  There is no particular limitation on the method of mixing the block copolymer (B) and asphalt. The mixing method is not particularly limited. For example, a stirring tank (the stirring method includes a stirrer such as a vertical impeller, a side arm type impeller, a homogenizer including an emulsifier, or a stirring by a pump), an extruder, a kneader, and a banbury. They can be mixed with a melt kneader such as a mixer.

  As mixing temperature, it can carry out at the temperature of 160 degreeC or more and 200 degrees C or less (usually around 180 degreeC). The stirring time is usually 30 minutes to 6 hours, and a shorter one is better in terms of economy. What is necessary is just to select a stirring speed timely with the apparatus to be used, and it is 100 ppm or more and 8,000 rpm or less normally.

≪Adhesive modified asphalt mixture≫
The modified asphalt mixture for adhesion according to the present embodiment contains the modified asphalt composition for adhesion according to the present embodiment and an aggregate.
The method for mixing the modified asphalt composition for bonding and the aggregate is not particularly limited. The mixing temperature is preferably 90 ° C to 200 ° C. If it is 90 ° C. or lower, it is difficult to uniformly mix the aggregate and the modified asphalt composition for adhesion, and if it exceeds 200 ° C., the modified asphalt composition for adhesion may be decomposed or crosslinked, which is not preferable. As the mixing and stirring mixer, either a continuous type or a batch type can be used. As a preferable mixing method, for example, an aggregate heated to 90 ° C. to 200 ° C. is put into a mixer, and after kneading for 20 seconds to 30 seconds, the asphalt composition of the present invention heated to the same temperature as the aggregate is used. A good mixture can be produced by charging and mixing for 40 to 60 seconds.

  The aggregate is not limited, and for example, an aggregate conforming to the “asphalt pavement outline” issued by the Japan Road Association can be applied. In addition, it can be used in the present invention regardless of the material such as various other low-grade aggregates and recycled aggregates. Aggregates include, for example, crushed stones, cobblestones, gravel, steel slag, etc., similar granular materials, artificially fired aggregates, fired foam aggregates, artificial lightweight aggregates, ceramic grains, loxobite, aluminum grains, plastics Grains, ceramics, emery, construction waste, fibers, etc. can also be used.

Aggregates are generally classified into coarse aggregates, fine aggregates, and fillers.
Coarse aggregate is an aggregate that remains on a 2.36 mm sieve, 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 No. 4 crushed stone having a particle size range of 20 to 30 mm. In the present embodiment, an aggregate obtained by mixing one or more kinds of coarse aggregates having various particle diameter ranges, a synthesized aggregate, or the like can be used. These coarse aggregates may be coated with about 0.3 to 1% by weight of straight asphalt with respect to the aggregates.

  Fine aggregate means an aggregate that passes through a 2.36 mm sieve and stops on a 0.075 mm sieve. For example, river sand, hill sand, mountain sand, sea sand, crushed sand, fine sand, screenings, crushed stone dust , Silica sand, artificial sand, glass cullet, foundry sand, recycled aggregate crushed sand and the like.

  The filler passes through a 0.075 mm sieve, and examples thereof include screening filler content, stone powder, slaked lime, cement, incinerator ash, clay, talc, fly ash, and carbon black. In addition, as filler, even rubber particles, cork powder, wood powder, resin powder, fiber powder, pulp, artificial aggregate, etc., as long as it passes through a 0.075 mm sieve, It can be used as a filler.

  The particle size of the aggregate and the content of the modified asphalt composition for adhesion are described in, for example, “Types of Asphalt Mixture” described in “Asphalt Paving Guidelines”, Japan Road Association, December 1992, page 92. And a particle size range ”can be set as appropriate. For example, the asphalt mixture for adhesion containing 2 to 15% by mass of the modified asphalt composition for adhesion and 85 to 98% by mass of the aggregate of the present embodiment is preferable.

≪Use of modified asphalt composition for adhesion and modified asphalt mixture for adhesion≫
The adhesive modified asphalt composition and the adhesive modified asphalt mixture of the present embodiment are not particularly limited as long as they are used for adhesion to an adherend, and for example, used as a laminate with an adherend. be able to.

  The laminate of this embodiment includes a first layer of at least one adherend selected from the group consisting of polar resin, metal, inorganic oxide, asphalt, asphalt mixture, and composites thereof, and modified asphalt for adhesion It is a laminated body which laminated | stacked the composition or the 2nd layer of the modified asphalt mixture for adhesion | attachment. Since the adherend has been described above, the description thereof is omitted here.

  The laminated body in this embodiment may have another layer as long as the first layer and the second layer are in contact with each other, and the order of lamination is not limited.

  The manufacturing method of the laminated body in this embodiment is not specifically limited, For example, a thermal construction method, a torch construction method, a self-adhesion construction method, and a composite construction method are mentioned. Since the wear-modified asphalt composition or mixture of this embodiment has high heat aging resistance, a heat method or a torch method can also be suitably used.

  The laminated body of this embodiment can be used suitably for a road pavement use and an asphalt waterproof sheet use, for example.

  Use of the modified asphalt composition for adhering or the mixture of the present embodiment for road pavement is preferable in terms of anti-aggregation resistance.

  In road pavement applications, the content of the block copolymer (B) in the modified asphalt composition for adhesion is 2% by mass or more to 15% from the viewpoint of aggregate peeling resistance, flow resistance, and workability. The content is preferably 3% by mass or less, more preferably 3% by mass or more and 12% by mass or less, and still more preferably 4% by mass or more and 10% by mass or less.

  In road pavement applications, for example, it is effective as an adhesive layer between the base layer and the surface pavement from the viewpoint of aggregate peeling resistance and fluid resistance, and as a surface pavement, the adhesive modification of this embodiment is effective. Quality asphalt mixture may be used. In general, for road paving applications, the base layer is an asphalt mixture containing aggregate and asphalt.

  By using the modified asphalt composition or mixture for adhesion of the present embodiment for asphalt tarpaulin applications, the fatigue fracture resistance, weather resistance, crack resistance at low temperature, resistance to misalignment and dripping at high temperature of the asphalt tarpaulin This is preferable in that the property and load resistance can be further improved.

  In asphalt tarpaulin applications, the content of the block copolymer (B) in the modified asphalt composition for adhesion includes high flexibility, crack resistance at lower temperatures, resistance to slippage and sagging at higher temperatures. From the viewpoint of heat resistance, high fatigue flexibility, and weather resistance, it is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 9% by mass or more. On the other hand, 20 mass% or less is preferable, 17 mass% or less is more preferable, and 14 mass% or less is further more preferable in the point of the manufacturability and economical efficiency of the modified asphalt composition for adhesion.

  When using the modified asphalt composition or mixture for adhesion of this embodiment at room temperature in asphalt tarpaulin applications, good low-temperature usability, low viscosity of the modified asphalt composition or mixture for adhesion, and high workability From this point of view, it is preferable to use asphalt having a high penetration. For example, asphalt having a penetration of 80 or more is preferable, 100 or more is more preferable, 130 or more is further preferable, and 160 or more is most preferable.

  In the asphalt waterproof sheet application, for example, it is effective for bonding with a polyester film or polyurethane as an adherend, and is also effective as an asphalt waterproof sheet for road pavement for bridges.

  When using the modified asphalt composition or mixture for adhesion of the present embodiment at a high temperature such as a torch method in asphalt waterproof sheet applications, the viscosity of the modified asphalt composition or mixture for adhesion should not be too low. It is preferable to use asphalt having a lower penetration than when constructing at normal temperature. For example, asphalt having a penetration of 30 to 150 is preferable, 60 to 120 is more preferable, and 80 to 100 is more preferable.

  In asphalt waterproof sheet applications, it is preferable to add a softener from the viewpoint of good low-temperature useability, low viscosity of the modified asphalt composition or mixture for adhesion, and high workability. In terms of obtaining a better effect, mineral oil softeners are preferable, and paraffinic hydrocarbons or naphthenic hydrocarbons are more preferable. Moreover, you may use an inorganic filler as needed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. The measuring method regarding the block copolymer in an Example and a comparative example is as follows.

≪Measurement method≫
<Content of vinyl aromatic monomer unit in block copolymer (styrene content)>
A certain amount of the polymer was dissolved in chloroform, and from the peak intensity of the absorption wavelength (262 nm) due to the vinyl aromatic monomer unit (styrene) using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450). The content of vinyl aromatic monomer units (styrene) was calculated using a calibration curve.
<Content of polymer block (a) in block copolymer>
Using a block copolymer before hydrogenation, M.M. Koithoff, et al. , J .; Polym. Sci. 1, p. 429 (1946), the vinyl aromatic monomer block content was measured by the osmium tetroxide method. For the decomposition of the block copolymer, an osmic acid 0.1 g / 125 mL tertiary butanol solution was used.

<Vinyl content in block copolymer and hydrogenation rate of unsaturated group in conjugated diene>
The vinyl content in the block copolymer and the hydrogenation rate of unsaturated groups in the conjugated diene were measured by nuclear magnetic resonance spectrum analysis (NMR) under the following conditions. In the measurement, the reaction solution containing the block copolymer after the hydrogenation reaction was poured into a large amount of methanol to precipitate and collect the block copolymer. Subsequently, the 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 condition)
Measuring instrument: 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

<Number average molecular weight>
The number average molecular weight was measured by gel permeation chromatography (hereinafter also referred to as “GPC”. The apparatus is manufactured by Waters Co., Ltd.) In the GPC measurement, tetrahydrofuran was used as a solvent and the temperature was set to 35 ° C. Chromatogram The molecular weight of the peak was determined using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from measurement of commercially available standard polystyrene, and the molecular weight was defined as the number average molecular weight (polystyrene equivalent molecular weight).
<Peak temperature and peak height of loss tangent (tan δ)>
The dynamic viscoelastic spectrum was measured by the following method to determine the peak temperature and peak height of loss tangent (tan δ). Torsion type geometry of device ARES (trade name, manufactured by TI Instruments Inc.), sample thickness 2mm, width 10mm, length 20mm, strain (initial strain) 0.5%, frequency 1Hz, measurement range The measurement was performed from −100 ° C. to 100 ° C. under conditions of a temperature increase rate of 3 ° C./min.

≪Example of block copolymer production≫
<Example of hydrogenation catalyst adjustment>
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.
<Block copolymer B-1>
Polymerization was carried out by the following method using a stirring apparatus having an internal volume of 10 L and a tank reactor with a jacket. After adding 20 parts by mass of cyclohexane to the reactor and adjusting the temperature to 70 ° C., 0.053 parts of n-butyllithium was added to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). Mass parts and 0.35 mol of TMEDA with respect to 1 mol of n-butyllithium were added.

  As a first step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. .

  As a second step, a cyclohexane solution containing 59 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 21 parts by mass of styrene (styrene monomer concentration of 22% by mass) are respectively 20 minutes and 10 minutes. And continuously fed to the reactor at a constant rate, and then allowed to react for 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a third step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, the reactor internal temperature is about 70 ° C., and the reactor internal pressure is 0.30 MPa. The mixture was reacted for 30 minutes while adjusting to obtain a block copolymer.

  After adding methanol to the block copolymer obtained in the third step to deactivate the polymerization active end, a hydrogenation reaction was performed using the hydrogenation catalyst to obtain a block copolymer B-1. Next, 0.3 mass% of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer with respect to the mass of the block copolymer B-1.

  The block copolymer B-1 has a styrene content of 41% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 92 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −31 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-2>
As a first step, a cyclohexane solution containing 3 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 86 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 8 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously supplied to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, in the third step. The polymer was polymerized in the same manner as the polymer B-1, except that a cyclohexane solution containing 3 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes.
The block copolymer B-2 has a styrene content of 14% by mass, a styrene block content of 6% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 65 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −54 ° C., and the tan δ peak height was 1.0.

<Block copolymer B-3>
As a first step, a cyclohexane solution containing 3 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 82 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 12 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously supplied to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, in the third step. The polymer was polymerized in the same manner as the polymer B-1, except that a cyclohexane solution containing 3 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes.
The block copolymer B-3 has a styrene content of 18% by mass, a styrene block content of 6% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 65 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −48 ° C., and the tan δ peak height was 1.0.

<Block copolymer B-4>
As a first step, a cyclohexane solution containing 15 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 45 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 25 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously supplied to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, in the third step. The polymer was polymerized in the same manner as the polymer B-1, except that a cyclohexane solution containing 15 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes.
The block copolymer B-4 has a styrene content of 55 mass%, a styrene block content of 30 mass%, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 90 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −10 ° C., and the tan δ peak height was 1.0.

<Block copolymer B-5>
As a first step, a cyclohexane solution containing 15 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 40 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 30 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, in the third step. The polymer was polymerized in the same manner as the polymer B-1, except that a cyclohexane solution containing 15 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes.
The block copolymer B-5 has a styrene content of 60% by mass, a styrene block content of 30% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 50 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was 2 ° C., and the tan δ peak height was 1.0.

<Block copolymer B-6>
As a first step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 38 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 42 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively. As described above, polymerization was carried out in the same manner as the polymer B-1, except that a cyclohexane solution (styrene monomer concentration: 20% by mass) containing 10 parts by mass of styrene as a monomer was added over about 3 minutes.
The block copolymer B-6 has a styrene content of 62% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 90 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was 14 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-7>
Cyclohexane containing 0.070 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers (the total amount of butadiene monomer and styrene monomer charged into the reactor), and as a first step, containing 8 parts by mass of styrene as a monomer A solution (styrene monomer concentration of 20% by mass) was added over about 5 minutes, and as a second step, a cyclohexane solution containing 48 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and cyclohexane containing 36 parts by mass of styrene. The solution (styrene monomer concentration 22% by mass) was continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, and as a third step, a cyclohexane solution (styrene) containing 8 parts by mass of styrene as a monomer. Add monomer concentration 20% by mass) over about 3 minutes Except were polymerized in the same manner as Polymer B-1 to.
The block copolymer B-7 had a styrene content of 52 mass%, a styrene block content of 16 mass%, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 99 mol%, and a number average molecular weight of 13. The tan δ peak temperature was 80,000, the tan δ peak temperature was −14 ° C., and the tan δ peak height was 1.7.

<Block copolymer B-8>
A block copolymer B-8 was produced in the same manner as the block copolymer B-1, except that the hydrogenation rate of the block copolymer B-1 was changed.
The block copolymer B-8 had a styrene content of 41% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 84 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −31 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-9>
A block copolymer B-9 was produced in the same manner as the block copolymer B-1, except that the hydrogenation rate of the block copolymer B-1 was changed.
The block copolymer B-9 had a styrene content of 41% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 50 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −32 ° C., and the tan δ peak height was 1.2.

<Block copolymer B-10>
A block copolymer B-10 was produced in the same manner as the block copolymer B-1, except that the hydrogenation rate of the block copolymer B-1 was changed.
The block copolymer B-10 had a styrene content of 41% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 20 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −34 ° C., and the tan δ peak height was 1.3.

<Block copolymer B-11>
As a first step, a cyclohexane solution containing 4 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 59 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 33 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, in the third step. The polymer was polymerized in the same manner as the polymer B-1, except that a cyclohexane solution containing 4 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes.
The block copolymer B-11 has a styrene content of 41% by mass, a styrene block content of 8% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 92 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −10 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-12>
As a first step, a cyclohexane solution containing 6.5 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 59 parts by mass of butadiene ( A butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 28 parts by mass of styrene (styrene monomer concentration of 22% by mass) were continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively. As 3 steps, it polymerized similarly to the polymer B-1 except adding the cyclohexane solution (styrene monomer concentration 20 mass%) containing 6.5 mass parts of styrene as a monomer over about 3 minutes.
The block copolymer B-12 had a styrene content of 41% by mass, a styrene block content of 13% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 92 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −26 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-13>
As a first step, a cyclohexane solution containing 22.5 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 45 parts by mass of butadiene ( A butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 10 parts by mass of styrene (styrene monomer concentration of 22% by mass) are continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively. As 3 steps, it polymerized similarly to the polymer B-1 except adding the cyclohexane solution (styrene monomer density | concentration of 20 mass%) containing 22.5 mass parts of styrene as a monomer over about 3 minutes.
The block copolymer B-13 had a styrene content of 55% by mass, a styrene block content of 45% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 92 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −40 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-14>
As a first step, a cyclohexane solution containing 26 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, a cyclohexane solution containing 42 parts by mass of butadiene (butadiene monomer) And a cyclohexane solution containing 6 parts by mass of styrene (styrene monomer concentration of 22% by mass) is continuously fed to the reactor at a constant rate over 20 minutes and 10 minutes, respectively, in the third step. As a polymer, polymerized in the same manner as the polymer B-1, except that a cyclohexane solution containing 26 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes.
The block copolymer B-14 has a styrene content of 58% by mass, a styrene block content of 52% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 92 mol%, and a number average molecular weight of 20%. The tan δ peak temperature was −48 ° C., and the tan δ peak height was 1.1.

<Block copolymer B-15>
Polymerization was carried out by the following method using a stirring apparatus having an internal volume of 10 L and a tank reactor with a jacket. After adding 20 parts by mass of cyclohexane to the reactor and adjusting the temperature to 70 ° C., 0.053 parts of n-butyllithium was added to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). Mass parts and 0.35 mol of TMEDA with respect to 1 mol of n-butyllithium were added.

  As a first step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. .

  As a second step, a cyclohexane solution containing 22 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 5 parts by mass of styrene (styrene monomer concentration of 22% by mass) are maintained at a constant rate over 15 minutes. Was continuously fed to the reactor. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a third step, a cyclohexane solution containing 22 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 11 parts by mass of styrene (styrene monomer concentration of 22% by mass) are maintained at a constant rate over 15 minutes. Was continuously fed to the reactor. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a fourth step, a cyclohexane solution containing 15 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 5 parts by mass of styrene (styrene monomer concentration of 22% by mass) are maintained at a constant rate over 15 minutes. Were continuously fed to the reactor and then reacted for 10 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a fifth step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, the reactor internal temperature is about 70 ° C., and the reactor internal pressure is 0.30 MPa. The mixture was reacted for 30 minutes while adjusting to obtain a block copolymer.

Methanol was added to the block copolymer obtained in the fifth step to deactivate the polymerization active end, and then hydrogenation reaction was performed using the hydrogenation catalyst to obtain a block copolymer B-15. Next, 0.3 mass% of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer with respect to the mass of the block copolymer B-15.
The block copolymer B-15 had a styrene content of 41% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 99 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −30 ° C., and the tan δ peak height was 0.7.

<Block copolymer B-16>
Polymerization was carried out by the following method using a stirring apparatus having an internal volume of 10 L and a tank reactor with a jacket. After adding 20 parts by mass of cyclohexane to the reactor and adjusting the temperature to 70 ° C., 0.053 parts of n-butyllithium was added to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). Mass parts and 0.35 mol of TMEDA with respect to 1 mol of n-butyllithium were added.

  As a first step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. .

  As a second step, a cyclohexane solution containing 61 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 19 parts by mass of styrene (styrene monomer concentration of 22% by mass) were respectively 20 minutes and 10 minutes. And continuously fed to the reactor at a constant rate, and then allowed to react for 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a third step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, the reactor internal temperature is about 70 ° C., and the reactor internal pressure is 0.30 MPa. The reaction was carried out for 10 minutes while adjusting, and then 0.9 mol of 1,3-dimethyl-2-imidazolidinone was added to 1 mol of n-butyllithium added before the first step.

  After adding methanol to the block copolymer obtained in the fourth step to deactivate the polymerization active end, a hydrogenation reaction was performed using the hydrogenation catalyst to obtain a block copolymer B-16. Next, 0.3 mass% of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer with respect to the mass of the block copolymer B-16.

  The block copolymer B-16 had a styrene content of 39% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 67 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −39 ° C., and the tan δ peak height was 0.7.

<Block copolymer B-17>
Polymerization was carried out by the following method using a stirring apparatus having an internal volume of 10 L and a tank reactor with a jacket. After adding 20 parts by mass of cyclohexane to the reactor and adjusting the temperature to 70 ° C., 0.053 parts of n-butyllithium was added to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). Mass parts and 0.35 mol of TMEDA with respect to 1 mol of n-butyllithium were added.

  As a first step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. .

  As a second step, a cyclohexane solution containing 59 parts by mass of butadiene (butadiene monomer concentration of 20% by mass) and a cyclohexane solution containing 21 parts by mass of styrene (styrene monomer concentration of 22% by mass) are respectively 20 minutes and 10 minutes. And continuously fed to the reactor at a constant rate, and then allowed to react for 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a third step, a cyclohexane solution containing 10 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, the reactor internal temperature is about 70 ° C., and the reactor internal pressure is 0.30 MPa. The reaction was carried out for 10 minutes while adjusting, and then 0.9 mol of 1,3-dimethyl-2-imidazolidinone was added to 1 mol of n-butyllithium added before the first step.

  Methanol was added to the block copolymer obtained in the third step to deactivate the polymerization active end, and then hydrogenation reaction was performed using the hydrogenation catalyst to obtain block copolymer B-17. Next, 0.3 mass% of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer with respect to the mass of the block copolymer B-16.

  The block copolymer B-17 had a styrene content of 41% by mass, a styrene block content of 20% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 71 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −30 ° C., and the tan δ peak height was 1.2.

<Block copolymer B-18>
As a first step, a cyclohexane solution containing 20 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes, and as a second step, 60 parts by mass of butadiene are added at a constant rate over 30 minutes. As in the case of the polymer B-1, except that the cyclohexane solution containing 20 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) is added over about 3 minutes as a third step. Was polymerized.
The block copolymer B-18 had a styrene content of 40% by mass, a styrene block content of 40% by mass, a hydrogenation rate of double bonds in the conjugated diene monomer unit of 92 mol%, and a number average molecular weight of 200,000. The tan δ peak temperature was −48 ° C., and the tan δ peak height was 1.0.

<Block copolymer B-19>
Polymerization was carried out by the following method using a stirring apparatus having an internal volume of 10 L and a tank reactor with a jacket. After 20 parts by mass of cyclohexane was put in the reactor and the temperature was adjusted to 70 ° C., n-butyllithium was 0.11 per 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). A mass part and 0.05 mol of TMEDA with respect to 1 mol of n-butyllithium were added.

  As a first step, a cyclohexane solution containing 15 parts by mass of styrene as a monomer (styrene monomer concentration 20% by mass) was added over about 5 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. .

  As a second step, a cyclohexane solution containing 70 parts by mass of butadiene (butadiene monomer concentration: 20% by mass) was continuously supplied to the reactor at a constant rate over 30 minutes, and then reacted for 20 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.

  As a third step, as a coupling agent, diglycidyl etherification modified product of 2,2-bis (4-hydroxyphenyl) propane with epichlorohydrin and diglycidyl of phenol-formaldehyde polycondensate with epichlorohydrin A block copolymer B-19 was obtained by adding a mixture containing the etherified modified product at a weight ratio of 1/1 and coupling the mixture.

  After completion of the reaction, methanol is added to deactivate the polymerization active end, then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is added as a stabilizer, and the mass of the block copolymer I 0.3 mass% was added with respect to.

In block copolymer B-19, the styrene content was 30% by mass, the styrene block content was 30% by mass, the hydrogenation rate of double bonds in the conjugated diene monomer unit was 0 mol%, and the diblock before coupling. And the triblock after coupling, the mass ratio was 70/30% by mass, the number average molecular weight ratio was 85,000 / 170,000, the tan δ peak temperature was −80 ° C., and the tan δ peak height was 0.5.
The analysis results of the block copolymers (B-1) to (B-19) are summarized in Table 1 below.

≪Example of manufacturing modified asphalt composition for adhesion≫
The materials used for the production of the modified asphalt composition for adhesion are as follows.
Asphalt: Straight asphalt 60-80 (manufactured by Nippon Oil Corporation, penetration 60-80)
Block copolymer: Block copolymers (B-1) to (B-19) prepared by the above method
Additives: C-1 (Mitsui Chemicals, maleic anhydride modified polyolefin elastomer, Tuffmer M: MH7010), C-2 (Zeon, tackifier, Quinton R100), C-3 (made by Idemitsu Kosan Co., Ltd., Softener, Diana Process Oil NS90S)

[Examples 1 to 23 and Comparative Examples 1 to 6]
Using the materials shown above, a modified asphalt composition for adhesion was produced by the following method.
Example 1
500 g of asphalt was put into a 750 mL metal can, and the metal can was sufficiently immersed in an oil bath at 180 ° C. to melt the asphalt. Next, while stirring 99.4% by mass of molten asphalt at a rotational speed of 4000 rpm, 0.6% by mass of the block copolymer (B-1) was added, and after the addition, the mixture was stirred for 60 minutes, The modified asphalt composition for adhesion of Example 1 was produced.
(Examples 2-16, 18, and 21 and Comparative Examples 1-6)
Each modified asphalt composition for adhesion was produced in the same manner as in Example 1 except that the composition was changed as shown in Tables 2 to 4. The block copolymer and the additive were added almost simultaneously.
(Examples 17, 19, and 20)
Each modified asphalt composition for adhesion was produced in the same manner as in Example 1 except that the composition was changed as shown in Table 4 and the stirring time was 90 minutes. The block copolymer and the additive were added almost simultaneously.
The evaluation method of the modified asphalt composition for adhesion is shown below.

≪Evaluation method≫
<Short-time manufacturability of the modified asphalt composition for adhesion>
The solubility when the modified asphalt composition for bonding was produced was visually observed, and the time from the start of stirring until the block copolymer was dissolved and the grains disappeared was defined as the production time. The shorter the production time, the better the short-time productivity. ◎, ○, △, × from the good order.
〔Evaluation criteria〕
Dissolves in less than 20 minutes: ◎
Dissolve in 20 minutes or more and less than 30 minutes: ○
Dissolved in 30 minutes or more and less than 40 minutes: △
Dissolve in 40 minutes or more: ×
<Processability of modified asphalt composition for adhesion>
The modified asphalt composition for adhesion was measured for melt viscosity at 180 ° C. using a Brookfield viscometer. The lower the melt viscosity, the better the workability. ◎, ○, △, × from the good order.
〔Evaluation criteria〕
Less than 500 mPa · s: ◎
500 mPa · s or more and less than 1000 mPa · s: ○
1000 mPa · s or more and less than 2000 mPa · s: Δ
2000 mPa · s or more: ×

<Peeling test of modified asphalt composition for adhesion>
The peel test was performed according to the standard of the tensile shear bond strength test method of adhesive-rigid adherend according to JIS K6850. Modified asphalt composition for adhesion prepared in Examples 1 to 21 and Comparative Examples 1 to 6 as samples on a stainless steel (SUS) plate (arithmetic surface roughness: 0.1 μm) as an adherend 0.1 g of SUS plate (width 25 mm × length 100 mm, thickness 2 mm plate) is placed on the center in the width direction 12.5 mm from the end of the SUS plate, and SUS as an adherend of the same shape is placed on the sample. The plate was placed so that the length overlaps 25 mm and the sample is in the center. Next, the test piece for peel strength measurement was produced by pressing with a hot press. The pressing conditions were a temperature of 110 ° C., a load of 5 kg, preheating for 5 minutes, pressing for 3 minutes, and cooling for 4 minutes. After standing for 18 hours, a peel test was performed at a temperature of 23 ° C. using a tensile tester, and the result was designated as “initial peel strength”.

Moreover, after immersing the said test piece in the water of temperature 23 degreeC for 14 days, the result of having done the peeling test similarly was made into the "peeling strength after being immersed in water."
Moreover, after setting the said test piece in the tensile tester with a thermostat and hold | maintaining at 0 degreeC for 1 hour, the result of having performed the peeling test as it was was set as "low temperature peeling strength."
Further, except that the adherend was changed to a polyethylene terephthalate (PET) plate, a urethane plate, and an asphalt mixture (AS mixture) plate, the initial peel strength and water were changed in the same manner as in the case of using the SUS plate. A peel strength test after immersion was conducted.

In addition, a polyethylene terephthalate (PET) plate was used as an adherend, and the test specimens were summer (July 21, 2014 to August 20, 2014) and winter (January 13, 2015 to 2015). On the 12th of February 12), after leaving in a place without an outdoor roof in Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture, the result of the peel test was similarly referred to as “peel strength after outdoor exposure”.
The peelability is better when the strength is higher, and in the order of goodness, ◎, ○, Δ, ×.

〔Evaluation criteria〕
(Initial peel strength)
A: 1.5 MPa or more ○: 1.3 MPa or more and less than 1.5 MPa Δ: 1.0 MPa or more and less than 1.3 MPa x: Less than 1.0 MPa (peel strength after water immersion, low-temperature peel strength, peel strength after outdoor exposure) )
A: 1.3 MPa or more O: 1.0 MPa or more and less than 1.3 MPa Δ: 0.7 MPa or more and less than 1.0 MPa x: Less than 0.7 MPa Evaluation results are summarized in Tables 2 to 4 below.

  The modified asphalt composition for adhesion and the modified asphalt mixture for adhesion according to the present embodiment can be used in fields such as road pavement, roofing and waterproofing sheets, and sealants. Among them, it is preferably used in the field of road pavement. it can.

Claims (10)

A modified asphalt composition for adhesion to at least one adherend selected from the group consisting of polar resin, metal, inorganic oxide, asphalt, asphalt mixture, and composites thereof,
20% to 99.5% by weight of asphalt (A),
Including 0.5% by mass or more and 80% by mass or less of the block copolymer (B),
The block copolymer (B) includes at least a conjugated diene monomer unit and a vinyl aromatic monomer unit,
The vinyl aromatic monomer unit in the block copolymer (B) is 15% by mass or more and 60% by mass or less,
The modified asphalt composition for adhesion, wherein a peak temperature of loss tangent (tan δ) by dynamic viscoelasticity measurement of the block copolymer (B) is −50 ° C. or more and −5 ° C. or less.   The block copolymer (B) is mainly composed of at least a polymer block (a) mainly composed of a vinyl aromatic monomer unit, a conjugated diene monomer unit and a vinyl aromatic monomer unit. The modified asphalt composition for adhesion according to claim 1, comprising a copolymer block (b).   The modified asphalt composition for adhesion according to claim 1 or 2, wherein a hydrogenation rate of a double bond in the conjugated diene monomer unit in the block copolymer (B) is 95 mol% or less. The modified asphalt composition for adhesion according to any one of claims 1 to 3, wherein the content of the polymer block (a) in the block copolymer (B) is 10 mass% or more and 50 mass% or less. object. The modified asphalt composition for adhesion according to any one of claims 1 to 4, wherein the block copolymer (B) comprises a modified block copolymer having a modifying group.   The adhesion according to claim 5, wherein the modifying group is at least one modifying 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. Modified asphalt composition for use.   For a total of 100 parts by mass of the asphalt (A) and the block copolymer (B), the tackifier contains 0 part by mass to 300 parts by mass or less, or the softener contains 0 part by mass and 50 parts by mass or less. The modified asphalt composition for adhesion according to any one of claims 1 to 6, comprising both of them.   A modified asphalt mixture for adhesion, comprising the modified asphalt composition for adhesion according to any one of claims 1 to 7 and an aggregate.   The first layer of at least one adherend selected from the group consisting of a polar resin, a metal, an inorganic oxide, asphalt, an asphalt mixture, and a composite thereof, and according to any one of claims 1 to 7. A laminate obtained by laminating a second layer of the modified asphalt composition for adhesion.   A first layer of at least one adherend selected from the group consisting of a polar resin, a metal, an inorganic oxide, asphalt, an asphalt mixture, and a composite thereof, and the modified asphalt mixture for adhesion according to claim 8, A laminate in which the second layer is laminated.