JP6628514B2 - Hydrogenated block copolymer, and adhesive composition, modified asphalt composition and modified asphalt mixture using the same - Google Patents

Description

  The present invention relates to a hydrogenated block copolymer, and an adhesive composition, a modified asphalt composition and a modified asphalt mixture using the same.

Conventionally, block copolymers have been widely used for adhesive compositions, asphalt compositions, and the like.
In recent years, hot-melt adhesive compositions have been widely used from the viewpoint of reducing environmental pollution and improving the working environment. Generally, the hot-melt adhesive composition contains a block copolymer. Examples of such a block copolymer include a block copolymer having a vinyl aromatic monomer unit and a conjugated diene monomer unit.

For example, Patent Documents 1 and 2 describe an adhesive composition using a triblock copolymer of styrene and butadiene and a diblock copolymer as the block copolymer.
Patent Document 3 discloses an adhesive composition using a hydrogenated block copolymer of styrene and butadiene. The Examples and Comparative Examples of Patent Document 3 describe various types of adhesive compositions containing a hydrogenated block copolymer of styrene and butadiene, a tackifier resin, and oil.
Further, Patent Document 4 discloses an adhesive composition containing a block copolymer of styrene and butadiene and a tackifier resin, wherein the block copolymer of styrene and butadiene is a partially hydrogenated block copolymer. An adhesive composition using a combination of an unionized block copolymer and a non-hydrogenated block copolymer and an adhesive composition using a partially hydrogenated block copolymer and a completely hydrogenated block copolymer are described.

  On the other hand, in the asphalt composition, various block copolymers were added as a modifier to the asphalt composition in order to add performance according to the use of the asphalt composition such as road pavement, a sound insulation sheet, and asphalt roofing. Modified asphalt compositions are widely used. As such a block copolymer as a modifier, for example, a block copolymer having a conjugated diene monomer unit and a vinyl aromatic monomer unit is used.

  For example, Patent Documents 5 to 7 disclose modified asphalt compositions containing a hydrogenated block polymer obtained by copolymerizing a conjugated diene monomer and a vinyl aromatic monomer.

JP-A-64-81877 JP-A-61-278578 International Publication No. 2001/85818 JP-A-7-157738 JP 2005-126485 A US Patent Application Publication No. 2003/0149140 JP 2012-246378 A

The adhesive composition is required to have a high adhesive strength, a high tackiness, and a high adhesive holding power, and a balance between each of these physical properties and a short dissolving time during production (hereinafter, also referred to as “solubility”). Is required. In addition, the modified asphalt composition is required to have high low-temperature elongation, high heat aging resistance, and high fluid resistance, and furthermore, a balance between these physical properties and the compatibility of the modified asphalt composition is required. .
However, the adhesive compositions described in Patent Literatures 1 to 4 and the modified asphalt compositions described in Patent Literatures 5 to 7 improve the balance between various physical properties and solubility or compatibility. There is a problem that there is room.

  Therefore, in the present invention, it is possible to improve the balance between each physical property and solubility such as high adhesive strength of the adhesive composition, high tackiness, high adhesive holding power, and high low temperature of the modified asphalt composition. To provide a hydrogenated block copolymer capable of improving the balance between physical properties such as elongation, high heat aging resistance and high fluidity and compatibility, and a pressure-sensitive adhesive composition using the same. And a modified asphalt composition.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a hydrogenated block copolymer having a specific vinyl content can solve the above problems, and have completed the present invention. .
That is, the present invention is as follows.

[1]
A hydrogenated block copolymer having a polymer block (A) mainly containing vinyl aromatic monomer units and a polymer block (B) containing conjugated diene monomer units,
The polymer block (B) is a polymer block (B1) mainly containing a conjugated diene monomer unit or a copolymer block (B2) containing a conjugated diene monomer unit and a vinyl aromatic monomer unit. Yes,
The polymer block (A) mainly containing the vinyl aromatic monomer unit contains at least 90% by mass of the vinyl aromatic monomer unit,
The polymer block (B1) mainly composed of the conjugated diene monomer unit contains 90% by mass or more of the conjugated diene monomer unit,
The copolymer block (B2) containing the conjugated diene monomer unit and the vinyl aromatic monomer unit contains 20% by mass or more and 50% by mass or less of the vinyl aromatic monomer unit,
The content of the vinyl aromatic monomer unit of the hydrogenated block copolymer is 10% by mass or more and 45% by mass or less,
In the polymer block (B), the first to sixth regions are set to have the same mass in order from the polymerization start terminal side, and the first to sixth regions have the maximum vinyl content before hydrogenation. A hydrogenated block copolymer having a value of _VH and a minimum value of _VL , wherein _VH - _VL = 5 mol% or more and 30 mol% or less.
[2]
The hydrogenated block copolymer according to [1], wherein a hydrogenation rate of the hydrogenated block copolymer is 95 mol% or less based on the total number of moles of the conjugated diene monomer units.
[3]
The hydrogenated block copolymer according to [1] or [2], wherein the hydrogenation rate of the hydrogenated block copolymer is 10 mol% or more based on the total number of moles of the conjugated diene monomer units. Coalescing.
[4]
The hydrogenated block copolymer according to any one of the above [1] to [3] , wherein the hydrogenated block copolymer contains a hydrogenated block copolymer (r1) having a radial structure.
[5]
100 parts by mass of the hydrogenated block copolymer according to any one of the above [1] to [4] ,
20 parts by weight or more and 400 parts by weight or less of tackifying resin,
And a pressure-sensitive adhesive composition.
[6]
An adhesive tape comprising the adhesive composition according to [5] .
[7]
A label containing the adhesive composition according to the above [5] .
[8]
The hydrogenated block copolymer according to any one of the above [1] to [3] , wherein the hydrogenated block copolymer has a weight average molecular weight (Mw) of 100,000 to 500,000.
[9]
Any of the above [1] to [3], [8] , wherein a peak temperature of a loss tangent (tan δ) by dynamic viscoelasticity measurement of the hydrogenated block copolymer is −50 ° C. or more and −5 ° C. or less. 2. The hydrogenated block copolymer according to item 1.
[10]
A peak temperature of a loss tangent (tan δ) measured by dynamic viscoelasticity measurement of the hydrogenated block copolymer is −50 ° C. or more and −5 ° C. or less;
The value of the peak height of the loss tangent (tan δ) in the range of −50 ° C. or more and −5 ° C. or less by dynamic viscoelasticity measurement of the hydrogenated block copolymer is more than 0.7 and not more than 1.6. The hydrogenated block copolymer according to any one of [1] to [3], [8], and [9] .
[11]
For 100 parts by mass of asphalt,
A modified asphalt composition comprising 1 to 20 parts by mass of the hydrogenated block copolymer according to any one of the above [1] to [3] and [8] to [10] .
[12]
A modified asphalt mixture comprising the modified asphalt composition according to [11] and an aggregate.

  According to the present invention, it is possible to improve the balance between various physical properties such as high adhesive strength of the adhesive composition, high tackiness, high adhesive holding power and solubility, and also to improve the low temperature of the modified asphalt composition. It is possible to provide a hydrogenated block copolymer that can improve the balance between physical properties such as elongation, high heat aging resistance, and high flow resistance, and compatibility, and to use this to provide adhesiveness. An agent composition and a modified asphalt composition can be provided.

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 embodiments, and can be implemented with various modifications within the scope of the gist.

(Hydrogenated block copolymer)
The hydrogenated block copolymer of the present embodiment is a water-containing block having a polymer block (A) mainly containing vinyl aromatic monomer units and a polymer block (B) containing conjugated diene monomer units. It is an addition block copolymer.
In the polymer block (B), the first region to the sixth region are set so as to have the same mass in order from the polymerization start terminal side, and of the vinyl content of the first region to the sixth region before hydrogenation, When the maximum value is _VH and the minimum value is _VL , _VH - _VL = 5 mol% or more and 30 mol% or less.

  The hydrogenated block copolymer of the present embodiment has a polymer block (A) mainly composed of a vinyl aromatic monomer unit and a polymer block (B) containing a conjugated diene monomer unit.

Here, in the specification of the present application, a structural unit constituting a polymer is referred to as a “monomer unit”, and when described as a material of the polymer, it is simply referred to as a “monomer”.
In the specification of the present application, “mainly” means that the content of a predetermined monomer unit in a polymer block is 70% by mass or more. The polymer block mainly composed of a predetermined monomer unit may have a content of the predetermined monomer unit of 70% by mass or more, preferably 80% by mass, more preferably 90% by mass or more.

In the polymer block (B), the hydrogenated block copolymer according to the present embodiment includes first to sixth regions in the polymer block (B) in order from the polymerization start end to have the same mass. When the maximum value of the vinyl content before hydrogenation is _VH and the minimum value is _VL , _VH - _VL = 5 mol% or more and 30 mol% or less.
V _H -V _L represents the difference in the vinyl content before hydrogenation in the polymer block (B) containing the conjugated diene monomer unit (hereinafter, also simply referred to as “Δ vinyl content”). .

When the Δvinyl content (V _H −V _L ) in the polymer block (B) is in the above range, the high adhesive strength of the adhesive composition containing the hydrogenated block copolymer of the present embodiment, High tackiness, it is possible to improve the balance between physical properties and solubility such as high adhesive holding power, and also high low-temperature elongation of the modified asphalt composition containing the hydrogenated block copolymer of the present embodiment, The balance between various physical properties such as high heat aging resistance and high fluidity and compatibility can be improved.

In the polymer block (B) included in the hydrogenated block copolymer of the present embodiment, the first to sixth regions are set to have the same mass in order from the polymerization start end side, and the first to sixth regions Assuming that the vinyl content before hydrogenation is V _{1 to} V ₆ , respectively, the distribution of the vinyl content is particularly limited if the Δvinyl content (V _H −V _L ) is 5 mol% or more and 30 mol% or less. Not limited.
The distribution of the vinyl content may be tapered, convex, or concave.

In the first to sixth regions in the polymer block (B), a plurality of regions having the highest vinyl content may be present.
For example, when the vinyl content of the first region and the second region are equal and the maximum value, both the vinyl contents of V ₁ and V ₂ are V _H.
Similarly, there may be a plurality of regions having the smallest vinyl content.

The tapered distribution means that the distribution of the vinyl content is V ₆ > V ₅ > V ₄ > V ₃ > V ₂ > V ₁ , and V ₆ -V ₁ = 5 mol% or more and 30 mol% or less, or vinyl content A distribution in which the amount distribution satisfies V ₆ <V ₅ <V ₄ <V ₃ <V ₂ <V ₁ , and V ₁ -V ₆ = 5 mol% or more and 30 mol% or less.

The convex distribution, V ₆ and V ₁ is smaller than V ₅ and V _2, V ₅ and V ₂ refers to a smaller distribution than V ₄ and V _3.
As the convex distribution, for example, the distribution of the vinyl content is V ₆ <V ₅ <V ₄ , V ₃ > V ₂ > V ₁ , V ₆ = V ₁ (= _VL ), V ₄ = V ₃ ( = _VH ) and _VH - _VL = 5 mol% or more and 30 mol% or less.

The concave profile, greater than V ₆ and V ₁ is V ₅ and V _2, V ₅ and V ₂ means a larger distribution than V ₄ and V _3.
As the concave distribution, for example, the distribution of the vinyl content is V ₆ > V ₅ > V ₄ , V ₃ <V ₂ <V ₁ , V ₆ = V ₁ (= V _H ), V ₄ = V ₃ (= _VL ) and _VH - _VL = 5 mol% to 30 mol%.

The distribution of the vinyl content of the polymer block (B) is determined from the viewpoint of the balance between the above-mentioned physical properties and solubility of the adhesive composition and the balance between the above-mentioned physical properties and compatibility of the modified asphalt composition. , A tapered distribution, and more preferably a distribution satisfying V ₆ <V ₅ <V ₄ <V ₃ <V ₂ <V ₁ .

The lower limit of the Δvinyl content (V _H −V _L ) is determined by the adhesive holding power and solubility of the adhesive composition containing the hydrogenated block copolymer of the present embodiment, and the hydrogenated block of the present embodiment. From the viewpoint of low-temperature elongation and compatibility of the modified asphalt composition containing the copolymer, it is sufficient that the content be 5 mol% or more, preferably 7 mol% or more, more preferably 8 mol% or more, and 10 mol%. The above is more preferred.
The upper limit of the Δvinyl content (V _H −V _L ) is determined by the adhesive holding power and solubility of the adhesive composition containing the hydrogenated block copolymer of the present embodiment, and the hydrogenated block of the present embodiment. From the viewpoints of low-temperature elongation and compatibility of the modified asphalt composition containing the copolymer, it is sufficient that the content is 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, and 15 mol%. The following are more preferred.

The distribution of the vinyl content and the Δvinyl content (V _H −V _L ) can be controlled by adjusting the method of adding the polar compound, the reaction temperature, and the like in the production of the hydrogenated block copolymer of the present embodiment. .

  The vinyl content can be measured by NMR, and specifically, can be measured by the method described in Examples described later.

The structure of the hydrogenated block copolymer of the present embodiment before hydrogenation (hereinafter, also referred to as “hydrogenation”) is not limited to the following, but is represented by, for example, the following formulas (1) to (6). Structure.
(AB) _n ... (1)
B- (AB) _n (2)
A- (BA) _n (3)
A- (BA) _n -X (4)
[(AB) _k ] _m -X (5)
[(AB) _k -A] _m -X (6)

  In the above formulas (1) to (6), A represents a polymer block mainly containing a vinyl aromatic monomer unit, B represents a polymer block containing a conjugated diene monomer unit, and X Represents a residue of a coupling agent or a residue of a polymerization initiator such as a polyfunctional organic lithium, and m, n, and k represent an integer of 1 or more, preferably an integer of 1 to 5.

In the block copolymer before hydrogenation, there are a plurality of polymer blocks (A) mainly containing vinyl aromatic monomer units and a plurality of polymer blocks (B) containing conjugated diene monomer units. In this case, the structures such as molecular weight and composition may be the same or different.
In the above formulas (1) to (6), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium.
The hydrogenated 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 in which X is a residue of a polymerization initiator. .
The boundaries and the extreme ends of each block do not necessarily need to be clearly distinguished. For example, a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit may be present.

  The distribution of the vinyl aromatic monomer units in the polymer block (A) mainly containing vinyl aromatic monomer units and the polymer block (B) containing conjugated diene monomer units is particularly limited. Instead, they may be distributed uniformly, or may be distributed in a tapered, stepped, convex, or concave shape. Further, a crystal part may be present in the polymer block. Further, in the polymer block (A) mainly composed of vinyl aromatic monomer units, a plurality of segments having different contents of vinyl aromatic monomer units may coexist.

  The conjugated diene monomer unit is not limited to the following, but for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene Conjugated diene monomer units derived from at least one monomer selected from the group consisting of 1,3-pentadiene, 2-methyl-1,3-pentadiene and 1,3-hexadiene. Among these, a conjugated diene monomer unit derived from at least one monomer selected from the group consisting of 1,3-butadiene and isoprene is preferred. In particular, a conjugated diene monomer unit derived from 1,3-butadiene is more preferable. The conjugated diene monomer units may be used alone or in combination of two or more.

  Examples of the vinyl aromatic monomer unit include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl- Examples include vinyl aromatic monomer units derived from at least one monomer selected from the group consisting of p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene. Among these, a vinyl aromatic monomer unit derived from styrene is preferable from the viewpoint of economy. The vinyl aromatic monomer units may be used alone or in combination of two or more.

  The hydrogenated block copolymer of the present embodiment includes, in addition to the conjugated diene monomer unit and the vinyl aromatic monomer unit, another copolymerizable with the conjugated diene monomer unit and the vinyl aromatic monomer unit. It may have a monomer unit.

  The hydrogenation rate of the hydrogenated block copolymer of the present embodiment is not particularly limited as long as it is more than 0 mol% and 100 mol% or less based on the total number of moles of the conjugated diene monomer unit.

  Balance between physical properties and solubility of the adhesive composition containing the hydrogenated block copolymer of the present embodiment, and physical properties of the modified asphalt composition containing the hydrogenated block copolymer of the present embodiment From the viewpoint of the balance between the hydrogenated block copolymer and the compatibility, the upper limit of the hydrogenation rate of the hydrogenated block copolymer is preferably 97 mol% or less based on the total number of moles of the conjugated diene monomer unit, It is more preferable that the content be 95 mol% or less.

  Balance between physical properties and solubility of the adhesive composition containing the hydrogenated block copolymer of the present embodiment, and physical properties of the modified asphalt composition containing the hydrogenated block copolymer of the present embodiment From the viewpoint of the balance between the hydrogenated block copolymer and the compatibility, the lower limit of the hydrogenation rate of the hydrogenated block copolymer is preferably 10 mol% or more based on the total number of moles of the conjugated diene monomer unit, More preferably, it is at least 15 mol%.

The hydrogenation rate of the hydrogenated block copolymer can be controlled by adjusting the hydrogenation amount and the hydrogenation reaction time in the hydrogenation step described below.
Further, the hydrogenation rate can be determined by a method described in Examples described later.

Balance between physical properties and solubility of the adhesive composition containing the hydrogenated block copolymer of the present embodiment, and physical properties of the modified asphalt composition containing the hydrogenated block copolymer of the present embodiment From the viewpoint of the balance between the polymer and the compatibility, the content of the vinyl aromatic monomer unit in the hydrogenated block copolymer of the present embodiment is preferably from 10% by mass to 60% by mass.
In addition, from the viewpoint of the adhesive holding power of the adhesive composition, the lower limit of the content of the vinyl aromatic monomer unit of the hydrogenated block copolymer of the present embodiment is preferably 10% by mass or more, and more preferably 12% by mass. The above is more preferable, 15% by mass or more is further preferable, and 20% by mass or more is still more preferable. In addition, the upper limit of the content is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and 30% by mass from the viewpoints of the solubility and viscosity of the adhesive composition. The following are even more preferred.
Further, from the viewpoint of the softening point of the modified asphalt composition described later, the lower limit of the content of the vinyl aromatic monomer unit in the hydrogenated block copolymer of the present embodiment is preferably 10% by mass or more, and more preferably 15% by mass. %, More preferably 25% by mass or more, even more preferably 35% by mass or more. Furthermore, the upper limit of the content is preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less, from the viewpoint of the compatibility and the viscosity of the modified asphalt composition. % By mass or less is even more preferred.
The content of the vinyl aromatic monomer unit of the hydrogenated block copolymer of the present embodiment is controlled by adjusting the amount of the vinyl aromatic monomer added in the polymerization step of the hydrogenated block copolymer. be able to.

(Method for producing hydrogenated block copolymer)
The hydrogenated block copolymer of the present embodiment is obtained by polymerizing at least a conjugated diene monomer and a vinyl aromatic monomer in a hydrocarbon solvent using a lithium compound as a polymerization initiator to obtain a block copolymer. A polymerization step is performed to obtain a block copolymer, and after the polymerization step, a hydrogenation step of adding hydrogen to a part of the double bond in the conjugated diene monomer unit of the obtained block copolymer is performed. It can be produced by performing a solvent removing step of removing the solvent of the solution containing the obtained hydrogenated block copolymer.

In the polymerization step, a block copolymer 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.
In the polymerization step, a polar compound may be added as a randomizing agent.

The distribution of the vinyl content and the Δvinyl content (V _H -V _L ) can be controlled by adjusting the method of adding the polar compound, the polymerization reaction temperature, and the like.

In the conventional polymerization method, generally, the reaction temperature is controlled to be constant by a predetermined temperature adjusting means from the start of the polymerization so that the reaction temperature does not rise due to the heat of the polymerization reaction. In the case of producing a polymer, for example, the distribution of the vinyl content and the Δvinyl content (V _H −V _L ) can be controlled by changing the reaction temperature during the polymerization reaction.
For example, by performing the polymerization while raising the reaction temperature by the reaction heat, the vinyl content at the end of the polymerization is smaller than the vinyl content at the start of the polymerization, and the vinyl content is V ₆ <V ₅ <V ₄ A tapered vinyl distribution satisfying <V ₃ <V ₂ <V ₁ can be obtained.
By setting the reaction temperature at the start of the polymerization high and lowering the reaction temperature during the polymerization, the vinyl content at the end of the polymerization becomes larger than the vinyl content at the start of the polymerization, and the vinyl content becomes V ₆ > V _{5> V 4> V 3>} V 2> V 1 can be tapered distribution satisfying.
Further, the Δvinyl content can be controlled by controlling the width of change in the reaction temperature.

  Further, in the polymerization reaction, by adding an excessive amount of the polar compound or adding the polar compound in the middle of the polymerization reaction, the vinyl content can have a concave distribution as described above.

  Further, in the polymerization reaction, the polymerization is performed while cooling, and the temperature is increased in the middle of the polymerization reaction, so that the vinyl content can have a convex distribution as described above.

Examples of the hydrocarbon solvent used in the polymerization step include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; cyclopentane, methylcyclopentane, cyclohexane, and methyl. Alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene.
These may be used alone or in combination of two or more.

The lithium compound used as a polymerization initiator in the polymerization step is not limited to the following. Organic lithium compounds.
Examples of such an organic lithium compound include, but are not limited to, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene di Lithium, butadienyldilithium, isoprenyldilithium and the like.
These may be used alone or in combination of two or more.

The conjugated diene monomer used in the polymerization step is not limited to the following. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1 And diolefins having a pair of conjugated double bonds such as 1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene.
Of these, 1,3-butadiene and isoprene are preferred.
Further, from the viewpoint of mechanical strength, 1,3-butadiene is more preferable.
These may be used alone or in combination of two or more.

Examples of the vinyl aromatic monomer used in the polymerization step include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N Vinyl aromatic compounds such as -dimethyl-p-aminoethylstyrene and 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 the production process of the hydrogenated block copolymer of the present embodiment, in addition to the conjugated diene monomer and the vinyl aromatic monomer, Can also be used.

  In the polymerization step, the polymerization rate is adjusted, the microstructure (ratio of cis, trans, and vinyl) of the polymerized conjugated diene monomer unit is adjusted, and the reaction ratio between the conjugated diene monomer and the vinyl aromatic monomer is adjusted. A polar compound (also referred to as a “randomizing agent”) may be used for the purpose of, for example, adjusting the concentration of the compound.

  Examples of the polar compound (also referred to as a “randomizing agent”) include, but are not limited to, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether; triethylamine, N, N, N ′, N ′ Amines such as tetramethylethylenediamine (hereinafter also referred to as "TMEDA"); thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, and potassium and sodium alkoxides.

The polymerization method carried out in the polymerization step of the block copolymer is not particularly limited, and a known method can be applied.
Known methods are not limited to the following, but include, for example, JP-B-36-19286, JP-B-43-17979, JP-B-46-32415, and JP-B-49-36957. The methods described in JP-B-48-2423, JP-B-48-4106, JP-B-56-28925, JP-A-59-166518, JP-A-60-186577 and the like are exemplified. .

The block copolymer may be coupled using a coupling agent.
The coupling agent is not limited to the following, but any bifunctional or higher coupling agent can be used.
Examples of the bifunctional coupling agent include, but are not limited to, difunctional silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; diphenyldimethoxysilane, diphenyldiethoxysilane, and dimethyl Bifunctional alkoxysilanes such as dimethoxysilane and dimethyldiethoxysilane; difunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride and dibromomethane; dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin and diethyl Bifunctional tin halides such as dichlorotin, monobutyldichlorotin and dibutyldichlorotin; dibromobenzene, benzoic acid, CO, 2-chloropropene and the like.

  Examples of the trifunctional coupling agent include, but are not limited to, trifunctional halogenated alkanes such as trichloroethane and trichloropropane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; Trifunctional alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; and the like.

  Examples of the tetrafunctional coupling agent include, but are not limited to, tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; and tetrafunctional alkane such as tetrachlorosilane and tetrabromosilane. Functional halogenated silanes; tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; tetrafunctional tin halides such as tetrachlorotin and tetrabromotin; and the like.

  Examples of the coupling agent having five or more functional groups include, but are not limited to, 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, and decabromo. And polyhalogenated hydrocarbon compounds such as diphenyl ether. In addition, polyvinyl compounds such as epoxidized soybean oil, compounds having 2 to 6 functional epoxy groups, carboxylic acid esters, and divinylbenzene can also be used.

  One type of coupling agent may be used alone, or two or more types may be used in combination.

After the polymerization step, it is preferable to perform a deactivation step of deactivating the active terminal of the block copolymer.
By reacting a compound having active hydrogen with an active terminal, the active terminal of the polymer can be deactivated.
The compound having active hydrogen is not limited to the following, but from the viewpoint of economy, alcohol and water are exemplified.

In the hydrogenation step, hydrogen is added to a part of the double bond in the conjugated diene monomer unit of the block copolymer obtained in the polymerization step.
Examples of the hydrogenation catalyst used in the hydrogenation step include, but are not limited to, metals such as Ni, Pt, Pd, and Ru supported on a carrier such as carbon, silica, alumina, and diatomaceous earth. Supported heterogeneous catalyst; a so-called Ziegler catalyst using an organic salt such as Ni, Co, Fe, Cr or the like or an acetylacetone salt and a reducing agent such as organic Al; an organic metal compound such as Ru or Rh; A so-called organic complex catalyst; and a homogeneous catalyst using an organic Li, organic Al, organic Mg or the like as a reducing agent for the titanocene compound, and the like.
Among these, a homogeneous catalyst system using an organic Li, organic Al, organic Mg, or the like as a reducing agent for the titanocene compound is preferable from the viewpoints of economy, coloring property of the polymer, and adhesive strength.

The method of the hydrogenation step is not limited to the following. For example, the method described in JP-B-42-8704, JP-B-43-6636, or preferably JP-B-63-4841 And the method described in JP-B-63-5401.
Specifically, the hydrogenation step is performed in an inert solvent in the presence of a hydrogenation catalyst to obtain a hydrogenated block copolymer solution.
The hydrogenation step is preferably performed after the deactivation step from the viewpoint of high hydrogenation activity. The hydrogenation step can be performed in any of a batch process, a continuous process, or a combination thereof.

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

  In the production process of the hydrogenated block copolymer of the present embodiment, as a polymerization initiator, a monomer, a coupling agent, and a terminator, a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol Group, and a compound having at least one functional group selected from the group consisting of alkoxysilane groups, the resulting hydrogenated block copolymer, hydroxyl group, acid anhydride group, epoxy group, amino group, amide group It is preferable to add at least one functional group selected from the group consisting of a silanol group, and an alkoxysilane group.

As the polymerization initiator containing a functional group, a polymerization initiator containing a nitrogen-containing group is preferable.
Examples of the polymerization initiator containing a nitrogen-containing group include, but are not limited to, dioctylaminolithium, di-2-ethylhexylaminolithium, ethylbenzylaminolithium, and (3- (dibutylamino) -propyl. ) Lithium, piperidinolithium and the like.

As the monomer containing a functional group, a monomer containing a nitrogen-containing group is preferable.
Examples of the monomer containing a nitrogen-containing group include, but are not limited to, N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, and N, N-dipropylvinylbenzyl. Amine, N, N-dibutylvinylbenzylamine, 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, -(2-hexamethyleneiminoethyl) styrene, 4- (2-morpholinoethyl Styrene, 4- (2-thiazinoethyl) styrene, 4- (2-N-methylpiperazinoethyl) styrene, 1-((4-vinylphenoxy) methyl) pyrrolidine, and 1- (4-vinylbenzyloxymethyl) And pyrrolidine.

Examples of the coupling agent and the terminating agent containing a functional group include, among the aforementioned coupling agents and terminating agents, 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 at least one functional group selected from the group consisting of a coupling agent and a terminator.
Among these, a coupling agent and a terminator containing a nitrogen-containing group or an oxygen-containing group are preferable.
Examples of the coupling agent and the terminating agent containing a nitrogen-containing group or an oxygen-containing group include, but are not limited to, N, N, N ', N'-tetraglycidylmethaxylenediamine, tetraglycidyl- 1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, γ-caprolactone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldiethylethoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2- Imidazolidinone, N, N'-dimethi Propylene urea, and N- methylpyrrolidone.

In the solvent removing step, the solvent of the polymer solution containing the hydrogenated block copolymer is removed.
Examples of the method of desolvation include, but are not limited to, a steam stripping method and a direct desolvation method.

The residual solvent amount in the hydrogenated block copolymer obtained by the solvent removing step is preferably as small as possible, more preferably 2% by mass or less, more preferably 0.5% by mass or less. The content is more preferably 2% by mass or less, even more preferably 0.05% by mass or less, even more preferably 0.01% by mass or less, and particularly preferably 0% by mass.
From the viewpoint of economy, the amount of the residual solvent in the hydrogenated block copolymer is usually preferably in the range of 0.01% by mass to 0.1% by mass.

It is preferable to add an antioxidant to the block copolymer from the viewpoint of heat aging resistance and suppression of gelation of the hydrogenated block copolymer.
Examples of the antioxidant include a phenolic antioxidant such as a radical scavenger, a phosphorus antioxidant such as a peroxide decomposer, and a sulfur antioxidant.
Further, an antioxidant having both properties may be used.
These may be used alone or in combination of two or more.
Among these, a phenolic antioxidant is preferred from the viewpoint of heat aging resistance of the block copolymer and suppression of gelation.

  From the viewpoint of preventing coloring of the hydrogenated block copolymer and improving mechanical strength, before the desolvation step, a deashing step of removing metals in the solution containing the block copolymer, and the pH of the solution containing the block copolymer May be performed, for example, an acid may be added and / or a carbon dioxide gas may be added.

(Adhesive composition and hydrogenated block copolymer used therein)
The hydrogenated block copolymer of the present embodiment can be used for an adhesive composition as a first embodiment.

  The adhesive composition of the present embodiment is, for example, used for assembling an adhesive tape, a label, and a diaper, and has a high adhesive strength, a high tackiness, and a high adhesive holding power, The balance between these properties and the short dissolution time during production (hereinafter also referred to as “meltability”) is good.

  That is, in the first embodiment, by using the hydrogenated block copolymer of the present embodiment in an adhesive composition, adhesive strength, tackiness, and excellent adhesive holding power, and of the adhesive composition It is possible to provide an adhesive composition having a short dissolution time during production and excellent in productivity.

(Hydrogenated block copolymer)
In the first embodiment, from the viewpoint of the adhesive strength of the adhesive composition, tackiness, tackiness, and dissolution time during production, the hydrogenated block copolymer of the present embodiment is a vinyl aromatic monomer. Having a polymer block (A) mainly composed of units and a polymer block (B) containing a conjugated diene monomer unit, and a polymer block (B) having a conjugated diene monomer unit, The first region to the sixth region were made to have the same mass in order from the polymerization start terminal side, and the maximum value of the vinyl content before hydrogenation of the first region to the sixth region was V _H , and the minimum value was V _L. At this time, _VH - _VL = 5 mol% to 30 mol%.
The distribution of the vinyl content and the Δvinyl content (V _H −V _L ) are as described above.

  Further, in the first embodiment, from the viewpoint of the balance of the adhesiveness, tackiness, and adhesion holding power of the adhesive composition, and the balance between these physical properties and solubility, the hydrogenated block copolymer of the present embodiment includes: It is preferably a hydrogenated block copolymer having a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B1) mainly composed of conjugated diene monomer units.

In the first embodiment, the structure of the hydrogenated block copolymer of the present embodiment before hydrogenation is not limited to the following. For example, the structure is represented by the following formulas (7) to (12). Hydrogenated block copolymer having the following structure:
(A-B1) _n ... (7)
B1- (A-B1) _n (8)
A- (B1-A) _n (9)
A- (B1-A) _n -X (10)
[(A-B1) _k ] _m -X (11)
[(A-B1) _k -A] _m -X (12)

  In the above formulas (7) to (12), A represents a polymer block mainly composed of vinyl aromatic monomer units, B1 represents a polymer block mainly composed of conjugated diene monomer units, and X represents Represents a residue of a coupling agent or a residue of a polymerization initiator such as a polyfunctional organic lithium, and m, n and k represent an integer of 1 or more, preferably an integer of 1 to 5.

In the first embodiment, when a plurality of polymer blocks (A) and (B1) are present in the block copolymer before hydrogenation, even if the structures such as molecular weight and composition are the same, Good or different.
In the above formulas (7) to (12), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium. The hydrogenated 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 in which X is a residue of a polymerization initiator. . The boundaries and the extreme ends of each block do not necessarily need to be clearly distinguished. For example, a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit may be present.

In the first embodiment, a vinyl aromatic monomer in a polymer block (A) mainly containing a vinyl aromatic monomer unit or a polymer block (B1) mainly containing a conjugated diene monomer unit The distribution of the units is not particularly limited, and may be distributed uniformly, or may be distributed in a tapered, stepped, convex, or concave shape. Further, a crystal part may be present in the polymer block.
In the polymer block (A) mainly composed of a vinyl aromatic monomer unit, a plurality of segments having different contents of the vinyl aromatic monomer unit may coexist.

In the first embodiment, from the viewpoint of the adhesive strength of the adhesive composition, tackiness, and adhesive holding power, and the balance between these physical properties and solubility, the hydrogenated block copolymer of the present embodiment is a vinyl copolymer. A hydrogenated block copolymer (d1) having one polymer block (A) mainly composed of an aromatic monomer unit and one polymer block (B1) mainly composed of a conjugated diene monomer unit. It is preferred to contain.
Here, the hydrogenated block copolymer (d1) has a structure where n = 1 in the above formula (7).

In the first embodiment, a hydrogenation having one polymer block (A) mainly composed of a vinyl aromatic monomer unit and one polymer block (B1) mainly composed of a conjugated diene monomer unit is used. The lower limit of the content of the block copolymer (d1) is preferably 20% by mass or more based on 100% by mass of the hydrogenated block copolymer from the viewpoint of high tackiness of the adhesive composition. , 30% by mass or more, still more preferably 50% by mass or more, even more preferably 65% by mass or more, even more preferably 70% by mass or more.
Further, the upper limit of the content of the hydrogenated block copolymer (d1) is 90% by mass or less based on 100% by mass of the hydrogenated block copolymer from the viewpoint of the high adhesive strength of the adhesive composition. It is preferably at most 85% by mass, more preferably at most 80% by mass, even more preferably at most 75% by mass.

The hydrogenated block copolymer of the present embodiment in the first embodiment contains a hydrogenated block copolymer (r1) having a radial structure from the viewpoint of the low viscosity and high tackiness of the adhesive composition. Is preferred.
Here, in the present specification, the “radial structure” refers to a structure in which three or more polymers are bonded to a residue X. For example, A- (B1-A) _n -X (n ≧ 3), [(A-B1) _k ] _m- X (m≥3), and [(A-B1) _k- A] _m- X (m≥3).

In the first embodiment, as the structure of the hydrogenated block copolymer (r1) having a radial structure, from the viewpoint of the high adhesive strength, low viscosity, and high adhesive holding power of the adhesive composition of the present embodiment, [(A-B1) _k ] _m- X, and [(A-B1) _k- A] _m- X (in each formula, m represents an integer of 3 to 6, and k represents an integer of 1 to 4. More preferably, m represents an integer of from 3 to 4.).

  In the first embodiment, the hydrogenation rate of the hydrogenated block copolymer of the present embodiment is preferably 10 mol% to 97 mol%, based on the total number of moles of the conjugated diene monomer unit, and is preferably 10 mol% to 97 mol%. More preferably, it is from 20 mol% to 80 mol%, further preferably from 20 mol% to 80 mol%, more preferably from 31 mol% to 70 mol%, and more preferably from 33 mol% to 63 mol%. Is still more preferable, and it is particularly preferable that the amount is 35 mol% to 59 mol%.

In the first embodiment, the hydrogenation rate of the hydrogenated block copolymer of the present embodiment may have a distribution.
Here, the hydrogenation rate distribution H is an index indicating the distribution of the hydrogenation rate of the hydrogenated block copolymer, and can be obtained as follows.
Based on the molecular weight distribution (MD1) obtained by the ozonolysis method of the hydrogenated block copolymer and the molecular weight distribution (MD2) obtained by the osmic acid decomposition method, {(MD1) − (MD2)} is obtained, and the molecular weight distribution is obtained. (MD3) is obtained. The maximum peak height is H when the total area of the obtained molecular weight distribution (MD3) in a region having a molecular weight of 200 to 1,000,000 is defined as 1. The value of H is an index of the hydrogenation rate distribution, and the smaller the value of H, the wider the hydrogenation rate distribution.
From the viewpoints of the adhesive strength, tackiness, and adhesive holding power of the adhesive composition of the present embodiment, and the balance between these physical properties and solubility, the value of the hydrogenation rate distribution H is 0.001 to 0.1. 007 or less, more preferably 0.001 or more and 0.0055 or less, and even more preferably 0.001 or more and 0.004 or less.

The hydrogenation rate of the hydrogenated block copolymer can be adjusted by controlling the hydrogenation amount and the hydrogenation reaction time in the hydrogenation step described below.
Further, the hydrogenation rate can be determined by a method described in Examples described later.

  In the first embodiment, the vinyl aromatic monomer unit content (TS) of the hydrogenated block copolymer depends on the adhesive strength, tackiness, and high adhesive holding power of the adhesive composition, and the properties and dissolution of the adhesive composition. From the viewpoint of balance with the properties, the content is preferably 10% by mass to 45% by mass, more preferably 13% by mass to 40% by mass, and still more preferably 15% by mass to 35% by mass.

  In the first embodiment, the content (BS) of the polymer block (A) mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer is the same as that of the adhesive composition of the present embodiment. From the viewpoints of high adhesive strength, high tackiness, high adhesive holding power, and a balance between these properties and solubility, the content is preferably 12% by mass to 43% by mass, and more preferably 13% by mass to 40% by mass. Is more preferable, and it is still more preferably from 14% by mass to 34% by mass.

  The content (TS) of the vinyl aromatic monomer unit in the hydrogenated block copolymer and the content (BS) of the polymer block (A) mainly composed of the vinyl aromatic monomer unit are as follows: It can be measured by the method described in Examples described later.

In the first embodiment, the molecular weight distribution of the polymer block (A) mainly composed of a vinyl aromatic monomer of the hydrogenated block copolymer of the present embodiment is determined by the adhesiveness of the adhesive composition of the present embodiment. 1.46 or less are preferable, 1.44 or less are more preferable, 1.42 or less are more preferable, and 1.44 or less are preferable from a viewpoint of a force, tackiness, and high adhesive holding power, and the balance of these physical properties and solubility. The following are even more preferred. In addition, from the viewpoint of the adhesive strength, tackiness, and high adhesive holding power of the adhesive composition of the present embodiment, and the balance between these properties and solubility, 1.1 or more is preferable, and 1.12 or more is more preferable. Preferably, 1.14 or more is further preferable, and 1.16 or more is still more preferable. Here, the molecular weight distribution of the polymer block (A) mainly composed of a vinyl aromatic monomer can be determined by the following equation.
Molecular weight distribution = (molecular weight on high molecular weight side at full width at half maximum of peak molecular weight of polymer block (A)) / (molecular weight on low molecular weight side at full width at half maximum of peak molecular weight of polymer block (A))

The average vinyl content in the conjugated diene monomer unit of the hydrogenated block copolymer in the first embodiment before hydrogenation is preferably from 15 mol% to 75 mol%, and more preferably from 25 mol% to 55 mol%. Is more preferable, and 35 to 45 mol% is further preferable.
When the average vinyl content in the conjugated diene monomer unit before hydrogenation of the hydrogenated block copolymer in the first embodiment is 15 mol% or more, the tackiness and tackiness of the adhesive composition are obtained. , And adhesive holding power tend to be further improved.
In addition, the hydrogenated block copolymer in the first embodiment has an average vinyl content in the conjugated diene monomer unit of 75 mol% or less before hydrogenation, thereby improving the tackiness and tackiness of the adhesive composition. The heat aging resistance tends to be further improved.
Here, in the specification of the present application, the “average vinyl content” refers to a combination of 1,2-bond, 3,4-bond, and 1,4-bond of the conjugated diene monomer before hydrogenation. The ratio of the conjugated diene monomer unit incorporated by 1,2-bond and 3,4-bond to the total molar amount of the conjugated diene monomer unit.

In the first embodiment, the weight average molecular weight (Mw) of the hydrogenated block copolymer of the present embodiment is preferably 100,000 or more, more preferably 180,000 or more, from the viewpoint of high adhesive strength and adhesive holding power. More than 10,000 is more preferable.
Further, from the viewpoint of high productivity, the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 350,000 or less, more preferably 300,000 or less, and still more preferably 250,000 or less.

In the first embodiment, the lower limit of the molecular weight distribution (Mw / Mn) (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the hydrogenated block copolymer of the present embodiment is determined by the high productivity. From the viewpoint, it is preferably 1.1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, and still more preferably 1.4 or more. In addition, from the viewpoints of high value adhesion and adhesion holding power, the upper limit of the molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer of the present embodiment is preferably 3.0 or less, more preferably 2.0 or less. And 1.7 or less is more preferable.
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer can be determined by a method described in Examples described later.

In the first embodiment, from the viewpoint of the high adhesive strength of the adhesive composition, high tack, and high adhesive holding power, the hydrogenated block copolymer of the present embodiment has a hydroxyl group, an acid anhydride group, an epoxy group, an amino group. It preferably has at least one functional group selected from the group consisting of a group, an amide group, a silanol group, and an alkoxysilane group.
Among these, the hydrogenated block copolymer more preferably has at least one functional group selected from the group consisting of an amino group and an amide group, and more preferably has an amino group.

In the first embodiment, from the viewpoint of high adhesive strength after immersion in warm water, the hydrogenated block copolymer of the present embodiment has a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, an alkoxysilane It preferably has at least one functional group selected from the group consisting of groups.
In the first embodiment, the hydrogenated block copolymer of the present embodiment contains at least one functional group selected from the group consisting of an amino group and an amide group in an amount of 2 mol or more per 1 mol of the molecule. Is more preferable.

The hydrogenated block copolymer in the first embodiment preferably has a melt flow rate (MFR, 200 ° C, 5 kgf) of 0.1 g / 10 min to 50 g / 10 min, and 0.2 g / 10 min to It is more preferably 20 g / 10 min, more preferably 0.3 g / 10 min to 10 g / 10 min, and even more preferably 0.4 g / 10 min to 5 g / 10 min.
In the first embodiment, when the MFR of the hydrogenated block copolymer of the present embodiment is 0.1 g / 10 min or more, the tackiness, tackiness, and tackiness of the adhesive composition, and tape There is a tendency that the resistance to seepage from the edge during lamination is further improved.
Further, in the first embodiment, when the MFR of the hydrogenated block copolymer is 50 g / 10 minutes or less, the coating properties and the discoloration resistance of the adhesive composition tend to be further improved.

(Adhesive composition)
The adhesive composition according to the first embodiment contains 20 to 400 parts by mass of a tackifier resin based on 100 parts by mass of the hydrogenated block copolymer described above.

The content of the tackifying resin in the adhesive composition in the first embodiment may be 20 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the hydrogenated block copolymer, and is preferably 70 parts by mass. To 350 parts by mass, more preferably 120 to 300 parts by mass, still more preferably 140 to 250 parts by mass.
When the content of the tackifying resin is within the above range, tackiness, adhesive strength, adhesive holding power, coating properties, and discoloration resistance tend to be further improved.

In the first embodiment, the “tackifying resin” may be a resin (oligomer) having a number average molecular weight of 100 to less than 10,000, which can impart tackiness to the adhesive composition of the present embodiment. preferable.
The number average molecular weight of the tackifier resin can be measured by a method similar to the method for measuring the number average molecular weight described in Examples described later.

Examples of the tackifier resin include, but are not limited to, rosin derivatives (including tung oil resin), tall oil, tall oil derivatives, rosin ester resins, natural and synthetic terpene resins, and aliphatic hydrocarbons. Resin, aromatic hydrocarbon resin, mixed aliphatic-aromatic hydrocarbon resin, coumarin-indene resin, phenol resin, p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, monoolefin oligomer, Diolefin oligomer, aromatic hydrocarbon resin, hydrogenated aromatic hydrocarbon resin, cycloaliphatic hydrocarbon resin, hydrogenated hydrocarbon resin, hydrocarbon resin, hydrogenated tung oil resin, hydrogenated oil resin, hydrogenated oil Esters of a resin and a monofunctional or polyfunctional alcohol are exemplified.
These may be used alone or in combination of two or more.
In the case of hydrogenation, all the unsaturated groups may be hydrogenated, or some may be left.

The tackifying resin preferably contains a tackifying resin having a softening point of 80 ° C. or more from the viewpoints of adhesive strength, adhesive holding power, and high resistance to bleeding from the end when the tape is laminated.
The lower limit of the softening point of the tackifier resin is more preferably 85 ° C or higher, further preferably 95 ° C or higher, and still more preferably 100 ° C or higher.
The upper limit of the softening point of the tackifier resin is not particularly limited, but is preferably 145 ° C or lower, more preferably 140 ° C or lower, further preferably 135 ° C or lower, and further preferably 130 ° C or lower. Is even more preferred.
The softening point of the tackifier resin can be measured by JIS K2207 ring and ball method.

  In the first embodiment, from the viewpoints of high adhesiveness of the adhesive composition, reduction of the change over time in adhesive strength, and creep performance, etc., the non-glass phase of the hydrogenated block copolymer is contained in the adhesive composition. 20 to 75% by mass of a tackifier resin having affinity for the block (usually the polymer block (B1)) and the block of the glass phase of the hydrogenated block copolymer (usually the polymer block (A)) It is preferred to contain 3 to 30% by mass of an affinity tackifier resin.

The tackifier resin having affinity for the block of the glass phase of the hydrogenated block copolymer is not limited to the following, but for example, a terminal block tackifier resin is preferable.
Such tackifying resins are not limited to the following, but include, for example, vinyltoluene, styrene, α-methylstyrene, containing coumarone or indene, a resin having an aromatic group such as a homopolymer or a copolymer. Is mentioned.
Among these, Kristalex and Plastolyn (trade name, manufactured by Eastman Chemical Company) having α-methylstyrene are preferable.
The content of the tackifier resin having an affinity for the block of the glass phase of the partial viewpoint block copolymer is preferably 3 to 30% by mass, more preferably 5 to 30% by mass, based on the total mass of the adhesive composition. It is 20% by mass, and more preferably 6 to 12% by mass.

In the first embodiment, from the viewpoint of high initial adhesive strength of the adhesive composition, high wettability, low melt viscosity, and high coatability, the tackifier resin has an aroma content of 3 to 12 mass. %, More preferably a hydrogenated petroleum resin having an aroma content of 3 to 12% by mass.
The aroma content in the tackifier resin is preferably 3 to 12% by mass, and more preferably 4 to 10% by mass.
As used herein, “aroma” refers to a non-hydrogenated aromatic component.

In the first embodiment, the tackifying resin is preferably a hydrogenated tackifying resin from the viewpoints of higher weather resistance (low change in adhesive strength after UV irradiation) and low odor of the adhesive composition. .
"Hydrogenated tackifying resin" refers to an aliphatic tackifying resin containing an unsaturated bond, or an aromatic tackifying resin containing an unsaturated bond, which is hydrogenated so as to have an arbitrary hydrogenation rate. Refers to resin. The hydrogenation rate of the hydrogenated tackifying resin is preferably higher.

  Examples of the hydrogenated tackifying resin include, but are not limited to, Alcon M and Ascon P (trade name, manufactured by Arakawa Chemical Industry Co., Ltd.), Clearon P (trade name, manufactured by Yashara Chemical Co., Ltd.), And Imarve P (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

  In the first embodiment, the adhesive composition is, in addition to the hydrogenated block copolymer of the present embodiment and the tackifying resin, if necessary, oil, antioxidant, weathering agent, antistatic agent, lubricant , Fillers, and various additives such as waxes.

Examples of the oil include, but are not limited to, a paraffinic oil mainly containing paraffinic hydrocarbons, a naphthenic oil mainly containing naphthenic hydrocarbons, and an aromatic hydrocarbon mainly. Aromatic oils.
Of these, oils that are colorless and substantially odorless are preferred.
One type of oil may be used alone, or two or more types may be used in combination.

  The paraffin-based oil is not limited to the following, but for example, Diana Process Oil PW-32, PW-90, PW-150, PS-430 (made by Idemitsu Kosan), Syntax PA-95, PA-100 , PA-140 (manufactured by Kobe Oil Chemical), JOMO Process P200, P300, P500, 750 (manufactured by Japan Energy), Samper 110, 115, 120, 130, 150, 2100, 2280 (manufactured by Nippon Sun Oil) P-100, P-200, P-300, P-400, P-500 (manufactured by Fujikosan) and the like.

  Examples of the naphthenic oil include, but are not limited to, Diana Process Oil NP-24, NR-26, NR-68, NS-90S, NS-100, NM-280 (manufactured by Idemitsu Kosan), Syntax N-40, N-60, N-70, N-75, N-80 (manufactured by Kobe Oil Chemical), Shelflex 371JY (manufactured by Shell Japan), JOMO Process R25, R50, R200, R1000 (manufactured by Japan Energy) , Sansen Oil 310, 410, 415, 420, 430, 450, 380, 480, 3125, 4130, 4240 (manufactured by Nippon San Petroleum), Fuccoal New Flex 1060W, 1060E, 1150W, 1150E, 1400W, 1400E, 2040E, 2050N (Manufactured by Fujikosan), Petrex Process Oil PN-3, PN-3M, PN-3N-H (Yamabun Yuka), and the like.

Examples of the aromatic oil include, but are not limited to, Diana Process Oil AC-12, AC-640, AH-16, AH-24, AH-58 (manufactured by Idemitsu Kosan), and Syntax HA- 10, HA-15, HA-30, HA-35 (manufactured by Kobe Oil Chemical), Cosmo Process 40, 40A, 40C, 200A, 100, 1000 (manufactured by Cosmo Oil Lubricant), JOMO Process X50, X100E, X140 (Japan Energy) JSO Aroma 790, Nitoprene 720L (manufactured by Nippon Sun Oil), Fuccoal Aromax 1, 3, 5, EXP1 (manufactured by Fujikosan), Petrex Process Oil LPO-R, LPO-V, PF-2 (mountain) Manufactured by Bunyu Kayaku) and the like.
When higher weather resistance of the adhesive composition is required, it is preferable to use a paraffinic oil.

  In the first embodiment, from the viewpoint of the balance between the high adhesive holding power, the adhesive strength, and the adhesive residue resistance of the adhesive composition, the oil content is 10 parts by weight based on 100 parts by mass of the hydrogenated block copolymer. It is preferably from 150 to 150 parts by mass, more preferably from 30 to 130 parts by mass, and still more preferably from 50 to 100 parts by mass.

  Examples of the antioxidant include, but are not limited to, phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

  It is preferable to add a weathering agent from the viewpoint of high weather resistance of the adhesive composition (low adhesive force change after UV irradiation).

Examples of the weathering agent include, but are not limited to, benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, benzoate-based UV absorbers, hindered amine-based light stabilizers, and fine particle oxidation. An inorganic ultraviolet absorber such as cerium and the like can be mentioned.
From the viewpoint of higher weather resistance of the adhesive composition, a benzotriazole-based ultraviolet absorber and a hindered amine-based light stabilizer are preferable, and it is more preferable to use a benzotriazole-based ultraviolet absorber and a hindered amine-based light stabilizer in combination.

In the first embodiment, the lower limit of the content of the weathering agent in the adhesive composition, from the viewpoint of high weather resistance of the adhesive composition, the total mass of the adhesive composition of the present embodiment On the other hand, it is preferably at least 0.03 mass%, more preferably at least 0.05 mass%, even more preferably at least 0.07 mass%.
The upper limit of the content of the weathering agent in the adhesive composition of the first embodiment is 1% by mass based on the total mass of the adhesive composition from the viewpoint of suppressing bleeding of the weathering agent and economy. Is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

From the viewpoint of higher weather resistance of the adhesive composition, it is preferable to further use the above antioxidant in combination with the above weather agent.
When a weathering agent and an antioxidant are used in combination, among the antioxidants, it is preferable to use at least a phosphorus-based antioxidant in combination with the weathering agent from the viewpoint of higher weather resistance.

From the viewpoint of high weather resistance, the lower limit of the content of the antioxidant in the adhesive composition of the first embodiment is preferably 0.02% by mass or more based on the total mass of the adhesive composition. , 0.04% by mass or more, more preferably 0.06% by mass or more.
As the upper limit of the content of the antioxidant in the adhesive composition of the first embodiment, from the viewpoint of suppressing bleeding of the antioxidant and economical efficiency, 1 to the total mass of the adhesive composition. It is preferably at most 0.5 mass%, more preferably at most 1.25 mass%, even more preferably at most 1.0 mass%.

  In the first embodiment, from the viewpoint of preventing generation of static electricity of the tackifier resin, the adhesive composition preferably contains an antistatic agent.

  Examples of the antistatic agent include, but are not limited to, a surfactant, a conductive resin, and a conductive filler.

  In the first embodiment, the adhesive composition may include a lubricant from the viewpoint of improving the slipperiness of the product surface during and after the molding of the plastic.

  Examples of the lubricant include, but are not limited to, stearic acid amide and calcium stearate.

In a first embodiment, the adhesive composition may include a filler.
Examples of the filler include, but are not limited to, mica, calcium carbonate, kaolin, talc, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, and the like. The shape of these fillers is preferably spherical.

In the first embodiment, the tackifier composition may contain waxes from the viewpoint of the surface smoothness of the adhesive composition.
Examples of the waxes include, but are not limited to, paraffin wax, microcrystalline wax, low molecular weight polyethylene wax, and the like.

  In the first embodiment, the content of the waxes in the adhesive composition is preferably 10% by mass or less based on the total mass of the adhesive composition.

In the first embodiment, from the viewpoint of reducing the melt viscosity of the adhesive composition of the present embodiment to 130 ° C. or lower, the adhesive composition has a wax having a melting point of 50 ° C. to 110 ° C., for example, paraffin wax. It is preferable to contain 2 to 10% by mass of at least one wax selected from the group consisting of microcrystalline wax and Fischer-Tropsch wax.
The content of the wax having a melting point of 50 ° C to 110 ° C is preferably 5 to 10% by mass based on the total mass of the adhesive composition.
Further, the melting point of these waxes is preferably 65 ° C. or more, more preferably 70 ° C. or more, and further preferably 75 ° C. or more.
The softening point of the tackifier resin used at this time is preferably 70 ° C. or higher, more preferably 80 ° C. or higher.
At this time, the obtained adhesive composition has a storage elastic modulus G ′ (measurement conditions: 25 ° C., 10 rad / s) of 1 Mpa or less, and preferably has a crystallization temperature of 7 ° C. or less.

In the first embodiment, the adhesive composition may contain a polymer other than the hydrogenated block copolymer of the present embodiment (hereinafter, also simply referred to as “other polymer”).
Examples of other polymers include, but are not limited to, olefin elastomers such as natural rubber, polyisoprene rubber, polybutadiene rubber, styrene butadiene copolymer, ethylene propylene copolymer; chloroprene rubber, acrylic rubber And ethylene-vinyl acetate copolymer.
These may be liquid at room temperature or solid.

  In the first embodiment, from the viewpoint of the balance between the high adhesive strength of the adhesive composition, the high tackiness, and the high adhesiveness, the content of the other polymer is set to 100% in the hydrogenated block copolymer 100 of the present embodiment. It is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 40 parts by mass or less, even more preferably 20 parts by mass or less, based on parts by mass. It is even more preferable that the amount be 10 parts by mass or less.

The other polymer may be a block copolymer other than the hydrogenated block copolymer of the present embodiment (hereinafter, also simply referred to as “other block copolymer”).
Examples of other block copolymers include, but are not limited to, styrene-butadiene-based block copolymers, styrene-isoprene-based block copolymers, and hydrogenated styrene-butadiene-based block copolymers ( SEBS) and hydrogenated styrene-isoprene block copolymer (SEPS).
Other block copolymers include two or more types of hydrogenated block copolymers having different vinyl aromatic monomer unit contents, and non-hydrogenated or completely hydrogenated mainly composed of vinyl aromatic monomer units. It may be a block copolymer.

  In the first embodiment, the other block copolymer, from the viewpoint of the balance between high tackiness and high adhesive force of the adhesive composition, one polymer block mainly composed of vinyl aromatic monomer units and And a block copolymer having one polymer block mainly composed of a conjugated diene monomer unit.

  In the first embodiment, the other block copolymer preferably has a radial structure from the viewpoint of high holding power and low melt viscosity of the adhesive composition.

  In the first embodiment, the hydrogenation rates of other block copolymers are not particularly limited.

  In the first embodiment, when the adhesive composition contains a completely hydrogenated block copolymer as another polymer, from the viewpoint of the softness of the adhesive composition, the conjugate in the other polymer before hydrogenation. The average vinyl content in the diene monomer unit is preferably 35 mol% to 80 mol%, more preferably 40 mol% to 75 mol%, and more preferably 50 mol% to 75 mol%. Is more preferred.

In the first embodiment, the adhesive composition includes, as another polymer, a polymer mainly composed of a vinyl aromatic monomer unit having a weight average molecular weight (Mw) of 5,000 to 30,000 (hereinafter, referred to as “the polymer”). Low molecular weight vinyl aromatic polymer ").
The low-molecular-weight vinyl aromatic polymer is preferably composed mainly of a vinyl aromatic monomer unit contained in the polymer block (A) included in the hydrogenated block copolymer of the present embodiment. It is more preferable to mainly use the derived monomer unit.

In the first embodiment, in the adhesive composition, the lower limit of the content of the low-molecular-weight vinyl aromatic polymer, from the viewpoint of the solubility of the adhesive composition, the hydrogenated block copolymer of the present embodiment It is preferably at least 0.5 part by mass, more preferably at least 1.0 part by mass, even more preferably at least 2.0 parts by mass, and preferably at least 3.0 parts by mass, per 100 parts by mass. Is even more preferred.
Further, the upper limit of the content of the low-molecular-weight vinyl aromatic polymer is 100 parts by mass of the hydrogenated block copolymer of the present embodiment from the viewpoints of adhesiveness, tackiness, adhesion holding power, and the like of the adhesive composition. It is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, still more preferably 3.0 parts by mass or less, and more preferably 2.0 parts by mass or less. Is even more preferred.

In the first embodiment, the low-molecular-weight vinyl aromatic polymer is preferably mixed with the tackifier resin after being previously mixed with the hydrogenated block copolymer of the present embodiment.
The low-molecular-weight vinyl aromatic polymer may be prepared alone and mixed with the hydrogenated block copolymer of the present embodiment. You may.

  As a method for preparing a low molecular weight vinyl aromatic polymer at the same time as producing the hydrogenated block copolymer of the present embodiment, for example, a polymer block (A) mainly containing vinyl aromatic monomer units and When producing a living block copolymer having a polymer block (B) containing a conjugated diene monomer unit, a part of the vinyl aromatic monomer used has a weight average molecular weight (Mw) of 5,000.リ ビ ン グ 30,000 of vinyl aromatic monomer units to remain as a living polymer, and deactivate the living block copolymer and the remaining living polymer to obtain a vinyl aromatic monomer A block copolymer having a polymer block (A) mainly composed of units and a polymer block (B) containing a conjugated diene monomer unit, and a low molecular weight vinyl aromatic polymer are simultaneously prepared. How to, and the like.

  As a method for leaving a part of the vinyl aromatic monomer as a living polymer mainly composed of a vinyl aromatic monomer unit having a weight average molecular weight (Mw) of 5,000 to 30,000, a polymerization step Controlling the amount of the monomer to be added, the amount of the polymerization initiator, the reaction temperature, the reaction time and the like can be mentioned. From the viewpoint of controlling the molecular weight and content of the low-molecular-weight vinyl aromatic polymer, it is preferable that the reaction start temperature at the time of polymerizing the polymer block (A) is 55 ° C or higher and 65 ° C or lower. The reaction time for polymerizing the polymer block (A) is preferably 2 minutes or more and 5 minutes and 30 seconds or less after the temperature rises due to the polymerization reaction and the temperature shows the maximum value.

  As a method for preparing a low-molecular-weight vinyl aromatic polymer at the same time as producing the hydrogenated block copolymer of the present embodiment, for example, a vinyl aromatic monomer unit by polymerizing a vinyl aromatic monomer unit When preparing a polymer block (A) mainly composed of a low molecular weight vinyl aromatic polymer, a part of the living polymer block (A) is deactivated by adding an active hydrogen compound such as methanol. Is generated. Thereafter, a polymer block (B) containing a conjugated diene monomer unit is polymerized on the living polymer block (A) remaining without being deactivated to prepare a hydrogenated block copolymer of the present embodiment. be able to. Thereby, when the hydrogenated block copolymer of the present embodiment is prepared, a low molecular weight vinyl aromatic polymer can be prepared at the same time.

  As described above, the weight-average molecular weight (Mw) of the hydrogenated block copolymer of the present embodiment is measured for the low molecular weight vinyl aromatic polymer prepared simultaneously with the production of the hydrogenated block copolymer of the present embodiment. In this case, it is detected as a low molecular component, so that the presence of a low molecular weight vinyl aromatic polymer can be confirmed at that time, and its weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) Can be measured.

  A commercially available low molecular weight vinyl aromatic polymer may be mixed with the hydrogenated block copolymer of the present embodiment.

  In the first embodiment, when high low-temperature coatability (low viscosity), creep performance (smaller value is better), high strength or high elongation, etc. are required, It is preferable to use an ionomer in the range of 5% by mass or less as the polymer of (1).

  In the first embodiment, a carboxyl group and / or a carboxylic anhydride may be used as the other polymer in the adhesive composition in order to exhibit excellent adhesive strength to the wet hydrophilic porous substrate. It is preferable to add 0.5 to 8% by mass of a liquid rubber having a basic group in the molecule and / or an acid-modified polyethylene acid-modified with a carboxylic anhydride.

In the first embodiment, from the viewpoint of high-temperature storage stability, high elongation, and from the viewpoint of reducing the content of the tackifying resin in the adhesive composition, as another polymer, a copolymer using an α-olefin, Alternatively, the propylene homopolymer is preferably contained in the adhesive composition in a range of 20% by mass or less.
The melting point of these other polymers (conditions: DSC measurement, 5 ° C./min) is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 60 ° C. to 90 ° C.
These other polymers may be resins or elastomers.

In the first embodiment, from the viewpoint of elongation of the adhesive composition, it is preferable that the adhesive composition contains an olefin elastomer as another polymer.
The olefin-based elastomer is not limited to the following, but for example, an olefin-based elastomer having a Tg of at least −10 ° C. or less is preferable. Further, from the viewpoint of creep performance, an olefin-based elastomer having a block is more preferable.

  In the first embodiment, when the adhesive composition is used in a high-temperature environment, JP-A-2015-28130, JP-A-2007-56119, JP-A-2014-534303, and JP-A-2015-30854. It is preferable to improve heat resistance by using an additive capable of radical cross-linking, epoxy cross-linking, or urethane cross-linking in the adhesive composition as disclosed in Japanese Patent Application Laid-Open (JP-A) No. 2002-131131.

  In the first embodiment, the adhesive composition can be used for, but is not limited to, an adhesive tape and a label.

  In the first embodiment, the adhesive tape has the adhesive composition described above. In a first embodiment, the label has the adhesive composition described above.

In the first embodiment, the adhesive composition is preferably used by being laminated on an arbitrary substrate. Examples of the substrate include, but are not limited to, a film made of a thermoplastic resin, and a non-thermoplastic resin substrate such as paper, metal, woven fabric, and nonwoven fabric.
A release agent may be added to the base material. Examples of the release agent include a long-chain alkyl release agent and a silicon release agent.
Further, when higher weather resistance (a small change in adhesive strength after UV irradiation) is required, it is preferable to use a substrate having a low ultraviolet transmittance, and the ultraviolet transmittance is preferably 1% or less.

(Production method of adhesive composition)
In the first embodiment, the method for producing the adhesive composition is not particularly limited, and the tackifying resin is 20 parts by mass to 400 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer of the present embodiment. And can be produced by mixing the same.
If necessary, other components such as other block copolymers and oils may be mixed. Examples of the mixing method include known mixers, kneaders, single-screw extruders, twin-screw extruders, and Banbury mixers. The method used is mentioned.
The mixing conditions are not limited to the following, but for example, a method of uniformly mixing while heating is preferable.

(Method of manufacturing adhesive tape and label)
In the first embodiment, the adhesive tape and the label can be manufactured by applying the adhesive composition on an arbitrary substrate.
The method for applying the adhesive composition on the substrate is not limited to the following, but includes, for example, a T-die coating method, a roll coating method, a multi-bead coating method, and a spray coating method. Can be In addition, as a method for applying the adhesive composition of the first embodiment, either an extrusion coating (hot melt coating) method or a spread coating method may be used, and from the viewpoint of high heat aging resistance and economic efficiency, Extrusion coating is preferred.

  In the first embodiment, the adhesive composition comprises various adhesive tapes, labels, pressure-sensitive thin plates, pressure-sensitive sheets, surface protection sheets / films, back paste for fixing various lightweight plastic molded products, and carpet fixing. It can be suitably used as a back glue, a back glue for fixing tiles, an adhesive, a sealing agent, a masking agent at the time of paint repainting work, a sanitary article, and the like. Particularly, an adhesive tape is preferable.

(Modified asphalt composition and hydrogenated block copolymer used therein)
In the second embodiment, the hydrogenated block copolymer of the present embodiment can be used for a modified asphalt composition.

  By using the hydrogenated block copolymer of the present embodiment in a modified asphalt composition, low-temperature elongation, heat aging resistance during storage, and fluidity are excellent, and the balance between these properties and compatibility is excellent. The modified asphalt composition can be provided.

(Hydrogenated block copolymer)
In the second embodiment, the low-temperature elongation of the modified asphalt composition, heat aging during storage, resistance to flow, and from the viewpoint of high compatibility with asphalt, the hydrogenated block copolymer of the present embodiment is A hydrogenated block copolymer having a polymer block (A) mainly containing vinyl aromatic monomer units and a polymer block (B) containing conjugated diene monomer units, In the copolymer block (B) having a monomer unit, the first region to the sixth region are made to have an equal mass in order from the polymerization start terminal side, and the first region to the sixth region contain vinyl before hydrogenation. When the maximum value is _VH and the minimum value is _VL , _VH - _VL = 5 mol% to 30 mol%.
The Δvinyl content (V _H −V _L ) is as described above, and the description is omitted.

  In the second embodiment, the low-temperature elongation of the modified asphalt composition, heat aging resistance during storage, fluid resistance, and from the viewpoint of high compatibility with asphalt, the hydrogenated block copolymer of the present embodiment is A hydrogenated block having a polymer block (A) mainly composed of a vinyl aromatic monomer unit and a copolymer block (B2) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit It is preferably a copolymer.

The structure used in the second embodiment before hydrogenation (hereinafter, also referred to as “hydrogenation”) of the hydrogenated block copolymer of the present embodiment is not limited to the following. For example, the following formula (13) To (18).
(AB2) _n ... (13)
B2- (A-B2) _n (14)
A- (B2-A) _n (15)
A- (B2-A) _n -X (16)
[(A-B2) _k ] _m -X (17)
[(A-B2) _k -A] _m -X (18)

  In the above formulas (13) to (18), A represents a polymer block mainly composed of a vinyl aromatic monomer unit, and B2 contains a vinyl aromatic monomer unit and a conjugated diene monomer unit. Represents a copolymer block, 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, and preferably 1 or more. Represents an integer of from 5 to 5.

In the second embodiment, when a plurality of polymer blocks (A) and (B2) exist in the block copolymer before hydrogenation, even if the structures such as molecular weight and composition are the same, Good or different.
In the above formulas (13) to (18), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium.
The hydrogenated 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 in which X is a residue of a polymerization initiator. .
The boundaries and the extreme ends of each block do not necessarily need to be clearly distinguished.

In the second embodiment, in the polymer block (A) mainly containing a vinyl aromatic monomer unit, or in the copolymer block (B2) containing a conjugated diene monomer unit and a vinyl aromatic monomer unit. The distribution of the vinyl aromatic monomer units is not particularly limited, and may be distributed uniformly, or may be distributed in a tapered, stepped, convex, or concave shape.
Further, a crystal part may be present in the polymer block. In the polymer block (A) mainly composed of a vinyl aromatic monomer unit, a plurality of segments having different contents of the vinyl aromatic monomer unit may coexist.

  In the second embodiment, from the viewpoint of the low viscosity of the modified asphalt composition, the hydrogenated block copolymer is composed of one polymer block (A) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer. It is preferable to include a hydrogenated block copolymer (d2) having one hydrogenated polymer block (B2) containing a monomer and a vinyl aromatic monomer unit. Note that the hydrogenated block copolymer (d2) has a structure in which n = 1 in the above formula (13).

In the second embodiment, the lower limit of the content of the hydrogenated block copolymer (d2) is 15% by mass based on 100% by mass of the hydrogenated block copolymer from the viewpoint of the low viscosity of the modified asphalt composition. % Or more, more preferably 25% by mass or more, still more preferably 50% by mass or more, even more preferably 65% by mass or more, and preferably 70% by mass or more. Even more preferred.
In the second embodiment, the upper limit of the content of the hydrogenated block copolymer (d2) is set at 100 mass% from the viewpoint of a high softening point and a high elongation of the modified asphalt composition. %, Preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, even more preferably 75% by mass or less, based on 70% by mass. It is even more preferred that the content be not more than mass%.

In the second embodiment, from the viewpoint of low viscosity of the modified asphalt composition, the hydrogenated block copolymer preferably contains a hydrogenated block copolymer (r2) having a radial structure. Here, in the present specification, the “radial structure” refers to a structure in which three or more polymers are bonded to a residue X, for example, A- (B2-A) _n -X (n ≧ 3 ), [(AB2) _k ] _m- X (m≥3), and [(AB2) _k- A] _m- X (m≥3).

  As the structure of the hydrogenated block copolymer (r2) having a radial structure, [(A-B2) k] mx and [(A-B2) kA from the viewpoint of low viscosity and high adhesive strength. MX (wherein m represents an integer of 3 to 6, k represents an integer of 1 to 4, and more preferably m represents an integer of 3 to 4). Preferably, it has at least one structure.

In the second embodiment, from the viewpoint of compatibility with asphalt, the upper limit of the hydrogenation rate of the hydrogenated block copolymer is 97 mol% or less, based on the total number of moles of the conjugated diene monomer unit. It is preferably at most 95 mol%, more preferably at most 90 mol%, even more preferably at most 85 mol%, even more preferably at most 80 mol%. .
Further, from the viewpoint of heat aging resistance during storage of the modified asphalt composition and flow resistance of the modified asphalt mixture, the lower limit of the hydrogenation rate of the hydrogenated block copolymer may be 1 mol% or more. Preferably, it is at least 10 mol%, more preferably at least 30 mol%, even more preferably at least 40 mol%, even more preferably at least 50 mol%.

In the second embodiment, the hydrogenation rate of the hydrogenated block copolymer of the present embodiment may have a distribution.
As the index of the hydrogenation rate distribution, H shown in the first embodiment can be used, and the method of obtaining the index H of the hydrogenation rate distribution is the same as the method described in the first embodiment. it can.
From the viewpoint of the low-temperature elongation of the modified asphalt composition, the heat aging resistance during storage, the flow resistance, and the balance between these properties and compatibility, the value of the index H of the hydrogenation rate distribution is 0.001 to 0. 0.007 or less, more preferably 0.001 or more and 0.0055 or less, and even more preferably 0.001 or more and 0.004 or less.

  The hydrogenation rate of the hydrogenated block copolymer can be adjusted by controlling the hydrogenation amount and the hydrogenation reaction time in the hydrogenation step described below. Further, the hydrogenation rate can be determined by a method described in Examples described later.

In the second embodiment, the content (TS) of the vinyl aromatic monomer unit contained in the hydrogenated block copolymer is preferably 30 to 60% by mass. Excellent compatibility of modified asphalt composition, high softening point, high temperature storage stability of modified asphalt composition, high aggregate peeling resistance when mixed with modified asphalt composition and aggregate From the viewpoint, the lower limit of the content (TS) of the vinyl aromatic monomer unit in the hydrogenated block copolymer is preferably 30% by mass or more, more preferably 33% by mass or more, and 36% by mass. More preferably, the content is 40% by mass or more.
Further, the upper limit of the content (TS) of the vinyl aromatic monomer unit in the hydrogenated block copolymer is 60 mass% from the viewpoint of compatibility, low viscosity, and flexibility of the modified asphalt composition. %, Preferably at most 55% by mass, more preferably at most 50% by mass, even more preferably at most 45% by mass.

In the second embodiment, the lower limit of the content (BS) of the polymer block (A) mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer of this embodiment is modified asphalt. From the viewpoint of a high softening point of the composition, the content is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 17% by mass or more, and even more preferably 19% by mass or more.
In the second embodiment, the upper limit of the content (BS) of the polymer block (A) mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer of the present embodiment is asphalt. 40 mass% or less is preferable, 35 mass% or less is more preferable, 28 mass% or less is still more preferable, and 25 mass% or less is still more preferable from the point of high compatibility with the modified asphalt composition, and high flexibility. .

  The content (TS) of the vinyl aromatic monomer unit in the hydrogenated block copolymer and the content (BS) of the polymer block (A) mainly composed of the vinyl aromatic monomer unit are as follows: It can be measured by the method described in Examples described later.

In the second embodiment, the molecular weight distribution of the polymer block (A) mainly composed of a vinyl aromatic monomer is preferably 1.46 or less, more preferably 1.44, from the viewpoint of the flow resistance of the modified asphalt composition. The following is more preferable, 1.42 or less is still more preferable, and 1.40 or less is still more preferable.
In addition, from the viewpoint of the recoverability of the modified asphalt composition after tension, it is preferably 1.1 or more, more preferably 1.12 or more, still more preferably 1.14 or more, and even more preferably 1.16 or more.
Here, the molecular weight distribution of the polymer block (A) mainly composed of a vinyl aromatic monomer can be determined by the following equation.
Molecular weight distribution = (molecular weight on high molecular weight side at full width at half maximum of peak molecular weight of polymer block (A)) / (molecular weight on low molecular weight side at full width at half maximum of peak molecular weight of polymer block (A))

  In the second embodiment, the lower limit of the content (RS) of the vinyl aromatic monomer unit in the copolymer block (B2) containing the conjugated diene monomer unit and the vinyl aromatic monomer unit is modified. In view of the separation stability of the porous asphalt composition, the heat aging resistance during storage, and the recovery after tension, it is preferably 5% by mass or more based on the total mass of the copolymer block (B2), and 20% by mass. %, More preferably at least 25% by mass.

  In the second embodiment, the addition amount of the hydrogenated block copolymer of the present embodiment added to asphalt is reduced, the separation stability of the modified asphalt composition, and the flexibility of the modified asphalt composition and the hydrogenated block copolymer are increased. From the viewpoints of heat resistance, weather resistance, and peeling resistance of the modified asphalt composition, the vinyl aromatic unit in the copolymer block (B2) containing a conjugated diene monomer unit and a vinyl aromatic monomer unit is used. The upper limit of the content (RS) of the monomer unit is preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less based on the total mass of the copolymer block (B2).

The content (RS) of the vinyl aromatic monomer units in the copolymer block (B2) is calculated from the content (TS) of the vinyl aromatic monomer units in the hydrogenated block copolymer. It is a ratio (mass%) in the copolymer block (B2) of a value (TS-BS) obtained by subtracting the content (BS) of the polymer block (A) mainly composed of a group monomer unit.
The content (RS) of the vinyl aromatic monomer unit in the copolymer block (B2) can be determined by the following equation.
RS (% by mass) = (TS-BS) / (100-BS) × 100

In the second embodiment, the reaction time from the start of the polymerization of the copolymer block (B2) to the end of the polymerization is divided into three equal parts, which are referred to as a first stage, a middle stage, and a second stage, respectively. The vinyl aromatic monomer unit content in B2) is S1 (% by mass), the vinyl aromatic monomer unit content in the copolymer block (B2) at the end of the middle stage is S2 (% by mass), When the content of the vinyl aromatic monomer unit in the copolymer block (B2) at the end is S3 (% by mass), from the viewpoint of compatibility with asphalt, S2 / S1> 1, and S3 / A structure that satisfies the relationship of S2> 1 is more preferable.
In addition, "at the time of the start of polymerization" of the copolymer block (B2) is defined as when the raw material monomer of the copolymer block (B2) is charged into the reactor, and "at the end of polymerization" of the copolymer block (B2). The term “immediately before” means immediately before the raw material monomer of the copolymer block (A) is charged into the reactor. The vinyl aromatic monomer unit content S1 to S3 can be measured by sampling the polymer solution at each time of the end of the former stage, the end of the middle stage, and the end of the latter stage.

In the second embodiment, the content of the short-chain vinyl aromatic monomer polymerized portion in the copolymer block (B2) is preferably 50% by mass or more.
When the content of the short-chain vinyl aromatic monomer polymerized portion in the copolymer block (B2) is within the above range, the compatibility between the hydrogenated block copolymer of the present embodiment and asphalt is high. In this case, the modified asphalt composition tends to have improved recoverability after tension, heat aging resistance, and aggregate peeling resistance.
The lower limit of the content of the polymerized portion of the short-chain vinyl aromatic monomer in the copolymer block (B2) is more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably. It is preferably at least 90% by mass.
The upper limit of the content of the short-chain vinyl aromatic monomer polymerized portion in the copolymer block (B2) is not particularly limited, but is preferably 99% by mass or less, and more preferably 95% by mass or less. Is more preferably 90% by mass or less, and still more preferably 80% by mass or less.

In the specification of the present application, the “short-chain vinyl aromatic monomer polymerized portion” refers to a portion in which 2 to 6 vinyl aromatic monomer units are continuous in the copolymer block (B2).
The content of the polymerized portion of the short-chain vinyl aromatic monomer is set such that the content (RS) of the vinyl aromatic monomer unit in the copolymer block (B2) is 100% by mass, and 2 to 6 It is determined as the content (% by mass) of continuous vinyl aromatic monomer units.
The content of 2 to 6 consecutive vinyl aromatic monomer units can be measured by the method described below.
<Content of polymerized portion of short-chain vinyl aromatic monomer (short-chain styrene content)>
Oxide having a concentration of 1.5% (O ₃ ) was passed through a dichloromethane solution of the polymer at 150 mL / min to oxidatively decompose, and the resulting ozonide was reduced by dropping into diethyl ether mixed with lithium aluminum hydride. I do.
Next, pure water is dropped and hydrolyzed, potassium carbonate is added, salting out and filtration are performed to obtain a vinyl aromatic hydrocarbon component.
This vinyl aromatic hydrocarbon component is measured by GPC.
By calculating the area ratio of the peaks obtained here (the peak area corresponding to the polymerized portion of the short-chain vinyl aromatic monomer / the total area of the peaks), two to six consecutive short-chain vinyl aromatics in the polymer were obtained. The content of the group III monomer polymerized moiety is obtained.
At this time, the content of two consecutive vinyl aromatic monomer units and the content of three consecutive vinyl aromatic monomer units can be measured from the molecular weight of the obtained peak.
The ozone generator used was OT-31R-2 manufactured by Japan Ozone Co., Ltd., and the GPC measurement was performed using Waters 2487, chloroform as a solvent, a flow rate of 1.0 mL / min, and a column oven at 35 ° C. The column can be measured by connecting two Shodex columns-K803L.

In the copolymer block (B2) included in the hydrogenated block copolymer of the present embodiment in the second embodiment, the polymerized portion of the short-chain vinyl aromatic monomer polymerized by two continuous vinyl aromatic monomer units The content is preferably from 10% by mass to 45% by mass, more preferably from 13% by mass to 42% by mass, and still more preferably from 19% by mass to 36% by mass.
The content of two consecutive vinyl aromatic monomer units can be measured by the above method.

In the copolymer block (B2) according to the second embodiment, the content of the short-chain vinyl aromatic monomer polymerized portion in which three vinyl aromatic monomer units are continuous is 45% by mass or more and 80% by mass or less. The content is preferably 45% by mass or more and 75% by mass or less, and more preferably 45% by mass or more and 65% by mass or less.
The content of three consecutive vinyl aromatic monomer units can be measured by the above method.

In the second embodiment, the average vinyl content in the conjugated diene monomer unit in the block copolymer before hydrogenation of the hydrogenated block copolymer of the present embodiment is preferably from 15 mol% to 50 mol%. Is less than 18 mol% to 40 mol%, more preferably 21 mol% to 35 mol%, even more preferably 24 mol% to 32 mol%.
In the second embodiment, when the average vinyl content in the conjugated diene monomer unit in the block copolymer before hydrogenation is 15 mol% or more, the amount of the hydrogenated block copolymer added to asphalt is increased. Tend to be lower.
Further, since the average vinyl content in the conjugated diene monomer unit in the block copolymer before hydrogenation is less than 50 mol%, the heat resistance aging property and the weather resistance during storage of the modified asphalt composition are reduced. It tends to be higher.
Here, the “average vinyl content” refers to a conjugate incorporated in a 1,2-bond, 3,4-bond, or 1,4-bond bonding mode of a conjugated diene monomer unit before hydrogenation. The ratio of the conjugated diene monomer unit incorporated by 1,2-bond and 3,4-bond to the total molar amount of the diene monomer unit.
The average vinyl content can be measured by NMR, and specifically, can be measured by the method described in Examples described later.

In the second embodiment, the weight-average molecular weight (Mw) of the hydrogenated block copolymer is preferably 100,000 or more, from the viewpoints of the recovery property after tension of the modified asphalt composition and the peeling resistance of aggregate, and 15% or more. It is more preferably 10,000 or more, and still more preferably 170,000 or more.
Further, from the viewpoint of the productivity of the modified asphalt composition, the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 500,000 or less, more preferably 400,000 or less, further preferably 300,000 or less, and 27 Even less than 10,000 is even more preferred.

In the second embodiment, the lower limit of the molecular weight distribution (Mw / Mn) (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the hydrogenated block copolymer of the present embodiment is added to asphalt. From the viewpoint of reducing the addition amount of the hydrogenated block copolymer, it is preferably 1.03 or more, more preferably 1.05 or more, still more preferably 1.11 or more, and even more preferably 1.20 or more.
From the viewpoint of reducing the amount of the hydrogenated block copolymer to be added to the asphalt and the productivity of the modified asphalt composition, the upper limit of the molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer is 2 It is preferably at most 1.0, more preferably at most 1.7, still more preferably at most 1.4, even more preferably at most 1.3.
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer can be determined by the methods described in Examples described later.

In the second embodiment, the lower limit of the peak temperature of the loss tangent (tan δ) of the hydrogenated block copolymer of the present embodiment measured by dynamic viscoelasticity is high compatibility with asphalt, From the viewpoint of a short production time, the temperature is preferably −50 ° C. or higher, more preferably −47 ° C. or higher, further preferably −44 ° C. or higher, and still more preferably −42 ° C. or higher.
In addition, from the viewpoints of compatibility and flexibility of the modified asphalt composition, the upper limit of the peak temperature of the loss tangent (tan δ) of the hydrogenated block copolymer of the present embodiment may be −5 ° C. or less. Preferably, it is -10 ° C or less, more preferably -15 ° C or less, and even more preferably -25 ° C or less.

  In the second embodiment, the peak height of the loss tangent (tan δ) in the range of −50 ° C. or more and −5 ° C. or less according to the dynamic viscoelasticity measurement of the hydrogenated block copolymer of this embodiment is the same as that of the modified asphalt composition. From the viewpoints of compatibility, high post-tensile recovery, and heat aging resistance during storage, it is preferably more than 0.7 and 1.6 or less, more preferably 0.8 or more and 1.8 or less, 0.9 or more and 1.7 or less are still more preferable, and 1.0 or more and 1.5 or less are still more preferable.

In the second embodiment, the hydrogenated block copolymer of the present embodiment is selected from the viewpoints of compatibility of the modified asphalt composition, heat aging resistance during storage, and mechanical properties of the modified asphalt mixture. It is preferable that the polymer has at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group.
Among these, the hydrogenated block copolymer more preferably has at least one functional group selected from the group consisting of an amino group and an amide group, and more preferably has an amino group.
More preferably, the hydrogenated block copolymer of the present embodiment contains at least one functional group selected from the group consisting of an amino group and an amide group in an amount of 2 mol or more per 1 mol of the molecule.

In the second embodiment, the lower limit of the melt flow rate (MFR, 200 ° C., 5 kgf) of the hydrogenated block copolymer is 0.1 g / 10 min or more from the viewpoint of a short production time of the modified asphalt composition. It is preferably at least 1 g / 10 min, more preferably at least 2 g / 10 min.
The upper limit of the melt flow rate (MFR, 200 ° C., 5 kgf) of the hydrogenated block copolymer is such that the amount of the hydrogenated block copolymer to be added to asphalt is reduced, or the modified asphalt composition From the viewpoint of recoverability after tension, it is preferably 50 g / 10 minutes or less, more preferably 10 g / 10 minutes or less, and even more preferably 8 g / 10 minutes or less.

(Modified asphalt composition)
In the second embodiment, the modified asphalt composition of the present embodiment contains 1 part by mass or more and 20 parts by mass or less of the hydrogenated block copolymer described above with respect to 100 parts by mass of asphalt.

Examples of asphalt include, but are not limited to, those obtained as a by-product of petroleum refining (petroleum asphalt), natural products (natural asphalt), and mixtures of these with petroleum And the like.
The main component of asphalt is generally called bitumen (bitumen).

Examples of the asphalt include, but are not limited to, straight asphalt, semi-blown asphalt, blown asphalt, solvent deasphalted asphalt, tar, pitch, cutback asphalt with added oil, and asphalt emulsion.
From the viewpoint of availability, the asphalt is preferably straight asphalt. These may be used alone or as a mixture.
Further, an aromatic heavy mineral oil such as a petroleum-based solvent extraction oil, an aroma-based hydrocarbon-based process oil, or an extract may be added to various asphalts.

  The asphalt preferably has a penetration (measured by JIS-K2207) of 30 or more and 300 or less, more preferably 50 or more and 250 or less, even more preferably 60 or more and 200 or less.

In the second embodiment, the modified asphalt composition preferably contains a tackifying resin from the viewpoint of improving the compatibility of the modified asphalt composition and the resistance to peeling of aggregate.
In the second embodiment, the “tackifying resin” refers to a resin (oligomer) having a number average molecular weight of 100 to less than 10,000, which can impart tackiness to the modified asphalt composition.
The number average molecular weight of the tackifier resin can be measured by a method similar to the method for measuring the number average molecular weight described in Examples described later.

  In the second embodiment, the tackifier resin is not limited to the following, for example, rosin-based resin, hydrogenated rosin-based resin, terpene-based resin, cumarone-based resin, phenol-based resin, terpene-phenol-based Resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and the like.

As the tackifier resin, only one kind may be used alone, or two or more kinds may be used in combination.
In the second embodiment, examples of the tackifier resin include those described in “Rubber / Plastic Compound Chemicals” (edited by Rubber Digest).
From the viewpoint of high compatibility of the modified asphalt composition and improvement of the peeling resistance of the aggregate, an aromatic hydrocarbon resin is preferable as the tackifier resin.

In the second embodiment, the content of the tackifier resin in the modified asphalt composition is more than 0 parts by mass and 200 parts by mass or less when the hydrogenated block copolymer of the present embodiment is 100 parts by mass. It is more preferably 3 parts by mass or more and 100 parts by mass or less.
By adjusting the content in the above range, it is possible to more reliably obtain the effects of improving the compatibility and the peeling resistance of the aggregate.

In the second embodiment, the modified asphalt composition preferably contains an oil from the viewpoint of obtaining a low viscosity and high compatibility of the modified asphalt composition.
Examples of the oil include, but are not limited to, a mineral oil-based softener and a synthetic resin-based softener.
As the mineral oil-based softener, generally, paraffin-based oil, naphthenic-based oil, aromatic-based oil and the like can be mentioned.

  In general, those in which the number of carbon atoms of the paraffinic hydrocarbon accounts for 50% or more of the total carbon atoms contained in the oil are referred to as “paraffinic oils”, and the number of carbon atoms of the naphthenic hydrocarbons is Oils having 30% or more and 45% or less are called "naphthenic oils", and oils in which aromatic hydrocarbons have 35% or more carbon atoms are called "aromatic oils".

The workability of the modified asphalt composition is improved by including a mineral oil-based softener.
As the mineral oil-based softener, a paraffinic oil is preferred from the viewpoint of low viscosity of the modified asphalt composition and low-temperature performance, and a naphthene is preferred from the viewpoint of low viscosity of the modified asphalt composition and high compatibility. System oils are preferred.

  The synthetic resin-based softener is not limited to the following, but for example, polybutene, low molecular weight polybutadiene and the like are preferable.

  In the second embodiment, the content of the oil in the modified asphalt composition is controlled from the viewpoint of suppressing bleeding of the oil and ensuring sufficient mechanical strength of the modified asphalt composition for practical use. When the copolymer is 100 parts by mass, it is preferably more than 0 parts by mass and 100 parts by mass or less, more preferably more than 0 parts by mass and 50 parts by mass or less, more preferably 2 parts by mass or more and 30 parts by mass or less. The range is more preferred.

In the second embodiment, the modified asphalt composition preferably contains a crosslinking agent from the viewpoint of improving the high softening point, compatibility, and high-temperature storage stability of the modified asphalt composition.
Examples of the crosslinking agent include, but are not limited to, sulfur, sulfur compounds, inorganic vulcanizing agents other than sulfur, oximes, nitroso compounds, polyamines, organic peroxides, resin crosslinking agents, isocyanate compounds, Polyphosphoric acid, and a crosslinking aid.

  In the second embodiment, sulfur, a sulfur compound, and polyphosphoric acid are preferable as the crosslinking agent from the viewpoints of high softening point, compatibility, and heat aging resistance during storage of the modified asphalt composition.

In the second embodiment, the lower limit of the addition amount of the crosslinking agent in the modified asphalt composition is high compatibility between the conjugated diene copolymer and asphalt, and high mass resistance when the modified asphalt mixture adheres to oil. From the viewpoint of loss and high reduction in strength, the content is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, even more preferably 0.06% by mass or more based on the total mass of the modified asphalt composition.
In addition, the amount of the crosslinking agent added to the modified asphalt composition is, as described in JP-T-2013-520543, from the viewpoint of obtaining a modified asphalt composition having a high penetration, It may be used in a range of about 20% to 60% by weight based on the total weight of the composition.
The upper limit of the amount of the cross-linking agent added to the modified asphalt composition is determined based on the total mass of the modified asphalt composition from the viewpoint of obtaining a modified asphalt composition having a high penetration and economy. 0 mass% or less is preferable, 0.4 mass% or less is more preferable, and 0.2 mass% or less is still more preferable.

In the second embodiment, from the viewpoint of sufficiently reacting the conjugated diene copolymer and the crosslinking agent, the mixing time after adding the crosslinking agent to the modified asphalt composition is preferably 20 minutes or more, and 40 minutes or more. Is more preferably 60 minutes or more, and even more preferably 90 minutes or more.
In addition, from the viewpoint of suppressing thermal degradation of the conjugated diene copolymer, the mixing time after adding the crosslinking agent to the modified asphalt composition is preferably 5 hours or less, more preferably 3 hours or less, and more preferably 2.5 hours or less. Is more preferable, and 2 hours or less is still more preferable.

  In the second embodiment, a foaming agent may be blended during the production of the modified asphalt from the viewpoint of lowering the viscosity of the modified asphalt composition and further shortening the production time of the modified asphalt composition.

  In the second embodiment, examples of the foaming agent include, but are not limited to, sodium bicarbonate, ammonium carbonate, diazoaminobenzene, N, N′-dinitrosopentamethylenetetramine, and 2,2′-. Azobis (isobutyronitrile) and the like. From the viewpoint of compatibility with the modified asphalt, diazoaminobenzene, N, N'-dinitrosopentamethylenetetramine, and 2,2'-azobis (isobutyronitrile) are preferable as the blowing agent.

In the second embodiment, the amount of the foaming agent added to the modified asphalt composition is preferably 0.1% by mass or more, and more preferably 0.3% by mass, from the viewpoints of low viscosity and short production time of the modified asphalt composition. More preferably, the content is 0.5% by mass or more.
The amount of the foaming agent added to the modified asphalt composition is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of economy.

In a second embodiment, the modified asphalt composition may include other additives commonly used in blending thermoplastic resins and rubbery polymers.
Other additives include, but are not limited to, for example, inorganic fillers, lubricants, release agents, plasticizers, antioxidants, stabilizers, flame retardants, antistatic agents, organic fibers, glass Examples include reinforcing agents such as fibers, carbon fibers, and metal whiskers, coloring agents, pigments, viscosity modifiers, anti-stripping agents, and pigment dispersants.
The content of other additives is not particularly limited, and is usually 50 parts by mass or less based on 100 parts by mass of asphalt.

  In the second embodiment, examples of the inorganic filler include, but are not limited to, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, and wollast. Knight, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber and the like.

  In the second embodiment, examples of the lubricant and the mold release agent include, but are not limited to, carbon black, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, and stearic acid. Magnesium and ethylene bisstearamide.

  In the second embodiment, examples of the stabilizer include, but are not limited to, various stabilizers such as an antioxidant and a light stabilizer.

In the second embodiment, examples of the antioxidant include, but are not limited to, a phenolic antioxidant such as a radical scavenger, a phosphorus antioxidant such as a peroxide decomposer, and And sulfur-based antioxidants.
Further, an antioxidant having both properties may be used.
These may be used alone or in combination of two or more.
Among these, a phenolic antioxidant is preferred from the viewpoint of heat aging resistance of the block copolymer and suppression of gelation.
Examples of the antioxidant include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,4- Bis [(octylthio) methyl] -o-cresol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-di- t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ] Hindered phenolic antioxidants such as acrylates; sulfur-based antioxidants such as dilaurylthiodipropionate, laurylstearylthiodipropionate pentaerythritol-tetrakis (β-laurylthiopropionate); tris (nonylphenyl) ) Phosphite-based antioxidants such as phosphite and tris (2,4-di-t-butylphenyl) phosphite.

  In the second embodiment, examples of the light stabilizer include, but are not limited to, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3). Benzotriazole ultraviolet absorbers such as ', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole; 2 Benzophenone-based ultraviolet absorbers such as -hydroxy-4-methoxybenzophenone; hindered amine-based light stabilizers;

In the second embodiment, the peeling preventive agent can prevent peeling between the modified asphalt composition and the aggregate when the modified asphalt composition is mixed with the aggregate.
Examples of the anti-peeling agent include, but are not limited to, a resin acid, and a polycyclic diterpene having a carboxyl group and having 20 carbon atoms, such as abietic acid, dehydroabietic acid, and neoavietin. Rosin containing any one or more of acid, pimaric acid, isopimaric acid, and parastolic acid is exemplified.
In addition, the fatty acid or fatty acid amide can function as a peeling preventive and a lubricant.

In the second embodiment, the modified asphalt composition may contain a rubber component other than the hydrogenated block copolymer (hereinafter, also simply referred to as “other rubber component”).
Other rubber components are not limited to the following, but include, for example, natural rubber and synthetic rubber.
Examples of the synthetic rubber include, but are not limited to, polyisoprene rubber, polybutadiene rubber (BR), styrene butadiene rubber (SBR), modified styrene butadiene rubber (modified SBR), and styrene-butadiene-styrene block. Olefinic elastomers such as polymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butylene-butadiene-styrene copolymer (SBBS), ethylene propylene copolymer (EPDM); chloroprene Rubber, acrylic rubber, ethylene vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), nitrile butadiene rubber (NBR), and the like.

  Other rubber components include polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-butazine-styrene block copolymer, from the viewpoint of improving the compatibility of the modified asphalt composition and improving the peeling resistance of aggregate. , An ethylene-vinyl acetate copolymer is preferable, and a polybutadiene rubber and a styrene-butadiene-styrene block copolymer are more preferable.

Other rubber components may have a functional group.
From the viewpoint of improving the fluid resistance, it is preferable to use an olefin elastomer or an olefin elastomer having a functional group as the other rubber component.

When the other rubber component has a functional group, the functional group includes at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group. It preferably has a group.
As the other rubber components, only one type may be used alone, or two or more types may be used in combination.

In the second embodiment, the content of the rubber component other than the hydrogenated block copolymer in the modified asphalt composition is 0.5 to 400 when the hydrogenated block copolymer is 100 parts by mass. It is preferably 0.5 parts by mass, more preferably 0.5 parts by mass to 300 parts by mass, still more preferably 1 part by mass to 200 parts by mass, and even more preferably 5 parts by mass to 150 parts by mass.
By adjusting the content of the rubber component other than the hydrogenated block copolymer within the above range, the effect of improving the compatibility and the resistance to peeling of the aggregate of the modified asphalt composition can be obtained more reliably.

In the second embodiment, the modified asphalt composition may contain a resin component other than the hydrogenated block copolymer (hereinafter, also simply referred to as “other resin components”).
Examples of the resin component other than the hydrogenated block copolymer include, but are not limited to, polyethylene (PE), low-density polyethylene (low-density PE), polyvinyl chloride (PVC), and polyamide (PA). , Polystyrene (PS), acrylic resin, polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinylidene fluoride (PVDF), Teflon (registered trademark) (PTFE), polyetheretherketone (PEEK) And thermoplastic resins such as polyphenylene sulfide (PPS), polyimide (PI), and polyamide imide (PAI).

  As the resin component other than the hydrogenated block copolymer, polyethylene (PE), low-density polyethylene (low-density PE), and the like, from the viewpoint of improving the compatibility of the modified asphalt composition and improving the peeling resistance of aggregate, Polyvinyl chloride (PVC) and polyamide (PA) are more preferred.

Resin components other than the hydrogenated block copolymer may have a functional group. When the resin component has a functional group, the functional group includes at least one functional group selected from the group consisting of a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group. It is preferred to have.
As the resin component other than the hydrogenated block copolymer, only one type may be used alone, or two or more types may be used in combination.

In the second embodiment, the content of the resin component other than the hydrogenated block copolymer in the modified asphalt composition is 0.5 to 400 when the above-described hydrogenated block copolymer is 100 parts by mass. It is preferably 0.5 parts by mass, more preferably 0.5 parts by mass to 300 parts by mass, still more preferably 1 part by mass to 200 parts by mass, and even more preferably 5 parts by mass to 150 parts by mass.
By setting the content of the resin component other than the hydrogenated block copolymer in the above range, the effect of improving the compatibility and the peeling resistance of the aggregate asphalt of the modified asphalt composition can be obtained more reliably.

In the second embodiment, the modified asphalt composition contains, as another resin component, a polymer mainly composed of a vinyl aromatic monomer unit having a weight average molecular weight (Mw) of 5,000 to 30,000 (hereinafter, referred to as a polymer). "Low molecular weight vinyl aromatic polymer").
The low-molecular-weight vinyl aromatic polymer is preferably mainly composed of vinyl aromatic monomer units contained in the polymer block (A) of the hydrogenated block copolymer of the present embodiment, and is derived from polystyrene. It is more preferable that the monomer unit is mainly used.

In the second embodiment, from the viewpoint of reducing the viscosity of the modified asphalt composition, the lower limit of the content of the low molecular weight vinyl aromatic polymer is 0.5 to 100 parts by mass of the hydrogenated block copolymer. It is preferably at least 1.0 part by mass, more preferably at least 2.0 parts by mass, even more preferably at least 3.0 parts by mass.
Further, the upper limit of the content of the low-molecular-weight vinyl aromatic polymer is preferably 5.0 parts by mass or less based on 100 parts by mass of the hydrogenated block copolymer from the viewpoint of a low softening point of the modified asphalt composition. 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less.

  The method for preparing the low-molecular-weight vinyl aromatic polymer has been described in the first embodiment, and the description is omitted here.

(Production method of modified asphalt composition)
In the second embodiment, the modified asphalt composition can be produced by mixing 1 part by mass or more and 20 parts by mass or less of the hydrogenated block copolymer described above with 100 parts by mass of asphalt.

The mixing method is not particularly limited, and the mixing can be performed using an arbitrary mixer.
Examples of the mixer include, but are not limited to, an extruder, a kneader, a melt kneader such as a Banbury mixer, a vertical impeller, a stirrer such as a side arm impeller, a homogenizer including an emulsifier, and a pump. Is mentioned.

  In the production process of the modified asphalt composition, the asphalt, the hydrogenated block copolymer of the present embodiment, and optionally the additives may be mixed in a range of 140 ° C. to 220 ° C. using a stirring tank or the like. preferable.

(Modified asphalt mixture)
The modified asphalt mixture of the present embodiment includes the modified asphalt composition and the aggregate in the second embodiment described above.

Examples of the aggregate include, but are not limited to, aggregates for pavement described in “Asphalt Pavement Outlines” issued by the Japan Road Association.
Examples of the aggregate include, but are not limited to, crushed stone, cobblestone, gravel, steel slag, and the like. Asphalt-coated aggregates obtained by coating these aggregates with asphalt, recycled aggregates, and the like can also be used.
In addition, similar granular materials, artificially fired aggregates, fired expanded aggregates, artificial lightweight aggregates, ceramic particles, loxovites, aluminum particles, plastic particles, ceramics, emery, construction waste materials, fibers, etc. can also be used. .

  Aggregates are generally broadly classified into coarse aggregates, fine aggregates, and fillers.

Coarse aggregate is aggregate that stays on a 2.36 mm sieve, and is generally No. 7 crushed stone having a particle size range of 2.5 to 5 mm, No. 6 crushed stone having a particle size range of 5 to 13 mm, and particle size range of 13 to 20 mm. No. 5 crushed stone, and further, No. 4 crushed stone having a particle size range of 20 to 30 mm.
In the modified asphalt mixture of the present embodiment, an aggregate obtained by mixing one or more of these 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 mass of straight asphalt based on the aggregates.

  Fine aggregate refers to aggregate passing through a 2.36 mm sieve and stopping at a 0.075 mm sieve, and is not limited to, for example, river sand, hill sand, mountain sand, sea sand, Examples include screenings, crushed stone dust, silica sand, artificial sand, glass cullet, foundry sand, and crushed sand of recycled aggregate.

Fillers are aggregates that pass through a 0.075 mm sieve, and are not limited to the following. For example, fillers of screenings, stone powder, slaked lime, cement, incinerator ash, clay, talc, fly Ash, carbon black and the like.
In addition to these, as fillers, rubber powder, cork powder, wood powder, resin powder, fiber powder, pulp, artificial aggregate, etc., as long as they pass through a 0.075 mm sieve Can be used.

  As the coarse aggregate, the fine aggregate, or the filler, only one type may be used alone, or two or more types may be used in combination.

The modified asphalt mixture of the present embodiment can be manufactured by mixing at least the modified asphalt composition of the present embodiment and an aggregate.
The mixing method is not particularly limited, and a conventionally known mixing method can be applied.

  The mixing temperature of the modified asphalt composition and the aggregate is preferably in the range of 120 ° C or more and 200 ° C or less.

  The content of the aggregate in the modified asphalt mixture is preferably in the range of 85% by mass or more and 98% by mass or less, from the viewpoint of obtaining an asphalt mixture having a high mass loss resistance upon oil attachment and a high strength reduction. The content is more preferably from 97% by mass to 97% by mass.

  Further, as a method of producing a modified asphalt mixture, when asphalt and aggregate are mixed, a so-called plant mix method in which the hydrogenated block copolymer in the present embodiment is directly mixed to modify the asphalt, Can also be used.

(Method of using modified asphalt composition and modified asphalt mixture)
The modified asphalt mixture of the present embodiment has a D.I. Edited by Whiteoak and published by Shell Bitumen U.S.A. K. For the various applications described in The Shell Bitumen Handbook, published in the United Kingdom in 1990.
Other applications include tarpaulins, roof coatings, primer adhesives for tarpaulins, sealing binders for paving, adhesives for reclaimed asphalt pavement, cold prepared asphalt concrete, and for cold prepared asphalt concrete. Includes binders, fiberglass mat binders, slip coats for concrete, protective coats for concrete, sealing of cracks in pipelines and iron parts, and the like.

  Pavement forms using the modified asphalt mixture of this embodiment include, but are not limited to, dense-grain pavement, drainage pavement, permeable pavement, dense-gap gap asphalt pavement, crushed mastic asphalt pavement, color pavement, semi-flexible Pavement, water-retentive pavement, and thin-layer pavement.

  The method for producing the modified asphalt mixture for obtaining each pavement form is not limited to the following, and examples thereof include a hot method, a medium temperature method, and a normal temperature method.

From the viewpoint of improving flow resistance and slip resistance, the modified asphalt mixture used for dense-grain pavement has a coarse aggregate of 40 to 55% by mass and a fine aggregate of 40 to 55%, with the total amount of aggregate being 100% by mass. It is preferable to contain 55% by mass and 3 to 10% by mass of a filler.
The modified asphalt mixture used for the dense-grain pavement preferably has the modified asphalt composition in an amount of 5 to 7 parts by mass with respect to 100 parts by mass of the aggregate. Moreover, it is preferable that content of the hydrogenated block copolymer in this embodiment is 3-5.5 mass parts with respect to 100 mass parts of asphalts.

From the viewpoint of improving drainage, visibility, and noise, the modified asphalt mixture used for drainage pavement has a coarse aggregate of 60 to 85% by mass, a fine aggregate of 5 to 5%, with the total amount of aggregate being 100% by mass. It is preferable to contain 20% by mass and 3 to 20% by mass of a filler.
The modified asphalt mixture used for drainage pavement preferably contains 4 to 6 parts by mass of the modified asphalt composition with respect to 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer in the present embodiment is preferably 5 to 10 parts by mass with respect to 100 parts by mass of asphalt.

From the viewpoint of improving the water permeability, the modified asphalt mixture used for the water-permeable pavement has a coarse aggregate of 60 to 85% by mass, a fine aggregate of 5 to 20% by mass, and a filler of 100% by mass as a total amount of the aggregate. It is preferable to contain 3 to 20% by mass.
The modified asphalt mixture used for the water-permeable pavement preferably has 4 to 6 parts by mass of the modified asphalt composition with respect to 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer in this embodiment is preferably more than 0 to 6 parts by mass with respect to 100 parts by mass of asphalt.

From the viewpoint of improving abrasion, flow resistance, durability, and slip resistance, the modified asphalt mixture used for the dense-gap gap pavement has a coarse aggregate of 50 to 60% by mass with the total amount of the aggregate being 100% by mass. And 30 to 40% by mass of fine aggregate and 3 to 10% by mass of a filler.
The modified asphalt mixture used for the dense-gap gap pavement preferably has a modified asphalt composition in an amount of 4.5 to 6 parts by mass with respect to 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer in the present embodiment is preferably 5 to 12 parts by mass with respect to 100 parts by mass of asphalt.

From the viewpoints of abrasion, water impermeability, stress relaxation, flow resistance, and noise, the modified asphalt mixture used for the crushed mastic asphalt pavement has a total aggregate of 100% by mass and a coarse aggregate of 55 to 70%. It is preferable to contain 5% by mass, 15-30% by mass of fine aggregate and 5-15% by mass of filler.
The modified asphalt mixture used for the crushed stone mastic asphalt pavement preferably has a modified asphalt composition in an amount of 5.5 to 8 parts by mass with respect to 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer of the present embodiment is preferably 4 to 10 parts by mass with respect to 100 parts by mass of asphalt.

From the viewpoint of improving the scenery and visibility, the asphalt mixture used for the color pavement has a coarse aggregate (colored aggregate) of 40 to 55% by mass and a fine aggregate (colored bone) with the total amount of the aggregate being 100% by mass. Material), and preferably contains 3 to 10% by mass of a filler (pigment).
The modified asphalt mixture used for color pavement is 5 to 7 parts by mass of petroleum resin and 4 to 20 parts by mass of the hydrogenated block copolymer in the present embodiment, based on 100 parts by mass of aggregate. Is preferred.

From the viewpoints of visibility, oil resistance, and flow resistance, the modified asphalt mixture used for semi-flexible pavement has a coarse aggregate of 60 to 85% by mass and a fine aggregate of 5 to 5%, with the total amount of aggregate being 100% by mass. It is preferable to contain 20% by mass and 3 to 20% by mass of a filler. The modified asphalt mixture used for the semi-flexible pavement preferably has the modified asphalt composition in an amount of 4 to 6 parts by mass with respect to 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer in the present embodiment is preferably 4 to 10 parts by mass with respect to 100 parts by mass of asphalt.
Further, the modified asphalt mixture used for semi-flexible pavement preferably has a porosity of about 15 to 20%, and preferably has a void filled with a cement mortar.

From the viewpoint of suppressing the increase in the pavement temperature and improving the water retention, the modified asphalt mixture used for the water retention pavement has a total amount of the aggregate of 100% by mass, a coarse aggregate of 60 to 85% by mass, and a fine aggregate of 5%. -20% by mass and 3-20% by mass of a filler.
The modified asphalt mixture used for the water-retentive pavement preferably has 4 to 6 parts by mass of the modified asphalt composition based on 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer in the present embodiment is preferably 4 to 10 parts by mass with respect to 100 parts by mass of asphalt.
The modified asphalt mixture used for the water-retentive pavement preferably has a porosity of about 15 to 20%, and the pores are preferably filled with a cement-based or gypsum-based water retention material.

From the viewpoints of economy, shortening of construction period, and workability, the modified asphalt mixture used for thin-layer pavement is composed of coarse aggregate 60 to 85% by mass and fine aggregate 5 to 20 with the total amount of aggregate being 100% by mass. It is preferable to contain 3% to 20% by mass of a filler.
The modified asphalt mixture used for thin layer pavement preferably has a modified asphalt composition in an amount of 4 to 6.5 parts by mass based on 100 parts by mass of the aggregate. Further, the content of the hydrogenated block copolymer in the present embodiment is preferably 4 to 8 parts by mass with respect to 100 parts by mass of asphalt.
In the modified asphalt mixture used for the thin-layer pavement, the coarse aggregate is preferably No. 7 crushed stone having a particle size range of 2.5 to 5 mm.

  Hereinafter, the present embodiment will be described specifically with reference to examples and comparative examples, but the present embodiment is not limited to the following examples.

〔Measuring method〕
(Measurement of average vinyl content of hydrogenated block copolymer and hydrogenation rate of conjugated diene monomer unit)
The average vinyl content in the hydrogenated block copolymer and the hydrogenation rate of the conjugated diene monomer unit were measured by nuclear magnetic resonance spectrum analysis (NMR) under the following conditions.
In addition, the maximum value of the vinyl content before hydrogenation of the first to sixth regions having the same mass in the polymer block (B) containing the conjugated diene monomer unit constituting the hydrogenated block copolymer. Where _{VH is} the minimum value and _VL is the minimum value, Δvinyl content = _VH − _VL , and the average vinyl content is the average value of the vinyl content in the first to sixth regions.
The vinyl content before hydrogenation was measured using an infrared spectrophotometer (FT / IR-230: manufactured by JASCO Corporation).

By adding a large amount of methanol to the reaction solution containing the block copolymer before the hydrogenation reaction, the block copolymer was precipitated and recovered. Next, this block copolymer was extracted with acetone, and the block copolymer was dried under vacuum. Using this as a sample for ¹ H-NMR measurement, the average vinyl content was measured.

A large amount of methanol was added to the reaction solution containing the hydrogenated block copolymer after the hydrogenation reaction to precipitate and recover the hydrogenated block copolymer. Next, the hydrogenated block copolymer was extracted with acetone, and the hydrogenated block copolymer was dried under vacuum. Using this as a sample for ¹ H-NMR measurement, the hydrogenation rate was measured.

The conditions for ¹ H-NMR measurement are described below.
Measuring equipment: JNM-LA400 (manufactured by JEOL)
Solvent: deuterated chloroform Measurement sample: sampled before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift standard: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Scanning times: 64 Pulse width: 45 °
Measurement temperature: 26 ° C

(MFR)
Using a hydrogenated block copolymer, a melt indexer (L247: TECHNOL SEVENTO., LTD.) Was used to calculate by a method according to JIS K7210.
The conditions were as follows: the test temperature was 200 ° C., the test load was 5.00 kgf, and the unit of the measured value was g / 10 minutes.

(Measurement of content of vinyl aromatic monomer unit in hydrogenated block copolymer)
A certain amount of the hydrogenated block copolymer is dissolved in chloroform, and the absorption wavelength (attributable to the vinyl aromatic compound component (styrene) in the solution is measured using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation). 262 nm). From the obtained peak intensity, the content of the vinyl aromatic monomer unit (styrene) was calculated using a calibration curve.

(Measurement of content of polymer block mainly composed of vinyl aromatic monomer units in hydrogenated block copolymer)
I. M. Kolthoff, et al. , J. et al. Polym. Sci. , 1946, Vol. 1, p. 429, the content of the polymer block mainly composed of vinyl aromatic monomer units was measured using the following polymer decomposition solution.
Here, the “polymer block mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer” refers to the “conjugated diene monomer unit” contained in the hydrogenated block copolymer. The polymer block containing a vinyl aromatic monomer unit in the “polymer block containing (B)” is not included, and only the “polymer block (A) mainly containing a vinyl aromatic monomer unit” is used. means.
Measurement sample: Sample extracted from the reaction solution containing the block copolymer before hydrogenation of the hydrogenated block copolymer Polymer decomposition solution: A solution obtained by dissolving 0.1 g of osmium tetroxide in 125 mL of tertiary butanol

(Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) of hydrogenated block copolymer)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the hydrogenated block copolymer are determined by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from measurement of commercially available standard polystyrene. And the molecular weight of the peak in the chromatogram. The measurement software used was HLC-8320 EcoSEC collection, and the analysis software used was HLC-8320 analysis. The molecular weight distribution was determined as a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
The measurement conditions are shown below.
GPC; HLC-8320GPC (manufactured by Tosoh Corporation)
Detector; RI
Detection sensitivity: 3 mV / min Sampling pitch: 600 msec
Column: 4 TSKgel superHZM-N (6 mm ID × 15 cm) (manufactured by Tosoh Corporation)
Solvent; THF
Flow rate: 0.6 mm / min Concentration: 0.5 mg / mL
Column temperature; 40 ° C
Injection volume: 20 μL

(Peak temperature and peak height of loss tangent (tan δ))
The dynamic viscoelastic spectrum of the hydrogenated block copolymer was measured by the following method, and the peak temperature and peak height of the loss tangent (tan δ) were determined.
As a device, a torsion type geometry of ARES (trade name, manufactured by TA Instruments Co., Ltd.) was used.
The shape of the measurement sample was 2 mm in thickness, 10 mm in width, and 20 mm in length.
The measurement conditions were as follows: strain (initial strain) 0.5%, frequency 1 Hz, measurement range from -100 ° C to 100 ° C, and heating rate 3 ° C / min.

[Production Example 1 of hydrogenated block copolymer]
The hydrogenated block copolymers (P1) to (P4) for producing the adhesive composition and the adhesive tape were produced as follows.
(Production of hydrogenation catalyst)
First, a hydrogenation catalyst was produced as follows.
1 L of dried and purified cyclohexane was placed in a nitrogen-purged reaction vessel, 100 mmol of bis (cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. The reaction was carried out at room temperature for about 3 days to produce a hydrogenation catalyst.

(Production of hydrogenated block copolymer (P1))
A predetermined amount of cyclohexane was charged into a jacketed tank reactor, and the temperature in the reactor was adjusted to 50 ° C.
Thereafter, n-butyllithium was added from the bottom of the reactor so that n-butyllithium was 0.14 parts by mass with respect to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). Was added.
Further, cyclohexane of N, N, N ', N'-tetramethylethylenediamine is added so that N, N, N', N'-tetramethylethylenediamine is 0.27 mol per 1 mol of n-butyllithium. The solution was added.

Thereafter, as a polymerization reaction in the first step, a cyclohexane solution (styrene monomer concentration: 15% by mass) containing 15 parts by mass of a styrene monomer was supplied over about 10 minutes.
After stopping the supply of the styrene monomer, the reaction was continued for 15 minutes.
The internal temperature of the reactor at the end of the first step was 55 ° C.
The temperature was not adjusted and the internal temperature was raised by the heat of reaction.

Next, as a polymerization reaction in the second step, a cyclohexane solution (butadiene monomer concentration: 15% by mass) containing 85 parts by mass of a butadiene monomer was continuously supplied to the reactor at a constant rate over 50 minutes.
After stopping the supply of the butadiene monomer, the reaction was continued for 10 minutes while adjusting the temperature in the reactor to 50 ° C. to obtain a polystyrene-polybutadiene block copolymer.
The internal temperature of the reactor at the end of the second step was 84 ° C.
During the polymerization, the temperature was not adjusted and the internal temperature was raised by the heat of reaction.

  In the obtained polystyrene-polybutadiene block copolymer, the content of the vinyl aromatic monomer unit and the content of the block mainly composed of the vinyl aromatic monomer unit (polystyrene block) were both 15% by mass. The vinyl content of the conjugated diene monomer unit (vinyl content in butadiene) was 34 mol%, and the weight average molecular weight (hereinafter, also simply referred to as “Mw”) was 90000.

  A part of the obtained polystyrene-polybutadiene block copolymer was withdrawn, and tetraethoxysilane was added as a coupling agent so that the molar ratio to the total number of moles of n-butyllithium was 0.1, and the coupling reaction was performed for 10 minutes. Then, a coupling polymer was obtained.

Thereafter, using the hydrogenation catalyst, the obtained coupling polymer was hydrogenated at 80 ° C. to obtain a hydrogenated block copolymer (P1).
After the completion of the reaction, 0.25 parts by mass of a stabilizer (octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) is added to 100 parts by mass of the hydrogenated block copolymer (P1). Was added.
The hydrogenation rate of the hydrogenated block copolymer (P1) was 40 mol%, the MFR (200 ° C., 5 kgf) was 2.0 g / 10 min, and the Δvinyl content in the butadiene block: (V _H −V _L) ) Was 5.0 mol%.

The structure and composition of the hydrogenated block copolymer (P1)
(S-B): 65% by mass, Mw 90000
(SB) ₂ -X: 4% by mass, Mw 180000
(SB) ₃ -X: 8% by mass, Mw 270000
(S-B) _4- X: 23% by mass, Mw 360000
(In the formula, S represents a styrene block, B represents a butadiene block, and X represents a residue of a coupling agent. The same applies hereinafter.)

(Production of hydrogenated block copolymer (P2))
Except that N, N, N ', N'-tetramethylethylenediamine was 0.35 mol with respect to 1 mol of n-butyllithium, a method similar to that of the block copolymer (P1) was used. A hydrogenated block copolymer (P2) was produced.

The hydrogenation rate of the hydrogenated block copolymer (P2) is 38 mol%, the MFR (200 ° C., 5 kgf) is 5.0 g / 10 min, and the Δvinyl content in the butadiene block: (V _H −V _L ) is 6.0 mol%.

The structure and composition of the hydrogenated block copolymer (P2) are as follows:
(S-B): 64% by mass, Mw 90000
(SB) ₂ -X: 6% by mass, Mw 180000
(SB) ₃ -X: 15% by mass, Mw 270000
(S-B) _4- X: 15% by mass, Mw 360000
Met.

(Production of hydrogenated block copolymer (P3))
With respect to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), 0.16 parts by mass of n-butyllithium was used, and N, N, N ', N'-tetramethylethylenediamine was n- Except for adjusting the temperature to 0.40 mol with respect to 1 mol of butyllithium and adjusting the temperature in the reactor to 75 ° C. throughout the first to third polymerization steps, the block share A hydrogenated block copolymer (P3) was produced in the same manner as for the polymer (P1).

The hydrogenation rate of the hydrogenated block copolymer (P3) is 51 mol%, the MFR (200 ° C., 5 kgf) is 1.0 g / 10 min, and the Δvinyl content in the butadiene block: (V _H −V _L ) is It was 0 mol%.

The structure and composition of the hydrogenated block copolymer (P3)
(S-B): 65% by mass, Mw 75000
(SB) ₂ -X: 5% by mass, Mw 150000
(SB) ₃ -X: 18% by mass, Mw 225000
(S-B) _4- X: 12% by mass, Mw 300000
Met.

(Production of hydrogenated block copolymer (P4))
Except that N, N, N ', N'-tetramethylethylenediamine was set to 0.80 mol with respect to 1 mol of n-butyllithium, and the internal temperature of the reactor at the start of polymerization was set to 45 ° C. A hydrogenated block copolymer (P4) was produced in the same manner as in the block copolymer (P1).

The hydrogenation rate of the hydrogenated block copolymer (P4) was 61 mol%, the MFR (200 ° C., 5 kgf) was 1.0 g / 10 min, and the Δvinyl content in the butadiene block was (V _H −V _L ) 31.0 mol%.

The structure and composition of the hydrogenated block copolymer (P4) are as follows:
(S-B): 64% by mass, Mw 90000
(SB) ₂ -X: 7% by mass, Mw 180000
(SB) ₃ -X: 21% by mass, Mw 270000
(SB) ₄ -X: 8% by mass, Mw 360000
Met.

  Table 1 shows the analysis results of the hydrogenated block copolymers (P1) to (P4).

(Production Example of Adhesive Composition)
Using the hydrogenated block copolymers (P1) to (P4) produced as described above, an adhesive composition was produced as follows.
The following materials were used in addition to the hydrogenated block copolymers (P1) to (P4).

Block polymer (SBS): D1102 (manufactured by Kraton, polystyrene block content 29% by mass, diblock content 17% by mass)
Block polymer (SIS): Quintac 3433N (manufactured by Zeon Corporation, polystyrene block content 16% by mass, diblock content 56% by mass)
Tackifying resin (b1): Quintone R100 (manufactured by ZEON CORPORATION, 99% or more of polymer of hydrocarbon fraction of C4 to C5, softening point 96 ° C, aliphatic tackifying resin)
Tackifying resin (b2): Alcon M100 (Arakawa Chemical Industries, softening point 100 ° C, hydrogenated aromatic tackifying resin)
Oil (c1): Diana Process Oil PW-90 (Idemitsu Kosan Co., Ltd., paraffin oil)
Oil (c2): Diana Process Oil NS-90S (Naphthenic oil manufactured by Idemitsu Kosan Co., Ltd.)
Antioxidant: Irganox 1010 (BASF, phenolic antioxidant)

  With the composition shown in Table 2, the hydrogenated block copolymer, tackifier resin, oil, and antioxidant were stirred at a rotation speed of 500 rpm using a homogenizer (LART (trade name, manufactured by SILVERSON)). While heating to 170 ° C., the mixture was mixed with a propeller to produce the adhesive compositions of Examples 1 to 5 and Comparative Examples 1 and 2.

[Production example of adhesive tape]
The melted adhesive composition was cooled to room temperature, dissolved in toluene, and coated with an applicator on a transparent polyethylene terephthalate (PET) film having a thickness of 50 μm as a substrate.
Thereafter, toluene is completely evaporated at room temperature for 30 minutes and in a 70 ° C. oven for 7 minutes, and a 30 μm-thick adhesive composition having a 30 μm-thick adhesive composition is coated on a 50 μm-thick transparent PET film as a substrate. An adhesive tape was prepared.

(Evaluation method of adhesive composition)
The evaluation methods of the adhesive compositions of Examples 1 to 5 and Comparative Examples 1 and 2 are shown below.

(Dissolution time of the adhesive composition)
When each material was stirred by the method described in the above “[Production Example of Adhesive Adhesive Composition]”, the time during which all the materials were uniformly dissolved from the start of stirring was visually measured.
The shorter the stirring time, the better the productivity of the adhesive composition.
◎, ○, △, × were assigned in order from the best one.
Time to dissolution less than 80 minutes: ◎
80 minutes or more and less than 90 minutes: ○
90 minutes or more and less than 110 minutes: △
110 minutes or more: ×

(Tackiness of adhesive composition)
J. Dow [Proc. Inst. Rub. Ind. , 1.105 (1954)], on a slope on a glass plate having an inclination of 30 degrees, a sticky tape cut to a length of 10 cm, manufactured by the method described in the above-mentioned "[Production example of sticky adhesive tape]". An adhesive tape was attached with the adhesive layer side facing upward.
Roll 32 stainless steel balls of 1/32 inch to 1 inch in diameter from an upper position of 10 cm along the slope from the upper end of the adhesive tape at an initial speed of 0. The size of the largest diameter sphere that stopped at was measured.
The ball tackiness was evaluated according to the following evaluation criteria based on the size of the sphere.
In the evaluation, if the size of the sphere having the largest diameter stopped on the pressure-sensitive adhesive tape was larger than 7/32 inches, it was judged that the composition could be used as a pressure-sensitive adhesive composition without any practical problem, and was evaluated as ○.
When the size of the largest diameter sphere stopping on the adhesive tape was larger than 4/32 inches and smaller than 7/32 inches, it was evaluated as Δ.
When the size of the sphere having the largest diameter stopped on the adhesive tape was 4/32 inches or less, it was evaluated as x.
7/32 inch <Ball size: ○
4/32 inch <ball size ≦ 7/32 inch:
Ball size ≤ 4/32 inch ： ×

(Evaluation of adhesive strength of adhesive composition)
Method 1 for measuring peel strength according to JIS Z0237 1: Measured according to the method for measuring 180 ° peel strength of a test plate.
First, the adhesive tape manufactured as described in “[Production Example of Adhesive Tape]” was cut into a width of 25 mm to prepare an adhesive tape sample having a width of 25 mm.
The adhesive tape sample was attached to a stainless steel plate, and the 180 ° peeling force was measured at a peeling speed of 300 mm / min.
Based on the obtained peeling force, the adhesive force of the adhesive composition was evaluated according to the following criteria.
The evaluation was ◎, △, Δ, and × from the best order.
If it was Δ or more, it was evaluated that it could be used as a pressure-sensitive adhesive composition without practical problems.
Peeling force (N / 10 mm) 9 or more: ◎
8 or more and less than 9: ○
6 or more and less than 8:
Less than 6: ×

(Evaluation of adhesive holding power of adhesive composition)
The adhesive tape manufactured as described in “[Production Example of Adhesive Tape]” was cut to prepare an adhesive tape sample having a length of 25 mm and a width of 15 mm.
The adhesive tape sample was stuck on the stainless steel plate, the stainless steel plate was made vertical, and a load of 1 kg was applied vertically downward at 50 ° C. to measure the time until the adhesive tape came off.
The adhesive holding power of the adhesive composition was evaluated according to the following criteria.
The evaluations were evaluated as ○, Δ, and × in descending order.
If it is Δ or more, it can be used as a pressure-sensitive adhesive composition without practical problems.
Adhesive holding power (min) 10 minutes or more: ○
5 minutes or more and less than 10 minutes:
Less than 5 minutes: ×

[Production Example 2 of hydrogenated block copolymer]
Hydrogenated block copolymers (P5) to (P18) and hydrogenated block copolymer (I) for producing a modified asphalt composition were produced as follows.
(Production of hydrogenation catalyst)
First, a hydrogenation catalyst was produced as follows.
Into a nitrogen-purged reaction vessel, 1 L of dried and purified cyclohexane is added, 100 mmol of bis (cyclopentadienyl) titanium dichloride is added, and an n-hexane solution containing 200 mmol of trimethylaluminum is added with sufficient stirring. The reaction was carried out at room temperature for about 3 days to obtain a hydrogenation catalyst.

(Hydrogenated block copolymer (P5))
Polymerization was carried out by the following method using a stirrer having an inner volume of 10 L and a tank-type reactor equipped with a jacket.
After putting 20 parts by mass of cyclohexane into the reactor and adjusting the temperature to 55 ° C., n-butyllithium was added to 0.070 parts by mass with respect to 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor). Parts by mass and 0.35 mol of TMEDA were added to 1 mol of n-butyllithium.

  As a first step, a cyclohexane solution (styrene monomer concentration: 20% by mass) containing 8 parts by mass of styrene as a monomer was added over about 3 minutes, and reacted for 20 minutes.

  As a second step, a cyclohexane solution containing 47 parts by mass of butadiene (butadiene monomer concentration: 20% by mass) and a cyclohexane solution containing 38 parts by mass of styrene (styrene monomer concentration: 22% by mass) are mixed for 20 minutes and 10 minutes, respectively. Then, the mixture was continuously supplied to the reactor at a constant rate, and then reacted for 30 minutes. The internal temperature of the reactor was 80 ° C.

  As a third step, a cyclohexane solution (styrene monomer concentration: 20% by mass) containing 7 parts by mass of styrene as a monomer was added over about 3 minutes, and reacted for 20 minutes to obtain a block copolymer.

  The block copolymer obtained in the third step was subjected to a hydrogenation reaction using the above hydrogenation catalyst to obtain a hydrogenated block copolymer (P5). After completion of the reaction, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to the mass of the hydrogenated block copolymer (P5). 0.3% by mass was added.

The hydrogenated block copolymer (P5) has a styrene content of 53% by mass, a polystyrene block content of 15% by mass, a hydrogenation ratio of a double bond in a conjugated diene monomer unit of 99% by mol, and a weight average molecular weight. Was 140,000, the tan δ peak temperature was −14 ° C., the tan δ peak height was 1.7, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 8.5 mol%. .

(Hydrogenated block copolymer (P6))
The temperature was 50 ° C., the addition amount of n-butyl lithium was 0.055 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 60 parts by mass, and the styrene monomer was added. The polymerization was carried out in the same manner as the hydrogenated block copolymer (P5), except that the addition amount was 21 parts by mass, the addition amount of the styrene monomer in the third step was 9 parts by mass, and the hydrogenation ratio was changed. A polymer (P6) was produced.

The hydrogenated block copolymer (P6) has a styrene content of 40% by mass, a polystyrene block content of 19% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 90% by mol, and a weight average molecular weight. Was 200,000, the tan δ peak temperature was −31 ° C., the tan δ peak height was 1.1, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 13.6 mol%. .

(Hydrogenated block copolymer (P7))
The addition amount of n-butyllithium was 0.055 parts by mass, the addition amount of the styrene monomer in the first step was 11 parts by mass, the addition amount of the butadiene monomer in the second step was 58 parts by mass, and the addition amount of the styrene monomer was 21 parts by mass. Parts, the addition amount of the styrene monomer in the third step is 10 parts by mass, and polymerization is performed in the same manner as the hydrogenated block copolymer (P5) except that the hydrogenation ratio is changed. Manufactured.

The styrene content of the hydrogenated block copolymer (P7) is 42% by mass, the polystyrene block content is 21% by mass, the hydrogenation ratio of the double bond in the conjugated diene monomer unit is 86 mol%, and the weight average molecular weight. Was 200,000, the tan δ peak temperature was −33 ° C., the tan δ peak height was 1.1, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 9.9 mol%. .

(Hydrogenated block copolymer (P8))
The addition amount of n-butyllithium is 0.055 parts by mass, the addition amount of the styrene monomer in the first step is 10 parts by mass, the addition amount of the butadiene monomer in the second step is 60 parts by mass, and the addition amount of the styrene monomer is 20 parts by mass. Parts, the polymerization amount is the same as the hydrogenated block copolymer (P5) except that the amount of the styrene monomer added in the third step is 10 parts by mass and the hydrogenation ratio is changed to produce a hydrogenated block copolymer (P8). did.

The hydrogenated block copolymer (P8) has a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a hydrogenation ratio of a double bond in a conjugated diene monomer unit of 66 mol%, and a weight average molecular weight. Was 200,000, the tan δ peak temperature was −33 ° C., the tan δ peak height was 1.2, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 9.3 mol%. .

(Hydrogenated block copolymer (P9))
The temperature was 50 ° C., the addition amount of n-butyl lithium was 0.055 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 60 parts by mass, and the styrene monomer was added. Polymerized in the same manner as the hydrogenated block copolymer (P5) except that the addition amount was 20 parts by mass, the addition amount of the styrene monomer in the third step was 10 parts by mass, and the hydrogenation rate was changed. (P9) was produced.

The hydrogenated block copolymer (P9) has a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 32 mol%, and a weight average molecular weight. Was 200,000, the tan δ peak temperature was −35 ° C., the tan δ peak height was 1.1, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 17.6 mol%. .

(Hydrogenated block copolymer (P10))
The addition amount of n-butyllithium was 0.055 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 50 parts by mass, and the addition amount of the styrene monomer was 30 parts by mass. Parts, the amount of the styrene monomer added in the third step is 10 parts by mass, and the polymerization is carried out in the same manner as the hydrogenated block copolymer (P5) except that the hydrogenation ratio is changed to produce a hydrogenated block copolymer (P10). did.

The hydrogenated block copolymer (P10) has a styrene content of 50% by mass, a polystyrene block content of 20% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 86 mol%, and a weight average molecular weight. Was 200,000, the tan δ peak temperature was −21 ° C., the tan δ peak height was 1.1, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 9.4 mol%. .

(Hydrogenated block copolymer (P11))
The temperature was 50 ° C., the addition amount of n-butyllithium was 0.065 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 60 parts by mass, and the styrene monomer was Polymerized in the same manner as the hydrogenated block copolymer (P5) except that the addition amount was 21 parts by mass, the addition amount of the styrene monomer in the third step was 9 parts by mass, and the hydrogenation rate was changed. (P11) was produced.

The hydrogenated block copolymer (P11) has a styrene content of 40% by mass, a polystyrene block content of 19% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 87 mol%, and a weight average molecular weight. Was 160,000, the tan δ peak temperature was −33 ° C., the tan δ peak height was 1.2, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 14.3 mol%. .

(Hydrogenated block copolymer (P12))
The addition amount of n-butyllithium was 0.055 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 58 parts by mass, and the addition amount of the styrene monomer was 23 parts by mass. Part, the addition amount of the styrene monomer in the third step is 9 parts by mass, and polymerization is performed in the same manner as the hydrogenated block copolymer (P5) except that the hydrogenation ratio is changed to produce a hydrogenated block copolymer (P12). did.

The styrene content of the hydrogenated block copolymer (P12) is 42% by mass, the polystyrene block content is 19% by mass, the hydrogenation rate of the double bond in the conjugated diene monomer unit is 99 mol%, and the weight average molecular weight. Was 200,000, the tan δ peak temperature was −30 ° C., the tan δ peak height was 1.2, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 9.0 mol%. .

(Hydrogenated block copolymer (P13))
The addition amount of n-butyllithium was 0.058 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 61 parts by mass, and the addition amount of the styrene monomer was 19 parts by mass. Parts, the amount of the styrene monomer added in the third step is 10 parts by mass, and after the third step, 1,3-dimethyl-2-imidazolidinone is adjusted to 0.95 mol with respect to 1 mol of n-butyllithium. The mixture was added and allowed to react for 25 minutes, and polymerized in the same manner as the hydrogenated block copolymer (P5) except for changing the hydrogenation rate, to produce a hydrogenated block copolymer (P13).

The hydrogenated block copolymer (P13) has a styrene content of 39% by mass, a polystyrene block content of 20% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 68 mol%, and a weight average molecular weight. Was 190,000, the tan δ peak temperature was -32 ° C, the tan δ peak height was 1.2, and the Δ vinyl content (V _H -V _L ) in the styrene-butadiene copolymer block was 12.7 mol%. .

(Hydrogenated block copolymer (P14))
The addition amount of n-butyllithium was 0.058 parts by mass, the addition amount of the styrene monomer in the first step was 10.5 parts by mass, the addition amount of the butadiene monomer in the second step was 29 parts by mass, and the addition amount of the styrene monomer was After the polymerization in the second step, 10.5 parts by mass, N, N, N ', N'-tetraglycidylmetaxylenediamine was added as a coupling agent in an amount of 1 mol per mol of n-butyllithium. Polymerization was carried out in the same manner as for the hydrogenated block copolymer (P5) except for changing the hydrogenation ratio, to produce a hydrogenated block copolymer (P14).

The hydrogenated block copolymer (P14) has a styrene content of 42% by mass, a polystyrene block content of 20% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 73 mol%, and a weight average molecular weight. Was 220,000, the tan δ peak temperature was −28 ° C., the tan δ peak height was 1.2, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 10.2 mol%. .
The mass ratio of the content of the hydrogenated block copolymer (a) / (d) was 80/20.
The hydrogenated block copolymer (a) means a hydrogenated block copolymer having a structure having two or more branches after coupling.
(D) means a structure composed of a styrene block (A) and a styrene / butadiene copolymer block (B) (structure before coupling).

(Hydrogenated block copolymer (P15))
The addition amount of n-butyllithium was 0.058 parts by mass, the addition amount of the styrene monomer in the first step was 13 parts by mass, the addition amount of the butadiene monomer in the second step was 57 parts by mass, and the addition amount of the styrene monomer was 17 parts by mass. Parts, the amount of the styrene monomer added in the third step is 13 parts by mass, and after the third step, the polymerization is performed in the same manner as the hydrogenated block copolymer (P5) except that the hydrogenation rate is changed. (P15) was produced.

The hydrogenated block copolymer (P15) has a styrene content of 43% by mass, a polystyrene block content of 26% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 83% by mol, and a weight average molecular weight. Was 190,000, the tan δ peak temperature was -37 ° C, the tan δ peak height was 1.1, and the Δ vinyl content (V _H -V _L ) in the styrene-butadiene copolymer block was 9.0 mol%. .

(Hydrogenated block copolymer (P16))
The addition amount of n-butyllithium was 0.058 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, the addition amount of the butadiene monomer in the second step was 59 parts by mass, and the addition amount of the styrene monomer was 22 parts by mass. 10 minutes after the end of the monomer supply, the temperature was adjusted so that the internal temperature of the reactor became 60 ° C., the amount of the styrene monomer added in the third step was 9 parts by mass, and after the third step, the hydrogenation rate was increased. The polymerization was carried out in the same manner as for the hydrogenated block copolymer (P5) except for changing the above, to produce a hydrogenated block copolymer (P16).

The hydrogenated block copolymer (P16) has a styrene content of 41% by mass, a polystyrene block content of 19% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 99% by mol, and a weight average molecular weight. Was 190,000, the tan δ peak temperature was −29 ° C., the tan δ peak height was 0.7, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 7.0 mol%. .

(Hydrogenated block copolymer (P17))
At a temperature of 45 ° C., 0.055 parts by mass of n-butyllithium was added, and 0.55 mol of TMEDA was added to 1 mol of n-butyllithium. The addition amount of the styrene monomer in the first step is 10 parts by mass, the addition amount of the butadiene monomer in the second step is 61 parts by mass, the addition amount of the styrene monomer is 19 parts by mass, and the addition amount of the styrene monomer in the third step is 10 parts by mass. After the third step, polymerization was carried out in the same manner as the hydrogenated block copolymer (P5) except that the hydrogenation ratio was changed, to produce a hydrogenated block copolymer (P17).

The hydrogenated block copolymer (P17) has a styrene content of 39% by mass, a polystyrene block content of 20% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 89 mol%, and a weight average molecular weight. Was 200,000, the tan δ peak temperature was −32 ° C., the tan δ peak height was 1.1, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 30.1 mol%. .

(Hydrogenated block copolymer (P18))
The temperature was kept constant at 70 ° C. from the first step to the third step, the addition amount of n-butyllithium was 0.058 parts by mass, the addition amount of the styrene monomer in the first step was 10 parts by mass, and the butadiene monomer in the second step was Hydrogenated block copolymer except that the addition amount was 59 parts by mass, the addition amount of the styrene monomer was 22 parts by mass, the addition amount of the styrene monomer in the third step was 9 parts by mass, and the hydrogenation rate was changed after the third step. Polymerization was carried out in the same manner as in (P5) to produce a hydrogenated block copolymer (P18).

The hydrogenated block copolymer (P18) has a styrene content of 41% by mass, a polystyrene block content of 19% by mass, a hydrogenation rate of a double bond in a conjugated diene monomer unit of 86 mol%, and a weight average molecular weight. Was 190,000, the tan δ peak temperature was −30 ° C., the tan δ peak height was 1.0, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 2.4 mol%. .

(Block copolymer (I))
As the block copolymer (I), a styrene-butadiene-styrene block copolymer (D1101 manufactured by Kraton) was used. The styrene content of the block copolymer (I) is 30% by mass, the polystyrene block content is 29% by mass, the hydrogenation rate of the double bond in the conjugated diene monomer unit is 0 mol%, and the weight average molecular weight is 16%. The tan δ peak temperature was −75 ° C., the tan δ peak height was 1.0, and the Δ vinyl content (V _H −V _L ) in the styrene-butadiene copolymer block was 6.5 mol%.

  Table 3 below shows the analysis results of the block copolymers (P5) to (P18) and the block copolymer (I).

(Production Example of Modified Asphalt Composition)
(asphalt)
As the asphalt, the following two types of asphalts (a1) and (a2) were used.
The composition of each asphalt was analyzed by a measuring method based on JPI-5S-70-10, a petroleum test related standard of the Japan Petroleum Institute.
Asphalt (a1): The penetration is 80 to 100, and the asphalt composition has a saturated content of 8.5% by mass, an aromatic component of 47.4% by mass, a resin component of 20.8% by mass, and an asphaltene component of 23.3% by mass. Is straight asphalt.
Asphalt (a2): The penetration is 60 to 80, and the asphalt composition has a saturated content of 7.6 mass%, an aromatic content of 53.6 mass%, a resin content of 20.0 mass%, and an asphaltene content of 18.8 mass%. Is straight asphalt.

[ Reference Example 5, Examples 6 to 9, Reference Example 10, Examples 11 to 20 , 24, and Comparative Examples 3 to 5, 7, 8]
400 g of asphalt of the type shown in Tables 5 and 6 was placed in a 750 mL container, and
It was immersed in an oil bath at 80 ° C. to completely melt the asphalt.

Next, asphalt was homogenized (LART (SILVERSON), trade name)
), While stirring at a rotation speed of 3000 rpm, the hydrogenated block copolymers (P5) to (P18) or the block copolymer (I) obtained as described above were mixed with the following Table 5 and Table 6 was added in order.
When the addition is completed, the rotation speed is increased to 3500 rpm, and the mixture is kneaded for 1 hour to obtain Reference Example 5, Examples 6 to 9, Reference Example 10, Examples 11 to 20 , 24, and Comparative Examples 3 to 5, 7 , and 8. To obtain a modified asphalt composition.
Tables 5 and 6 show the physical properties of the obtained modified asphalt compositions.

[Examples 21 to 23 and Comparative Example 6]
400 g of asphalt of the type shown in Tables 5 and 6 was placed in a 750 mL container, and the container was immersed in an oil bath at 180 ° C. to completely melt the asphalt.

Next, while the asphalt was stirred using a homogenizer (LART (manufactured by SILVERSON, trade name)) at a rotation speed of 3000 rpm, the hydrogenated block copolymer obtained as described above was added to Tables 5 and 6. The composition was added in order.
When the addition is completed, the rotation speed is increased to 3500 rpm, and the mixture is kneaded for 1 hour. Thereafter, sulfur is added, and the mixture is further kneaded for 1 hour to obtain the modified asphalt compositions of Examples 21 to 23 and Comparative Example 6. Obtained.
Tables 5 and 6 show the physical properties of the obtained modified asphalt compositions.

(Production example of modified asphalt mixture)
[ Reference Example 5, Examples 6 to 9, Reference Example 10, Examples 11 to 24 , Comparative Examples 3 to 8]
A 27-liter capacity mixer equipped with a heating device is charged with a fine-grained aggregate 9 having a particle size shown in Table 4 below.
4.5 parts by mass were charged, and kneading was performed for 25 seconds.
Next, 5.5 parts by mass of the modified asphalt composition produced by the above method was charged into the above mixer, and the mixture was kneaded for 50 seconds, and Reference Example 5, Examples 6 to 9, Reference Examples 10, and Examples 11 to 11 were performed. 24 and the modified asphalt mixtures of Comparative Examples 3 to 8 were obtained.
The resulting modified asphalt mixture was a dense particle type modified asphalt mixture.
The total amount of the modified asphalt mixture was adjusted to 10 kg, and the mixing temperature was adjusted to 177 ° C. in both the empty kneading and the main kneading.
The aggregate used was a mixture of crushed stone and crushed sand from Iwafune-cho, Shimotsuga-gun, Tochigi prefecture, fine sand from Sakae-cho, Inba-gun, Chiba prefecture and stone powder from Yamasuga-machi, Sano city, Tochigi prefecture.
Table 4 below shows the particle size distribution of the aggregate used for the modified asphalt mixture.

(Evaluation method of modified asphalt composition and modified asphalt mixture)
The evaluation method for the modified asphalt composition and the modified asphalt mixture is as follows.

(Compatibility)
By measuring the average particle size of the hydrogenated block copolymer when producing the modified asphalt composition based on the above “[Production Example of Modified Asphalt Composition]”, the asphalt and hydrogenated block copolymer The compatibility of the polymer was evaluated. The average particle diameter was observed as follows using transmitted light by a digital microscope. In addition, the measuring device and the measuring conditions were as follows.
-Measuring device: Digital microscope VHX-2000 manufactured by KEYENCE
・ Measurement conditions Measurement temperature: 25 ℃
Magnification: 1000 × Measurement mode: Transmitted light Sample preparation method: From the modified asphalt composition being stirred, 10 mg of the modified asphalt composition is collected on a slide glass every 15 minutes, and placed on a hot plate heated to 180 ° C. For 20 seconds to melt. Thereafter, a cover glass was placed on the molten modified asphalt composition and spread thinly. After standing at room temperature for 30 minutes, observation was performed with a digital microscope. From the start of stirring, the production time when the dispersed particle diameter became 10 μm was measured. The shorter the production time, the better the compatibility. ◎, △, Δ, and × from the best order.
〔Evaluation criteria〕
Within 0.5 hours: ◎
More than 0.5 hours and less than 1.0 hour: ○
More than 1.0 hour and less than 2.0 hours: △
Over 2.0 hours: ×

(Low temperature elongation of modified asphalt composition)
According to JIS-K2207, the elongation of the modified asphalt composition produced by the above-mentioned production example of the modified asphalt composition was measured. A standard modified asphalt composition sample was pulled in water at 5 ° C. at a rate of 5 ° C./min, and the length (cm) until the sample was broken was measured. A longer length (cm) before breaking indicates higher low-temperature performance. ◎, △, Δ, and × from the best order.
30cm or more: ◎
20cm or more: ○
15cm or more: △
Less than 15cm: ×

(Heat aging resistance of modified asphalt composition during storage)
The modified asphalt composition produced according to the above-described modified asphalt composition production example was used as a test sample and allowed to stand in a gear oven set at 180 ° C. for 7 days.
The Brookfield-type melt viscosity at 140 ° C before and after standing in a gear oven was measured, and the rate of change (140 ° C melt viscosity after standing in a gear oven / 140 ° C melt viscosity before standing in a gear oven) was measured. I asked.
The smaller the change width of the Brookfield-type melt viscosity is, the smaller the molecular breakage (decrease in viscosity) and gelation (increase in viscosity) due to thermal degradation are, and the heat resistance is excellent.
◎, △, Δ, and × from the best order.
〔Evaluation criteria〕
0.9 or more and 1.3 or less: ◎
0.8 or more and less than 0.9, or more than 1.3 and less than 1.4: ○
0.7 or more and less than 0.8, or more than 1.4 and 1.5 or less: △
Less than 0.7 or greater than 1.5: ×

(Flow resistance of modified asphalt mixture)
The modified asphalt mixture produced according to the above-mentioned production example of the modified asphalt mixture was used as a test sample, and the test was carried out in accordance with Test Method Handbook B003.
A loaded small rubber wheel was repeatedly reciprocated at a specified temperature, a specified time, and a specified speed on a test piece having a predetermined size, and a dynamic stability (times / mm) was obtained from a deformation amount per unit time.
The higher the dynamic stability, the better the fluid resistance.
◎, △, Δ, and × from the best order.
〔Evaluation criteria〕
20,000 times / mm or more: ◎
Less than 20,000 times / mm 15,000 times / mm or more: ○
Less than 15000 times / mm 8000 times / mm or more: △
Less than 8000 times / mm: ×

The evaluation results of Reference Example 5, Examples 6 to 9, Reference Example 10, Examples 11 to 24 , and Comparative Examples 3 to 8 are summarized in Tables 5 and 6 below.

The hydrogenated block copolymer of the present invention has industrial applicability as a material for an adhesive composition, a modified asphalt composition, and a modified asphalt mixture.
The adhesive composition of the present invention includes various adhesive tapes / labels, pressure-sensitive thin plates, pressure-sensitive sheets, surface protection sheets / films, back glues for fixing various lightweight plastic molded products, back glues for carpet fixing, and tile fixing. There is industrial applicability as a material for backing paste, adhesives, sealing agents, masking agents for paint repainting operations, and sanitary articles.
The modified asphalt composition and the modified asphalt mixture of the present invention can be used for roads, tarpaulins, roof coatings, primer adhesives for tarpaulins, sealing binders for paving, adhesives for recycled asphalt pavement, low-temperature prepared asphalts. It has industrial applicability as a material in the field of binders for concrete, fiberglass mat binders, slip coats for concrete, protective coats for concrete, cracking of pipelines and iron parts.

Claims (12)

A hydrogenated block copolymer having a polymer block (A) mainly containing vinyl aromatic monomer units and a polymer block (B) containing conjugated diene monomer units,
The polymer block (B) is a polymer block (B1) mainly containing a conjugated diene monomer unit or a copolymer block (B2) containing a conjugated diene monomer unit and a vinyl aromatic monomer unit. Yes,
The polymer block (A) mainly containing the vinyl aromatic monomer unit contains at least 90% by mass of the vinyl aromatic monomer unit,
The polymer block (B1) mainly composed of the conjugated diene monomer unit contains 90% by mass or more of the conjugated diene monomer unit,
The copolymer block (B2) containing the conjugated diene monomer unit and the vinyl aromatic monomer unit contains 20% by mass or more and 50% by mass or less of the vinyl aromatic monomer unit,
The content of the vinyl aromatic monomer unit of the hydrogenated block copolymer is 10% by mass or more and 45% by mass or less,
In the polymer block (B), the first to sixth regions are set to have the same mass in order from the polymerization start terminal side, and the first to sixth regions have the maximum vinyl content before hydrogenation. A hydrogenated block copolymer having a value of _VH and a minimum value of _VL , wherein _VH - _VL = 5 mol% or more and 30 mol% or less. The hydrogenated block copolymer according to claim 1, wherein the hydrogenation rate of the hydrogenated block copolymer is 95 mol% or less based on the total number of moles of the conjugated diene monomer units. 3. The hydrogenated block copolymer according to claim 1, wherein the hydrogenation rate of the hydrogenated block copolymer is 10 mol% or more based on the total number of moles of the conjugated diene monomer units. 4. The hydrogenated block copolymer according to any one of claims 1 to 3 , wherein the hydrogenated block copolymer contains a hydrogenated block copolymer (r1) having a radial structure. 100 parts by mass of the hydrogenated block copolymer according to any one of claims 1 to 4 ,
20 parts by weight or more and 400 parts by weight or less of tackifying resin,
And a pressure-sensitive adhesive composition. An adhesive tape comprising the adhesive composition according to claim 5 . A label containing the adhesive composition according to claim 5 . The weight average molecular weight (Mw) of the hydrogenated block copolymer is 100,000 to 500,000.
The hydrogenated block copolymer according to any one of claims 1 to 3 . 9. The water according to claim 1, wherein a peak temperature of a loss tangent (tan δ) of the hydrogenated block copolymer measured by dynamic viscoelasticity is −50 ° C. or more and −5 ° C. or less. 10. Addition block copolymer. A peak temperature of a loss tangent (tan δ) measured by dynamic viscoelasticity measurement of the hydrogenated block copolymer is −50 ° C. or more and −5 ° C. or less;
The value of the peak height of the loss tangent (tan δ) in the range of −50 ° C. or more and −5 ° C. or less by dynamic viscoelasticity measurement of the hydrogenated block copolymer is more than 0.7 and not more than 1.6. The hydrogenated block copolymer according to any one of claims 1 to 3 , 8 , and 9 . For 100 parts by mass of asphalt,
A modified asphalt composition comprising 1 to 20 parts by mass of the hydrogenated block copolymer according to any one of claims 1 to 3 and 8 to 10 . A modified asphalt mixture comprising the modified asphalt composition according to claim 11 and an aggregate.