JP2019183124A - Additive for asphalt-containing waterproof sheet, manufacturing method of asphalt-containing waterproof sheet, asphalt composition, and asphalt-containing waterproof sheet - Google Patents

Abstract

To provide an additive for an asphalt-containing waterproof sheet low in mixing temperature during manufacturing, high in softening point, excellent in low viscosity, having high adhesiveness in an area from low temperature to high temperature, low in oil bleeding property, and providing an asphalt composition excellent in low temperature flexure property.SOLUTION: There is provided an additive for asphalt-containing waterproof sheet containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and an additive (A) having hydrogenation rate of a double bond contained in the conjugated diene monomer of 10 mol% to 85 mol%.SELECTED DRAWING: None

Description

  The present invention relates to an additive for asphalt-containing waterproof sheets, a method for producing an asphalt-containing waterproof sheet, an asphalt composition, and an asphalt-containing waterproof sheet.

Conventionally, asphalt compositions have been widely used in applications such as road pavement, waterproof sheets, sound insulation sheets, and roofing.
When the asphalt composition is used in various applications, many attempts have been made to add various polymers to the asphalt to improve its properties.
As the polymer, for example, a block copolymer having a conjugated diene monomer unit and a vinyl aromatic monomer unit is used.
In addition, in the construction of asphalt roofing and asphalt tarpaulin, in recent years, from the viewpoint of energy saving, environmental load reduction, work environment improvement, etc., a cooling method was adopted in which a roofing material with a self-adhesive layer on the back surface was attached to the base material. A lot of construction has been done.
As an asphalt composition in which a block copolymer as described above is added to asphalt, an asphalt composition to which block copolymers having various specific structures are added has been conventionally disclosed (for example, Patent Document 1). To 3).

JP-A-1-101371 JP 2006-299024 A JP 2001-164081 A

However, the techniques disclosed in Patent Documents 1 to 3 are still sufficient from the viewpoint of the balance of properties, such as a high softening point, excellent low viscosity, and high tackiness from low temperature to high temperature. However, further improvement is desired.
Further, the conventionally known asphalt composition also has a problem that when other compounding agents such as oil are added, bleeding occurs and the adhesiveness deteriorates with the passage of time.

Moreover, when constructing an asphalt waterproof sheet in winter, the waterproof sheet may be cracked in the process of sticking the rolled waterproof sheet while feeding it out.
Therefore, in order to improve the low-temperature bendability of the asphalt-containing waterproof sheet, the amount of oil added to the asphalt composition should be increased, or a styrene butadiene styrene copolymer with a hydrogenation rate of 0% should be added to the asphalt. However, problems such as oil bleed easily occur, and sufficient properties are not obtained in balance of physical properties, and further improvement is desired.

  Therefore, in the present invention, the mixing temperature during production is low, the softening point is high, the low viscosity is excellent, the adhesiveness is high in the low temperature to high temperature range, the oil bleeding property is low, and the low temperature bendability is excellent. It is an object to provide an additive for an asphalt-containing waterproof sheet from which an asphalt composition can be obtained.

As a result of intensive investigations to solve the above-described problems of the prior art, the inventors of the present invention have a low mixing temperature during production due to the asphalt-containing waterproof sheet additive containing a predetermined polymer having a specified molecular structure. The present invention has found that an asphalt composition having a high softening point, excellent low viscosity, high adhesiveness in a low temperature to high temperature region, low oil bleeding property and excellent low temperature bendability can be obtained. It came to complete.
That is, the present invention is as follows.

[1]
An additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein a hydrogenation rate of a double bond contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less. An additive for asphalt-containing waterproof sheets.
[2]
The additive (A) is an additive for an asphalt-containing waterproof sheet according to [1], wherein the content of the vinyl aromatic monomer unit is 20% by mass or more and 45% by mass or less.
[3]
The additive (A) contains the block copolymer (a) in an amount of 30% by mass to 95% by mass, the block copolymer (b) in an amount of 5% by mass to 70% by mass,
The block copolymer (a) contains a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units, and has a peak molecular weight of 30,000. A block copolymer of 150,000 or less and
The block copolymer (b) is a block copolymer containing a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units. ,
The ratio of the peak molecular weight of the block copolymer (b) to the peak molecular weight of the block copolymer (a) is 1.5 or more and less than 6.0.
The additive for asphalt-containing waterproof sheets according to [1] or [2].
[4]
The block copolymer (b) includes a block copolymer (b-2),
The ratio of the weight average molecular weight of the block copolymer (b-2) to the weight average molecular weight of the block copolymer (a) is 2.4 or more and less than 3.5.
The additive for asphalt-containing waterproof sheets according to [3].
[5]
The block copolymer (b) includes a block copolymer (b-3),
The ratio of the weight average molecular weight of the block copolymer (b-3) to the weight average molecular weight of the block copolymer (a) is 3.4 or more and less than 4.5.
The additive for asphalt-containing waterproof sheets according to [3] or [4].
[6]
An additive (B) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the hydrogenation rate of the double bond contained in the conjugated diene monomer unit is 0 mol%,
The additive for an asphalt-containing waterproof sheet according to any one of [1] to [5].
[7]
The additive (A) is
Having 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;
The additive for an asphalt-containing waterproof sheet according to any one of [1] to [6].
[8]
The additive (B) is
Having 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;
The additive for asphalt-containing waterproof sheets according to [6] or [7].
[9]
The asphalt-containing additive for waterproof sheet according to any one of [1] to [8], 5% by mass or more and 30% by mass or less,
3 to 30% by mass of a tackifier,
The softener is 2% by mass or more and 25% by mass or less,
Having a step of forming a layer of asphalt composition containing asphalt in an amount of 30% by mass to 90% by mass,
Manufacturing method of asphalt-containing waterproof sheet.
[10]
The additive for asphalt-containing waterproof sheets according to any one of [1] to [8], in an amount of 5% by mass to 30% by mass,
3 to 30% by mass of a tackifier,
The softener is 2% by mass or more and 25% by mass or less,
And asphalt, 30% by mass or more and 90% by mass or less,
An asphalt composition containing.
[11]
The asphalt composition according to [10], further including a rubber component and / or a resin component other than the additive for asphalt-containing waterproof sheets according to any one of [1] to [8].
[12]
An asphalt-containing waterproof sheet comprising the asphalt composition according to [10] or [11].

  According to the present invention, the mixing temperature during production is low, the softening point is high, the low viscosity is excellent, the adhesiveness is high in the low temperature to high temperature region, the oil bleeding property is low, and the low temperature bendability is excellent. It is possible to provide an additive for an asphalt-containing waterproof sheet from which an asphalt composition can be obtained.

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

[Additive for asphalt-containing waterproof sheet]
The additive for asphalt-containing waterproof sheets of the present embodiment,
An additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein a hydrogenation rate of a double bond contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less, contains.

  Here, additive (A) consists of a block copolymer, and the structural unit which comprises the said block copolymer is called "-monomer unit", and when describing as a polymer material, The “unit” is omitted, and simply described as “˜monomer”.

In the present specification, “mainly” means that the content of a predetermined monomer unit in the polymer block is 60% by mass or more, preferably 80% by mass or more, and more Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more.
Although there is no restriction | limiting in particular in an upper limit, It is preferable that it is 100 mass% or less, and it is preferable that it is 99 mass% or less.

(Structure of additive (A))
In the present embodiment, the additive (A) contains a block copolymer (a) and a block copolymer (b) described later from the viewpoint of high adhesiveness in the low temperature to high temperature region of the asphalt-containing waterproof sheet. Is preferred.
The block copolymer (a) is a low molecular weight component, and the block copolymer (b) is a high molecular weight component. For the expression of adhesiveness, it is important to balance the adherence of the asphalt composition to the adherend and the elastic force after application, but by adding both low and high molecular weight components together, From the viewpoint of easy adjustment so that the agent has a desired performance, it is a preferable embodiment to contain the block copolymers (a) and (b).
By increasing the ratio of the block copolymer (a) which is a low molecular weight component, the sticking property is improved, but the elastic force tends to be lowered. On the other hand, when the ratio of the block copolymer (b), which is a high molecular weight component, is increased, the sticking property is lowered, but the elastic force tends to be improved. In particular, the effect of sticking tends to be strong in the low temperature region, and the influence of elastic force tends to be strong in the high temperature region.

The block copolymer (b) as the high molecular weight component includes a predetermined block copolymer (b-2), and the block copolymer (b) with respect to the weight average molecular weight of the block copolymer (a). -2) The weight average molecular weight ratio is preferably 2.4 or more and less than 3.5, more preferably 2.5 or more and less than 3.4, and more preferably 2.6 or more and less than 3.3. More preferably.
It is preferable that content of the said block copolymer (b-2) is the range of 15-80 mass% in a block copolymer (b).
When the block copolymer (b) contains the block copolymer (b-2), there is obtained an effect that the characteristic balance between the high softening point and the low viscosity of the asphalt composition is excellent. It is done.

The block copolymer (b) as the high molecular weight component contains a predetermined block copolymer (b-3), and the block copolymer (b) with respect to the weight average molecular weight of the block copolymer (a). The ratio of the weight average molecular weight of -3) is preferably 3.4 or more and less than 4.5, more preferably 3.4 or more and less than 4.4, and more preferably 3.4 or more and less than 4.3. More preferably.
It is preferable that content of the said block copolymer (b-3) is the range of 15-80 mass% in a block copolymer (b).
The block copolymer (b) contains the block copolymer (b-3), thereby obtaining an effect that the characteristic balance between the high softening point and the low viscosity of the asphalt composition is excellent. It is done.

The block copolymer (a), which is a low molecular weight component contained in the additive (A), is mainly composed of a polymer block mainly composed of vinyl aromatic monomer units and a conjugated diene monomer unit. A block copolymer containing a polymer block and having a peak molecular weight of 30,000 to 150,000, and a block copolymer (b) which is a high molecular weight component contained in the additive (A) is vinyl. It contains a polymer block mainly composed of aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units.
From the viewpoint of the high softening point and low viscosity of the asphalt composition of the present embodiment, the peak molecular weight of the block copolymer (b) is 1.5 times or more the peak molecular weight of the block copolymer (a). It is less than 0 times, preferably 1.7 times or more and 5.0 times or less, and more preferably 1.8 times or more and 4.5 times or less.
The peak molecular weights of the block copolymer (a) and the block copolymer (b) can be controlled by adjusting the monomer amount with respect to the initiator during polymerization and / or adjusting the coupling reaction rate, and The ratio can be controlled within the above numerical range.
The peak molecular weight of the block copolymer can be measured by the method described in Examples described later.

The block copolymer (a) has one polymer block mainly composed of vinyl aromatic monomer units and one polymer block mainly composed of conjugated diene monomer units. From the viewpoint of the productivity of the block copolymer, the softening point of the asphalt composition, and the viscosity of the asphalt composition.
The block copolymer (b) has two or more polymer blocks mainly composed of vinyl aromatic monomer units and one or more polymer blocks mainly composed of conjugated diene monomer units. It is preferable from the viewpoint of the productivity of the block copolymer, the softening point of the asphalt composition, and the viscosity of the asphalt composition.

  The block copolymer (a) preferably contains at least one block copolymer selected from the group consisting of SB and the following formulas (i) to (iii), and the block copolymer (b) Preferably contains at least one block copolymer selected from the group consisting of the following formulas (i) to (vi).

(SB) _n (i)
B- (SB) _n (ii)
S- (B-S) _n (iii)
S- (B-S) _n -X (iv)
[(SB) _k ] _m -X (v)
[(S−B) _k −S] _m −X (vi)
In the SB and the formulas (i) to (vi), S represents a polymer block mainly composed of vinyl aromatic monomer units, and B is mainly composed of conjugated diene monomer units. Represents a polymer block.
X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium, m is an integer of 2 to 6, and n and k are each independently an integer of 1 to 4. .
The values of m, n, and k in formulas (i) to (vi) may be the same or different.

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

  In the formulas (iv) to (vi), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium as described above. From the viewpoint of controlling the molecular weight of the block, X is preferably a residue of a coupling agent.

Examples of coupling agents include, but are not limited to, silicon tetrachloride, tin tetrachloride, epoxy compounds, polyhalogenated hydrocarbon compounds, carboxylic acid ester compounds, polyvinyl compounds, alkoxysilane compounds, and halogenated compounds. Examples include silane compounds and ester compounds.
The block copolymer (b) may be a mixture of a coupling body in which X is a residue of a coupling agent and a block copolymer having no X.

  From the viewpoint of the heat deterioration resistance of the block copolymer during the production of the asphalt composition, X is preferably a residue of a coupling agent composed of an alkoxysilane compound or an epoxy compound.

Examples of the alkoxysilane compound that is a coupling agent include, but are not limited to, tetraalkoxysilane compounds such as tetramethoxysilane and the like, and tetraaryls such as tetraphenoxysilane and the same. Alkyloxysilane compounds having two or more alkoxy groups such as methyltriethoxysilane and the like, and alkyls having two or more aryloxy groups such as methyltriphenoxysilane and the like Aryloxysilane compounds; alkenylalkoxysilane compounds having two or more alkoxy groups such as vinyltrimethoxysilane and the like; and halogenoalkoxys such as trimethoxychlorosilane and the like Orchid compounds.
Among these, alkylalkoxysilanes having 2 to 4 alkylalkoxy groups are preferred from the viewpoint of heat deterioration resistance and block copolymer productivity.

Examples of the epoxy compound that is a coupling agent include, but are not limited to, polyepoxidized vegetable oils such as epoxidized soybean oil or epoxidized linseed oil, epoxidized polybutadiene, or epoxidized tetraallyl ether penta And erythritol.
In these, the epoxy compound which has a phenyl group from a viewpoint of heat-resistant deterioration and the manufacture property of a block copolymer is preferable.

  The number of alkoxysilyl groups and epoxy groups in the alkoxysilane compound and the epoxy compound is determined from the viewpoint of the low mixing temperature of the asphalt composition of the present embodiment, the low viscosity of the asphalt composition, and the small deterioration of the polymer in the asphalt composition. 2-5 are preferable per molecule, 2-4 are more preferable, 3-4 are more preferable, and 4 are even more preferable.

In addition, the boundary of each block and the most end part of the said block copolymer do not necessarily need to be distinguished clearly.
For example, a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit may be present. A plurality of the copolymer blocks may coexist. In the polymer block (S) mainly composed of vinyl aromatic monomer units, a plurality of segments having different contents of vinyl aromatic monomer units may coexist.

The block copolymer (b), which is a high molecular weight component contained in the additive (A), has a low mixing temperature during production of the asphalt composition of the present embodiment, a low viscosity of the asphalt composition, (SB) _m -X (m = 2 to 4 is an integer from the viewpoint of low deterioration of the polymer and a high softening point of the asphalt composition, and S is a weight mainly composed of vinyl aromatic monomer units. And B is a polymer block mainly composed of a conjugated diene monomer unit, and X is a residue of a coupling agent or a residue of a polymerization initiator.) (SB) ₄ -X (S is a polymer block mainly composed of vinyl aromatic monomer units, and B is a polymer block mainly composed of conjugated diene monomer units. And X is the residue of the coupling agent .) And more preferably contains a block copolymer represented by.
From the viewpoint of the low viscosity of the asphalt composition of the present embodiment and the high softening point of the asphalt composition, the block copolymer (b) is composed of (SB) ₃ -X and (SB) ₄ -X. It is more preferable to contain.

The ratio of the block copolymer (a) to the total amount of the block copolymer (a) and the block copolymer (b) is low mixing temperature of the asphalt composition, low viscosity of the asphalt composition, high of the asphalt composition. From the viewpoint of adhesiveness, 30% by mass or more is preferable, 40% by mass or more is more preferable, 50% by mass or more is more preferable, and 60% by mass or more is even more preferable.
In addition, from the viewpoint of high elongation recovery of the asphalt composition and a high softening point of the asphalt composition, 95% by mass or less is preferable, 90% by mass or less is more preferable, 85% by mass or less is further preferable, and 80% by mass or less is preferable. Even more preferred.
In this specification, “extension recovery property of asphalt composition” means whether the asphalt composition is molded using a dumbbell-shaped mold, then stretched and cut at the center, and then returned to the original length. Shows performance (elastic recovery).
Specifically, the stretch recovery property of the asphalt composition is determined by the measurement according to the following (1) to (6).
(1) The molten asphalt composition is poured into a mold having a dumbbell shape (for example, length × width × thickness = about 12 cm × 5 cm × 1 cm).
(2) Place the cooled asphalt composition (both ends with dumbbell jigs) in a 25 ° C. water bath.
(3) Grab both ends of the dumbbell with a jig and pull it at a constant speed.
(4) Extend 20 cm and stop for about 5 minutes.
(5) While holding both ends of the dumbbell, cut the middle of the dumbbell.
(6) If the rubber elasticity remains, the cut dumbbell will return to the length (about 12 cm) before extending the dumbbell (from the length of 20 cm-α on both sides immediately after cutting). Therefore, measure how much it returns after a certain period of time. Note that α represents the amount that the dumbbell has returned when a certain time has already passed during measurement.

Further, the ratio of the block copolymer (b) to the total amount of the block copolymer (a) and the block copolymer (b) is high in the elongation recovery property of the asphalt composition of the present embodiment and high in the asphalt composition. From the viewpoint of the softening point and the excellent low temperature bendability of the asphalt composition, 5% by mass or more is preferable, 10% by mass or more is more preferable, 15% by mass or more is further preferable, and 20% by mass or more is even more preferable.
Further, from the viewpoint of the low mixing temperature of the asphalt composition and the low viscosity of the asphalt composition, it is preferably 70% by mass or less, more preferably 65% by mass or less, further preferably 60% by mass or less, and further more preferably 50% by mass or less. preferable. Since the high molecular weight block copolymer (b) has higher rubber elasticity than the block copolymer (a), the ratio of the block copolymer (b) is relatively high. It is thought that it acts positively on the indices contributed by rubber elasticity such as the softening point of objects and low temperature bendability.

The peak molecular weight of the block copolymer (a) is 30,000 or more, preferably 40,000 or more, more preferably 45,000 or more, from the viewpoint of the high softening point of the asphalt composition. Further, from the viewpoint of low mixing temperature of the asphalt composition, low viscosity of the asphalt composition, and little deterioration of the polymer in the asphalt composition, it is 150,000 or less, preferably 130,000 or less, and 120,000 or less. More preferably, 110,000 or less is more preferable, and 100,000 or less is even more preferable.
As described above, the peak molecular weight of the block copolymer (b) is from 1.5 to the peak molecular weight of the block copolymer (a) from the viewpoint of the high softening point of the asphalt composition and the low viscosity of the asphalt composition. It is less than 6.0 times, preferably 1.7 to 5.0 times, and more preferably 1.8 to 4.5 times.

When the block copolymer (b) is (SB) _m -X, the peak molecular weight of (SB) _m -X is from the viewpoint of a high softening point and high tensile recovery of the asphalt composition. The peak molecular weight is preferably m times that of the block copolymer (a) represented by S-B or S-B-X. In addition, the peak molecular weight of a polymer can be calculated | required by the method as described in the Example mentioned later.

Further, the content of the vinyl aromatic monomer unit in the additive (A) is 20% by mass from the viewpoint of a high softening point of the asphalt composition of the present embodiment and a small deterioration of the polymer in the asphalt composition. It is preferable that it is above, 22 mass% or more is more preferable, 24 mass% or more is further more preferable, and 26 mass% or more is further more preferable.
Further, the content of the vinyl aromatic monomer unit in the additive (A) is excellent low temperature bendability of the asphalt composition, excellent adhesiveness in the low temperature region of the asphalt composition, low viscosity of the asphalt composition, From the viewpoint of low oil bleeding property of the asphalt composition, it is preferably 45% by mass or less, more preferably 42% by mass or less, further preferably 40% by mass or less, and further more preferably 38% by mass or less. Since the content of the vinyl aromatic monomer unit is likely to affect the hardness of the additive (A), setting the upper limit to a low value is positive for performance that requires softness such as low-temperature bendability. It is thought to work.

Here, the content of the vinyl aromatic monomer unit in the additive (A) is not the value for each component, but the content of the vinyl aromatic monomer unit as a whole additive (A), that is, each It is an average value of the content of vinyl aromatic monomer units of the component.
In addition, in this embodiment, content of the vinyl aromatic monomer unit in an additive (A) can be measured by the method as described in the Example mentioned later.

The ratio of the vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in the additive (A) (block ratio) is a high softening point of the asphalt composition and a high asphalt composition. From the viewpoint of elongation recovery, 90% or more is preferable, 93% or more is more preferable, 95% or more is further preferable, and 96% or more is even more preferable.
Further, the block ratio is preferably 99% or less, more preferably 98% or less, from the viewpoint of the deterioration of the polymer in the asphalt composition and the flexibility of the asphalt composition.

  The ratio (block ratio) of vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in additive (A) is (vinyl vinyl monomer block content in additive) Amount) / (total content of vinyl aromatic monomer units in the additive) × 100.

  The vinyl aromatic monomer block means a polymer block mainly composed of a vinyl aromatic monomer unit.

  In addition, the vinyl aromatic monomer block content in the additive (A) and the total content of vinyl aromatic monomer units in the additive (A) are determined by the method described in the examples described later. Can do.

The ratio of the vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in the additive (A) is, for example, molecular weight, polymerization temperature, monomer addition rate, added first. It can be controlled by adjusting the time interval for adding the monomer and the next monomer, the polar compound, the randomizing agent, the stirring speed of the polymerization reactor, and the like.
Specifically, the conjugated diene monomer after 1 minute or more and less than 21 minutes have elapsed since reaching the peak temperature appearing at the end of the polymerization of the vinyl aromatic monomer unit, and after the temperature has decreased by 1 ° C. or more from the peak temperature By adding the unit, the block ratio can be 90% or more and 99% or less.

  Here, the ratio of the vinyl aromatic monomer block content to the total content of the vinyl aromatic monomer units in the additive (A) is not a value for each component, but the block copolymer weight contained. It is a value as a whole, that is, an average value of each component.

The melt flow rate (MFR, 200 ° C., 5 kgf) of the additive (A) is preferably 0.5 g / 10 min or more, more preferably 0.75 g / 10 min or more from the viewpoint of manufacturability, and 1 g / 10 min. The above is more preferable.
In addition, the melt flow rate (MFR, 200 ° C., 5 kgf) of the additive (A) is low in the amount of polymer added to the asphalt, that is, from the viewpoint of reducing the amount of polymer added to the asphalt, and recoverability after tension. From the viewpoint, 100 g / 10 min or less is preferable, 50 g / 10 min or less is more preferable, and 30 g / 10 min or less is more preferable.

The additive (A) is added to the conjugated diene monomer unit in the polymer from the viewpoint of the high softening point of the asphalt composition of the present embodiment, the high heat deterioration resistance of the polymer, and the low oil bleeding property of the asphalt composition. At least some of the double bonds involved are hydrogenated.
From the viewpoint of the high softening point of the asphalt composition and the high heat deterioration resistance of the polymer, the additive (A) has a hydrogenation rate of double bonds contained in the conjugated diene monomer unit of 10 mol% or more, 20 mol% or more is preferable, 25 mol% or more is more preferable, and 35 mol% or more is more preferable.
In addition, the additive (A) has a hydrogenation rate of double bonds contained in the conjugated diene monomer unit, excellent low-temperature bendability of the asphalt composition, and excellent adhesiveness in the low-temperature region of the asphalt waterproof sheet. Therefore, it is 85 mol% or less, preferably 60 mol% or less, more preferably 55 mol% or less, and further preferably 50 mol% or less. By adding hydrogen, the glass transition point in the low temperature region shifts to the high temperature side, so it is considered that the low temperature bendability that requires softness in the low temperature region tends to decrease, but it is practical if it is 85 mol% or less. There is no problem with the above performance.

In the present specification, the conjugated diene monomer unit is referred to as a “conjugated diene monomer unit” regardless of before and after hydrogenation.
That is, when the conjugated diene monomer is polymerized, there is an unsaturated bond part before hydrogenation, but after hydrogenation, there is no unsaturated bond derived from the conjugated diene. Components derived from body units are referred to as “conjugated diene monomer units”.

  The hydrogenation rate of the double bond amount can be controlled within the above numerical range by adjusting the hydrogenation amount and the hydrogenation reaction time in the hydrogenation step. Moreover, in this embodiment, a hydrogenation rate can be calculated | required by the method as described in the Example mentioned later.

  The vinyl content in the conjugated diene monomer unit before hydrogenation of the additive (A) contained in the asphalt-containing waterproof sheet additive of the present embodiment is high compatibility with asphalt, the asphalt composition From the viewpoint of low viscosity, 8 mol% or more is preferable, 10 mol% or more is more preferable, 12 mol% or more is more preferable, and 20 mol% or more is even more preferable. Further, the vinyl content in the conjugated diene monomer unit before hydrogenation is preferably 50 mol% or less, more preferably 45 mol% or less, and more preferably 42 mol% or less, from the viewpoint of little deterioration of the polymer in the asphalt composition. More preferred is 38 mol% or less.

(Additive (B))
The asphalt-containing waterproof sheet additive of the present embodiment may contain the additive (B) in addition to the additive (A) described above.
The additive (B) contains a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the hydrogenation rate of double bonds contained in the conjugated diene monomer unit is 0 mol%.
From the viewpoint of the low viscosity of the asphalt composition of the present embodiment, the asphalt-containing waterproof sheet additive of the present embodiment preferably includes an additive (B).
Moreover, when using the tackifier mentioned later, it is preferable that an additive (B) is included from a compatible viewpoint with a highly polar tackifier.

Additive (B) has the following different block copolymers from the viewpoints of low mixing temperature during production of the asphalt composition, low viscosity of the asphalt composition, high softening point of the asphalt composition, and high adhesiveness of the asphalt adhesive sheet. It is preferable that a polymer (c) and a block copolymer (d) are included.
The block copolymer (c) has a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units. The peak molecular weight of the block copolymer (c) is preferably from 50,000 to 150,000.
The block copolymer (d) has a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units.
The peak molecular weight of the block copolymer (d) is 1. which is the peak molecular weight of the block copolymer (c) from the viewpoint of a low mixing temperature during production, a high softening point of the asphalt composition, and a low viscosity of the asphalt composition. 5 to 6.0 times less.
From the viewpoint of the low viscosity and high softening point of the asphalt composition, the block copolymer (c) is mainly composed of one polymer block mainly composed of vinyl aromatic monomer units and conjugated diene monomer units. Preferably, the block copolymer (d) has two or more polymer blocks mainly composed of vinyl aromatic monomer units and conjugated diene monomer units. It is preferable to have one or more main polymer blocks.

As a structure of a block copolymer (c), the structure of SB and said Formula (i)-(iii) can be illustrated similarly to the above-mentioned block copolymer (a).
As a structure of a block copolymer (d), the structure of said Formula (i)-(vi) can be illustrated similarly to the above-mentioned block copolymer (b).

From the viewpoint of the high softening point of the asphalt composition and the tensile recovery properties of the asphalt composition, the additive (B) is SSB, (SB) ₂ -X, (SB) ₄ -X. It is preferable to contain the block copolymer represented.

  When the additive (B) contains the block copolymer (c) and the block copolymer (d), the content of the block copolymer (c) in the total mass of the additive (B) is the asphalt composition. From the viewpoint of the high softening point of the product and the excellent low temperature bendability of the asphalt composition, it is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and 80% by mass. % Or less is even more preferable. Further, from the viewpoint of high adhesiveness of the asphalt composition and low viscosity of the asphalt composition, 10% by mass or more is preferable, 20% by mass or more is more preferable, 40% by mass or more is further preferable, and 60% by mass or more is even more. preferable.

The content of the block copolymer (d) in the total mass of the additive (B) is preferably 95% by mass or less from the viewpoint of the low viscosity of the asphalt composition and the high tackiness of the asphalt composition. More preferably, it is more preferably 60% by mass or less, and still more preferably 40% by mass or less.
Further, from the viewpoint of the high softening point of the asphalt composition and the excellent low temperature bendability of the asphalt composition, 5% by mass or more is preferable, 15% by mass or more is more preferable, 40% by mass or more is further preferable, and 70% by mass or more. Is even more preferred.
Since the high molecular weight block copolymer (d) has a higher rubber elasticity than the block copolymer (c), the ratio of the block copolymer (d) is relatively high. It is thought that it has a positive effect on the indices contributed by rubber elasticity, such as the softening point of objects and low temperature bendability.

The additive (B) is a mixture of SBS, (SB) ₂ -X (block copolymer (d)) and SB (block copolymer (c)), (S- B) A mixture of _3- X (block copolymer (d)) and SB (block copolymer (c)), (SB) _4- X (block copolymer (d)) and S -B (block copolymer (c)) is preferable, from the viewpoint of the high softening point of the asphalt composition, the low viscosity of the asphalt composition, and the tackiness in the high temperature region of the asphalt composition (S -B) A mixture of _4- X (block copolymer (d)) and SB (block copolymer (c)) is more preferable.
Furthermore, the peak molecular weight of the block copolymer (c) is preferably 50,000 or more, more preferably 60,000 or more, further preferably 70,000 or more, from the viewpoint of a high softening point. 80,000 or more is even more preferable. Moreover, 150,000 or less are preferable from a viewpoint of the low mixing temperature and low viscosity at the time of manufacture, 130,000 or less are more preferable, 120,000 or less are more preferable, and 110,000 or less are still more preferable.
The peak molecular weight of the block copolymer (d) is 1. which is the peak molecular weight of the block copolymer (c) from the viewpoint of a low mixing temperature during production, a high softening point of the asphalt composition, and a low viscosity of the asphalt composition. It is less than 5 to 6.0 times, preferably 1.7 to 5.0 times, and more preferably 1.8 to 4.5 times.

From the viewpoint of the viscosity and adhesiveness of the asphalt composition, the mass ratio of the block copolymer (c) to the block copolymer (d) is particularly (c) / (d) = 60 to 95 / 40-5 are preferable, 65-95 / 35-5 are more preferable, and 70-90 / 30-10 are more preferable.
Further, the content of the vinyl aromatic monomer unit in the additive (B) is 8% by mass or more from the viewpoint of a high softening point of the asphalt composition and little deterioration of the polymer in the asphalt composition. Is preferable, 10 mass% or more is more preferable, 12 mass% or more is further preferable, and 15 mass% or more is further more preferable.
Further, the content of the vinyl aromatic monomer unit in the additive (B) is 50% by mass or less from the viewpoint of excellent low temperature bendability of the asphalt composition and excellent adhesiveness in the low temperature region of the asphalt waterproof sheet. It is preferably 46% by mass or less, more preferably 42% by mass or less, and even more preferably 35% by mass or less. Since the content of the vinyl aromatic monomer unit in the additive (B) tends to affect the hardness of the additive (B), softness such as low-temperature bendability can be obtained by setting the upper limit value low. It is thought that it works positively on the required performance.

  Here, the content of the vinyl aromatic monomer unit in the additive (B) is not a value for each component, but the content of the vinyl aromatic monomer unit as a whole of the additive (B), that is, each component It is an average value of the content of vinyl aromatic monomer units.

  In addition, content of the vinyl aromatic monomer unit in an additive (B) can be measured by the method as described in the Example mentioned later.

  The ratio of the vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in the additive (B) (block ratio) is high in the softening point of the asphalt composition and high in the asphalt composition. From the viewpoint of elongation recovery, 90% or more is preferable, 93% or more is more preferable, 95% or more is further preferable, and 96% or more is even more preferable.

  In addition, the block ratio is preferably 99% or less from the viewpoint of a low mixing temperature of the asphalt composition, a low viscosity of the asphalt composition, a small deterioration of the polymer in the asphalt composition, and a flexibility of the asphalt composition. % Or less is more preferable.

The ratio (block ratio) of vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in additive (B) is:
(Vinyl aromatic monomer block content in additive (B)) / (total content of vinyl aromatic monomer units in additive (B)) × 100.
Here, the vinyl aromatic monomer block means a polymer block mainly composed of vinyl aromatic monomer units.

  In this embodiment, the vinyl aromatic monomer block content in the additive (B) and the total content of vinyl aromatic monomer units in the additive (B) are described in the examples described later. It can be determined by the method described.

The ratio of vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in additive (B) is, for example, molecular weight, polymerization temperature, monomer addition rate, added first It can be controlled by adjusting the time interval for adding the monomer and the next monomer, the polar compound, the randomizing agent, the stirring speed of the polymerization reactor, and the like.
Specifically, for example, the amount of the conjugated diene after 1 minute or more and less than 21 minutes have elapsed since reaching the peak temperature appearing at the end of the polymerization of the vinyl aromatic monomer unit and after the temperature has decreased by 1 ° C. or less from the peak temperature. By adding a body unit, the block ratio can be 90% or more and 99% or less.

  Here, the ratio of the vinyl aromatic monomer block content to the total content of the vinyl aromatic monomer units in the additive (B) is not a value for each component, but the additive (B) as a whole. Is the average value of each component.

The melt flow rate (MFR, 200 ° C., 5 kgf) of the additive (B) is preferably 0.1 g / 10 min or more, more preferably 0.2 g / 10 min or more from the viewpoint of manufacturability, and 1 g / 10 min. The above is more preferable.
In addition, the melt flow rate (MFR, 200 ° C., 5 kgf) of the additive (B) is low in the amount of polymer added to the asphalt, that is, from the viewpoint of reducing the amount of polymer added to the asphalt, and recoverability after tension. From the viewpoint, 100 g / 10 min or less is preferable, 50 g / 10 min or less is more preferable, and 30 g / 10 min or less is more preferable.

The ratio of the additive (A) to the total mass of the additive (A) and the additive (B) described above is from the viewpoint of the low oil bleeding property of the asphalt composition and the excellent adhesiveness in the low temperature region of the asphalt composition. , Additive (A) / (additive (A) + additive (B)) × 100 (mass%) is preferably 8 mass% or more, more preferably 12 mass% or more, and further preferably 15 mass% or more. 20% by mass or more is even more preferable. Further, from the viewpoint of the low viscosity of the asphalt composition and the excellent low temperature bendability of the asphalt composition, 55% by mass or less is preferable, 45% by mass or less is more preferable, 40% by mass or less is further preferable, and 30% by mass or less is preferable. Even more preferred.
Since the additive (A) is hydrogenated, the glass transition point in the low temperature region is shifted to the high temperature side, and when the ratio of the additive (A) increases, the softness in the low temperature region tends to decrease. it is conceivable that. Therefore, when the additive (A) having the same polymer structure and the additive (B) are mixed, it is considered that when the ratio of the additive (B) is increased, the low-temperature bendability is excellent.

(Additive (A) and Additive (B))
The copolymer constituting the additive (A) and / or the additive (B) is a hydroxyl group from the viewpoint of excellent adhesiveness in the high temperature region of the asphalt composition of the present embodiment and low oil bleeding property of the asphalt composition. It preferably has at least one functional group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group.
Among these functional groups, those containing a nitrogen atom in the functional group are more preferred, and those containing both a nitrogen atom and an oxygen atom are more preferred.

Since the additives (A) and (B) have the functional group, the additives interact with polar components in the asphalt, whereby the additive is finely dispersed in the asphalt. Therefore, the low molecular weight component in the asphalt composition and the softener tend to inhibit bleeding on the surface of the asphalt composition.
Moreover, when the polar group on the adherend surface to which the asphalt-containing waterproof sheet is attached interacts with the functional group of the additive, the adhesiveness in the low temperature to high temperature region tends to be excellent.
Therefore, the functional groups of the additives (A) and (B) tend to preferably have nitrogen atoms and oxygen atoms having high electronegativity, and if the number of functional groups is large, the above-described effect is obtained. More preferably, the additive (A) and / or the additive (B) both have a functional group.

The copolymer constituting the additives (A) and (B) has at least one function 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. Examples of the method for imparting a group include a method using a polymerization initiator, a monomer and a terminal modifier having these functional groups.
Among these, a method using a terminal modifier having a functional group is preferable from the viewpoint of ease of production.

As the monomer used for imparting the predetermined functional group to the copolymer constituting the additive, the monomer used for the polymerization includes a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide. And compounds containing a group, a silanol group, and an alkoxysilane group.
Among these, monomers containing an N group are preferable, for example, N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-dibutylvinylbenzyl. Amine, N, N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis (trimethylsilyl) aminoethylstyrene, 1- (4-N, N-dimethylaminophenyl) -1- Phenylethylene, N, N-dimethyl-2- (4-vinylbenzyloxy) ethylamine, 4- (2-pyrrolidinoethyl) styrene, 4- (2-piperidinoethyl) styrene, 4- (2-hexamethyleneiminoethyl) Styrene, 4- (2-morpholinoethyl) styrene, 4- (2-thia Aminoethyl) styrene, 4- (2-N-methyl-piperazino-ethyl) styrene, 1 - ((4-vinyl) methyl) pyrrolidine, 1- (4-vinyl benzyloxycarbonyl) pyrrolidine, and the like.

The terminal modifier used for imparting the predetermined functional group to the copolymer constituting the additive is not limited to the following, and examples thereof include tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bis. Aminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, γ-caprolactone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysila Bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4- Epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4- Epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyl-dimethylethoxysilane, 1,3-di Chill-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethyl propylene urea, N- methylpyrrolidone and the like.
It is preferable that the usage-amount of a terminal modifier is 0.5-5 equivalent with respect to 1 equivalent of the living terminal of the polymer used as a base.

[Method for producing additive for asphalt-containing waterproof sheet]
The additive for asphalt-containing waterproof sheets of the present embodiment obtains a polymer 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, for example. A polymerization step, a hydrogenation step of hydrogenating the double bond in the conjugated diene monomer unit of the polymer obtained as necessary, and a desolvation step of removing the solvent of the solution containing the polymer are sequentially performed. Can be manufactured.
The additive for asphalt-containing waterproof sheets of this embodiment can also be produced by preparing the additive (A) and additive (B) described above and mixing them.

(Polymerization process)
In the polymerization step, a polymer is obtained by polymerizing a monomer containing at least a conjugated diene monomer and a vinyl aromatic monomer in a hydrocarbon solvent using a lithium compound as a polymerization initiator.

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

(Polymerization initiator)
Examples of the lithium compound used as a polymerization initiator in the polymerization step include, but are not limited to, for example, a compound in which one or more lithium atoms are bonded in a molecule such as an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound. It is done.
Examples of such an organic lithium compound include, but are not limited to, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadiene. Examples include enildilithium and isoprenyldilithium. These may be used alone or in combination of two or more.

(Monomer used for polymerization)
Examples of the conjugated diene monomer include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3, for example. -Diolefins having a pair of conjugated double bonds such as pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of economy.
From the viewpoint of mechanical strength, 1,3-butadiene is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the vinyl aromatic monomer include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene. And vinyl aromatic compounds such as N, N-diethyl-p-aminoethylstyrene. Of these, styrene is preferred from the viewpoint of economy. These may be used alone or in combination of two or more.

  As the polymerization monomer, in addition to the conjugated diene monomer and the vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer can also be used.

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

  Examples of polar compounds and randomizing agents include, but are not limited to, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; amines such as triethylamine and tetramethylethylenediamine; thioethers, phosphines, phosphoramides, alkylbenzenes Examples thereof include sulfonates, potassium and sodium alkoxides, and the like.

  It does not specifically limit as a polymerization method implemented at a superposition | polymerization process, A well-known method is applicable. Known methods include, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, and Japanese Patent Publication No. Sho. Examples thereof include methods described in Japanese Patent No. 48-4106, Japanese Patent Publication No. 56-28925, Japanese Patent Application Laid-Open No. 59-166518, Japanese Patent Application Laid-Open No. 60-186777 and the like.

(Deactivation process)
It is preferable to deactivate the active terminal of the polymer by the deactivation step. The method of deactivating the active terminal of the polymer can be achieved by reacting with a compound having an active terminal and active hydrogen. Although the compound which has active hydrogen is not specifically limited, Alcohol and water are preferable at the economical point.

(Hydrogenation process)
The hydrogenation step is a step in which a hydrogenation reaction is performed on a part of the double bond in the conjugated diene monomer unit of the polymer obtained in the polymerization step.
It carries out in the manufacturing process of an additive (A).
The hydrogenation catalyst used in the hydrogenation reaction is not limited to the following. For example, a supported catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on a carrier such as carbon, silica, alumina, or diatomaceous earth. Homogeneous catalysts; so-called Ziegler type catalysts using organic salts such as Ni, Co, Fe, Cr or the like and acetylacetone salts and reducing agents such as organic Al; so-called organic complex catalysts such as organometallic compounds such as Ru and Rh, or titanocene Examples of the catalyst include a homogeneous catalyst using organic Li, organic Al, organic Mg, or the like as a reducing agent.
Among these, a homogeneous catalyst system using organic Li, organic Al, organic Mg, or the like as a reducing agent for the titanocene compound is preferable from the viewpoints of economy, heat aging resistance or weather resistance of the polymer.

Examples of the hydrogenation method include, but are not limited to, the methods described in JP-B-42-8704 and JP-B-43-6636, and preferably JP-B-63-4841 and JP-B-63- The method described in 5401 gazette is mentioned.
Specifically, hydrogenation is performed in an inert solvent in the presence of a hydrogenation catalyst to obtain a hydrogenated block copolymer solution.

The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
The hydrogenation reaction is not particularly limited, but is preferably performed after the step of deactivating the active terminal of the polymer described above from the viewpoint of high hydrogenation activity.

A predetermined polymer is obtained by adding predetermined hydrogen using the hydrogenation catalyst described above. By adjusting the number of moles of hydrogen added to the reaction system, the hydrogenation rate in the additive (A) can be made 10 mol% or more and 85 mol% or less.
In the hydrogenation step, the conjugated bond of the vinyl aromatic monomer unit may be hydrogenated. The hydrogenation rate of the conjugated bond in all vinyl aromatic monomer units is preferably 30 mol% or less, more preferably 10 mol% or less, and further preferably 3 mol% or less. Moreover, the minimum of the hydrogenation rate of the conjugated bond in all vinyl aromatic monomers is although it does not specifically limit, Preferably it is 0 mol% or more, More preferably, it is 1 mol% or more. When the hydrogenation rate of the conjugated bond in the total vinyl aromatic monomer is within the above range, the amount of polymer added to the asphalt tends to be low or the compatibility with the asphalt tends to be high.

(Desolvation process)
The solvent removal step is a step of removing the solvent of the solution containing the polymer.
The solvent removal method is not particularly limited, and examples thereof include a steam stripping method and a direct solvent removal method.

  The amount of residual solvent in the polymer obtained by the solvent removal step is preferably 2% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and even more. Preferably it is 0.05 mass% or less, More preferably, it is 0.01 mass% or less. Further, the lower limit of the residual solvent amount in the copolymer is not particularly limited, but a smaller one is preferable, and more preferably 0% by mass. However, in terms of economy at the time of solvent removal, it is usually 0.01% by mass. % Or more and 0.1% by mass or less.

From the viewpoint of heat aging resistance of the copolymer and suppression of gelation, it is preferable to add an antioxidant to the copolymer.
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 a sulfur antioxidant.
Moreover, you may use the antioxidant which has both performances together. These may be used alone or in combination of two or more.

Among the antioxidants, it is preferable to add at least a phenol-based antioxidant from the viewpoints of heat aging resistance of the additives (A) and (B) and the asphalt composition and suppression of gelation.
The addition amount of the phenolic antioxidant is 0.05 parts by mass or more with respect to 100 parts by mass of the additives (A) and (B), from the viewpoint of high low-temperature productivity and little deterioration of the polymer during mixing. Preferably, 0.10 mass part or more is more preferable, and 0.20 mass part or more is further more preferable.
Moreover, the addition amount of the phenolic antioxidant is preferably 1.00 parts by mass or less with respect to 100 parts by mass of the additives (A) and (B) from the viewpoint of high peeling resistance and economic efficiency of the aggregate. 0.5 parts by mass or less is more preferable, 0.4 parts by mass or less is more preferable, and 0.3 parts by mass or less is even more preferable.

  In addition, from the viewpoint of preventing coloring of the polymer and improving mechanical strength, a deashing process for removing metal in the polymer and a neutralization process for adjusting the pH of the polymer, for example, addition of an acid, before the solvent removal process Or carbon dioxide gas may be added.

[Asphalt composition]
The asphalt composition of this embodiment contains asphalt.
In the present specification, the “asphalt composition” means a composition containing an asphalt prepared in the step of producing an asphalt-containing waterproof sheet and a polymer that is an additive, and is typically composed of an asphalt-containing waterproof sheet. It is a composition which contains all the components and becomes an asphalt-containing waterproof sheet upon curing.

(asphalt)
The asphalt that can be used in the present embodiment is not particularly limited. For example, the asphalt that is obtained as a by-product (petroleum asphalt) during petroleum refining, or a natural product (natural asphalt), or these And a mixture of petroleum and the like.
The main component of asphalt is called bitumen.
Specific examples include, but are not limited to, straight asphalt, semi-blown asphalt, blown asphalt, solvent deasphalted asphalt, tar, pitch, and cutback asphalt with added oil, asphalt emulsion, and the like. These may be used alone or in combination of two or more.
Moreover, you may add aromatic heavy mineral oils, such as petroleum-type solvent extraction oil, aroma-type hydrocarbon process oil, and extract, to various asphalts.

  The asphalt used in the asphalt composition of the present embodiment preferably has a penetration (measured according to JIS-K2207) of 30 or more and 300 or less, more preferably 40 from the viewpoint of high temperature physical properties, low temperature physical properties, and economic efficiency. The straight asphalt is 250 or more and 250 or less, more preferably 45 or more and 200 or less.

In the asphalt composition of the present embodiment, the content of the additive for the asphalt-containing waterproof sheet of the present embodiment described above is that the asphalt composition has a high softening point, high tackiness, excellent low-temperature bendability, and low oil bleeding properties. In view of the above, the content is 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, and further preferably 12% by mass or more.
Moreover, from a viewpoint of the low viscosity of an asphalt composition and economical efficiency, it is 30 mass% or less, 27 mass% or less is preferable, 25 mass% or less is more preferable, and 23 mass% or less is further more preferable.
The total content of the additive (A) and the additive (B) in the asphalt composition of this embodiment is a high softening point of the asphalt composition, excellent low-temperature bendability of the asphalt composition, and a high asphalt composition. From the viewpoint of adhesiveness and low oil bleed property of the asphalt composition, it is 5% by mass or more, preferably 8% by mass or more, more preferably 15% by mass or more, and further preferably 21% by mass or more.
Moreover, the total content of the additive (A) and the additive (B) in the asphalt composition is the low mixing temperature of the asphalt composition, the low viscosity of the asphalt composition, the little deterioration of the polymer in the asphalt composition, From the economical viewpoint, it is 30% by mass or less, preferably 27% by mass or less, more preferably 25% by mass or less, and further preferably 23% by mass or less.
The content of asphalt in the asphalt composition of the present embodiment is 90% by mass or less from the viewpoint of a high softening point of the asphalt composition, elongation recovery of the asphalt composition, and excellent low-temperature bendability of the asphalt composition. 88 mass% or less is preferable, 84 mass% or less is more preferable, and 80 mass% or less is further more preferable.
Further, the content of asphalt in the asphalt composition is 30% by mass or more from the viewpoint of low mixing temperature of the asphalt composition, low viscosity of the asphalt composition, little deterioration of the polymer in the asphalt composition, and economical efficiency. Yes, 35 mass% or more is preferable, 40 mass% or more is more preferable, and 45 mass% or more is more preferable.

(Tackifier)
The asphalt composition of the present embodiment can contain various tackifiers selected as required according to need.
By adding a tackifier, the tackiness of the asphalt composition tends to be improved, and peeling of the asphalt-containing waterproof sheet can be suppressed.
Examples of the tackifier include, but are not limited to, natural rosin, modified rosin, natural rosin glycerol ester, modified rosin glycerol ester, natural rosin pentaerythritol ester, modified rosin pentaerythritol ester, hydrogenated rosin, hydrogen Rosin compounds such as pentaerythritol ester of added rosin; natural terpene copolymer, three-dimensional polymer of natural terpene, aromatic modified terpene resin, hydrogenated derivative of aromatic modified terpene resin, terpene phenol resin, hydrogenation of terpene phenol resin Terpene compounds such as derivatives, terpene resins (monoterpenes, diterpenes, triterpenes, polyterpenes, etc.), hydrogenated terpene resins, hydrogenated derivatives of hydrogenated terpene resins; aliphatic petroleum hydrocarbon resins C5 resin), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated derivatives of aromatic petroleum hydrocarbon resins, dicyclopentadiene resins, dicyclopentadiene resins Hydrocarbon derivatives of C5 / C9 copolymer resins, hydrogenated derivatives of C5 / C9 copolymer resins, cycloaliphatic petroleum hydrocarbon resins, hydrogenated derivatives of cycloaliphatic petroleum hydrocarbon resins, etc. Examples thereof include compounds and aromatic group-containing resins.
These tackifiers can be used alone or in combination of two or more. The C5 / C9 copolymer resin is a copolymerized petroleum resin polymerized using a mixture of C5 fraction and C9 fraction as a raw material.

<Aliphatic tackifier>
The asphalt composition of this embodiment preferably contains an aliphatic tackifier as a tackifier from the viewpoint of excellent tackiness and economy of the asphalt composition.
Examples of the aliphatic tackifier include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 resins), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 resins), and C5 / C9 copolymer systems. Examples thereof include hydrogenated derivatives of resins and C5 / C9 copolymer resins.
The aliphatic tackifier has an aliphatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. More preferably, it refers to a tackifier that is 88% by mass or more, and more preferably 95% by mass or more. When the content of the aliphatic hydrocarbon group is within the above range, the excellent tackiness and economy of the asphalt composition tend to be further improved.

The aliphatic tackifier can be produced by homopolymerizing or copolymerizing a monomer having an aliphatic group and a polymerizable unsaturated group. Although it does not specifically limit as a monomer which has an aliphatic group and a polymerizable unsaturated group, For example, the natural or synthetic | combination terpene containing a C5 or C6 cyclopentyl or a cyclohexyl group is mentioned.
Further, other monomers that can be used in the copolymerization are not particularly limited. For example, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3- Examples include butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, and terpene-phenol resin.

<Aromatic tackifier>
The asphalt composition of this embodiment preferably uses an aromatic tackifier as a tackifier from the viewpoint of excellent tackiness and economy of the asphalt composition.
The aromatic tackifier is not particularly limited, and examples thereof include aromatic petroleum hydrocarbon resins (C9 resins) and C5 / C9 copolymer resins.
The aromatic tackifier has an aromatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. More preferably, the tackifier is 88% by mass or more, and more preferably 95% by mass or more. When the content of the aromatic hydrocarbon group is within the above range, the excellent tackiness and economy of the asphalt composition tend to be further improved.

  The aromatic tackifier can be produced by homopolymerizing or copolymerizing monomers each having an aromatic group and a polymerizable unsaturated group. The monomer having an aromatic group and a polymerizable unsaturated group is not particularly limited. For example, styrene, α-methylstyrene, vinyltoluene, methoxystyrene, TERT-butylstyrene, chlorostyrene, indene monomer (methylindene) Are included). Further, other monomers that can be used in the copolymerization are not particularly limited. For example, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3- Examples include butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, and terpene-phenol resin.

Although the compounding quantity of a tackifier is not specifically limited, From a viewpoint of the outstanding adhesiveness of an asphalt composition, 3.3 mass parts or more are preferable with respect to 100 mass parts of asphalt, and 8 mass parts or more are preferable. More preferably, 12 parts by mass or more is more preferable, and 15 parts by mass or more is even more preferable.
Further, from the viewpoint of excellent adhesiveness and economical efficiency in the low temperature region of the asphalt composition, 100 parts by mass or less is preferable, 70 parts by mass or less is more preferable, 50 parts by mass or less is further preferable, and 40 parts by mass or less is even more preferable. preferable.

(Combination agent)
The asphalt composition of this embodiment can mix | blend arbitrary compounding agents as needed.
The kind of compounding agent is not particularly limited as long as it is generally used for compounding thermoplastic resins and rubber-like polymers.
For example, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber Inorganic fillers such as carbon black, iron oxide and other pigments; Lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide; release agents, paraffinic process oils, Softeners and plasticizers such as naphthenic process oils, aromatic process oils, paraffins, organic polysiloxanes and mineral oils; synthetic liquid oligomers, hindered phenolic antioxidants, antioxidants such as phosphorus thermal stabilizers; Hi Dardamine-based light stabilizers, benzotriazole-based UV absorbers; flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, reinforcing agents such as metal whiskers, and coloring agents, other compounding agents, Examples thereof include those described in “rubber / plastic compounding chemicals” (edited by Rubber Digest, Japan). The compounding quantity of a compounding agent is not specifically limited, Usually, it is 85 mass parts or less with respect to 100 mass parts of asphalt.

(Softener)
Among the above-mentioned compounding agents, it is preferable to use a softener from the viewpoint of the low viscosity of the asphalt composition of the present embodiment, the low temperature of the asphalt composition, and the excellent tackiness in the normal temperature region. Although it does not specifically limit as a softening agent, For example, oils, a plasticizer, a synthetic liquid oligomer, and mixtures thereof are mentioned.
Among these, from the viewpoints of low viscosity of the asphalt composition, low temperature of the asphalt composition, excellent tackiness in the normal temperature region, and economical efficiency, it is preferable to include paraffinic process oil, naphthenic process oil, and aromatic process oil. .

The blending amount of the softening agent is not particularly limited, but from the viewpoint of low viscosity of the asphalt composition, low temperature of the asphalt composition, and excellent tackiness in the normal temperature region, It is preferably at least 4 parts by mass, more preferably at least 6 parts by mass, even more preferably at least 8 parts by mass.
In addition, from the viewpoint of a high softening point of the asphalt composition, excellent adhesiveness in the high temperature region of the asphalt composition, low oil bleeding property of the asphalt composition, and economical viewpoint, 83 parts by mass or less is preferable, and 60 parts by mass or less is more preferable. 40 parts by mass or less is more preferable, and 25 parts by mass or less is even more preferable.

The asphalt composition of the present embodiment preferably has the following composition from the viewpoint of the high softening point, low viscosity, high tackiness from low temperature to high temperature range, and oil bleed resistance of the asphalt composition.
Additive for asphalt-containing waterproof sheet: 5% by mass to 30% by mass Tackifier: 3% by mass to 30% by mass Softener: 2% by mass to 25% by mass Asphalt: 30% by mass to 90% by mass

  The content of the tackifier in the asphalt composition of the present embodiment is 3% by mass or more, preferably 6% by mass or more from the viewpoints of the softening point, 5 ° C. adhesive, 23 ° C. adhesive, and 50 ° C. adhesive. 10 mass% or more is more preferable, and 14 mass% or more is further more preferable. Further, from the viewpoint of 5 ° C. adhesive, 23 ° C. adhesive, 50 ° C. adhesive, and low temperature bending, it is 30% by mass or less, preferably 28% by mass or less, more preferably 26% by mass or less, and more preferably 24% by mass or less. Further preferred.

  The content of the softening agent in the asphalt composition of the present embodiment is 2% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more, and 6% by mass or more from the viewpoints of melt viscosity and low temperature bending. Is more preferable. Further, from the viewpoint of softening point, 5 ° C. adhesive, 23 ° C. adhesive, 50 ° C. adhesive, and oil bleed resistance, it is 25% by mass or less, preferably 23% by mass or less, more preferably 21% by mass or less, 18 mass% or less is more preferable.

  The asphalt content in the asphalt composition of the present embodiment is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and more preferably 45% by mass or more from the viewpoints of melt viscosity and economy. Further preferred. Moreover, from a viewpoint of a softening point and low temperature bending, it is 90 mass% or less, 88 mass% or less is preferable, 84 mass% or less is more preferable, and 80 mass% or less is further more preferable.

  It should be noted that the low temperature bendability required when processing asphalt compositions into waterproof sheets and installing them in a low temperature environment varies depending on the temperature and environment in which they are applied. When assuming winter etc., about −10 ° C., and assuming a colder environment, that is, a cold district, winter in a cold zone, etc., assumes −15 to −20 ° C. or lower, and the required low temperature resistance It can be adjusted according to performance.

(Rubber component and / or resin component other than additive (A) and additive (B))
The asphalt composition of this embodiment may contain the rubber component and / or resin component other than the additive for asphalt-containing waterproof sheets of this embodiment and additives (A) and (B) described above.
Examples of the rubber component include natural rubber and synthetic rubber.
Synthetic rubbers include, for example, polyisoprene rubber, polybutadiene rubber (BR), styrene butadiene rubber (SBR), modified styrene butadiene rubber (modified SBR), olefin elastomers such as ethylene propylene copolymer (EPDM), chloroprene rubber, Examples include acrylic rubber, ethylene vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer (EEA).

  Examples of the resin component include, but are not limited to, polyethylene (PE), low density polyethylene (low density PE), polyvinyl chloride (PVC), polyamide (PA), polystyrene (PS), acrylic resin, and polycarbonate (PC). , Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinylidene fluoride (PVDF), Teflon (registered trademark) (PTFE), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyimide (PI), polyamide Examples thereof include thermoplastic resins such as imide (PAI).

  The content of the rubber component and / or the resin component in the asphalt composition of the present embodiment is preferably 1 to 200 parts by mass with respect to 100 parts by mass of asphalt from the viewpoint of compatibility of the asphalt composition. The amount is more preferably 1 to 160 parts by mass, still more preferably 1 to 100 parts by mass, and even more preferably 2 to 100 parts by mass.

(Other ingredients)
It is preferable that the asphalt composition of this embodiment contains a crosslinking agent from the viewpoint of a high softening point and excellent compatibility of the asphalt composition. Although it does not specifically limit as a crosslinking agent, For example, sulfur, sulfur compounds, inorganic vulcanizing agents other than sulfur, oximes, nitroso compounds, polyamines, organic peroxides, resin crosslinking agents, isocyanate compounds, polyphosphoric acid, and crosslinking Auxiliaries are mentioned.

  The addition amount of the crosslinking agent in the asphalt composition is preferably 0.01% by mass or more from the viewpoint of excellent compatibility between the additive for asphalt composition and asphalt and a high softening point of the asphalt composition. % By mass or more is more preferable, 0.03% by mass or more is more preferable, and 0.05% by mass or more is even more preferable. Further, from the viewpoint of high penetration of the asphalt composition, low viscosity of the asphalt composition, and economical efficiency, it is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and 0.4% by mass or less. More preferably, 0.2 mass% or less is still more preferable.

[Method for producing asphalt composition]
Although it does not specifically limit regarding the manufacturing method of the asphalt composition of this embodiment, It is preferable to perform a mixing process at the temperature of 120 to 200 degreeC. The stirring time is usually 30 minutes to 6 hours, but a shorter one is preferable from the viewpoint of economy. The stirring speed may be appropriately selected depending on the apparatus to be used, but is usually 100 ppm or more and 8,000 rpm or less.

[Asphalt-containing tarpaulin]
The asphalt-containing waterproof sheet of the present embodiment includes the above-described asphalt composition.

Examples of the asphalt-containing waterproof sheet according to the present embodiment include, but are not limited to, a waterproof sheet for a heat method, a waterproof sheet for a torch method, a waterproof sheet for a cold method, and a roofing roof material.
From the viewpoint of the excellent adhesiveness of the asphalt composition, a waterproof sheet for a cooling method and a roofing roof material are particularly preferable.
In the present specification, the asphalt-containing tarpaulin includes all forms of products as long as the tarpaulin has a layer mainly composed of asphalt, and all the roof coverings having a layer composed mainly of asphalt. A product of the embodiment is included.
The asphalt-containing waterproof sheet containing the additive of the present embodiment is preferably a sheet having an adhesive layer.

  About the waterproofing sheet for cold construction method and / or the roof underlaying material, for example, it has the following layer structure, and becomes an antiblocking layer, an asphalt layer, a base material layer, an asphalt layer, an adhesive layer, and a release layer in order from the top. Yes. The asphalt composition of the present embodiment is particularly preferably used for the adhesive layer from the viewpoint of excellent adhesiveness.

  For example, the thickness of each layer is 0.003 mm to 1 mm for the anti-blocking layer, 0.05 mm to 5 mm for the asphalt layer, 0.01 mm to 10 mm for the base material layer, 0.05 mm to 5 mm for the adhesive layer, and the release layer. Is 0.003 mm to 1 mm.

Furthermore, the anti-blocking layer may be a plastic layer or a rubber layer, and may be a layer containing fine particles such as mineral powder.
In order to ensure adhesion between the anti-blocking layer and the asphalt layer, an anchor coat layer or a corona discharge treatment may be performed.
In addition, from the viewpoint of improving the weather resistance of the anti-blocking layer, the composition constituting the anti-blocking layer may contain an ultraviolet ray inhibitor, a stabilizer, and a pigment. A good plastic layer may be used.

The base material layer may be reinforced with a predetermined reinforcing material.
Although it will not specifically limit about the reinforcing material of a base material layer, if it is a material which has a function which reinforces a waterproof sheet, For example, a woven fabric, a nonwoven fabric, a film, etc. are mentioned.
Here, the nonwoven fabric and the woven fabric are made of synthetic resin fibers or chemical fibers, and are particularly preferably nonwoven fabrics made of synthetic resin fibers.
Here, the synthetic resin can be appropriately selected according to the intended waterproof sheet, for example, polyester such as aromatic polyester such as polyethylene terephthalate; polyamide such as nylon 6 or nylon 66; polyacrylonitrile, polyethylene or polypropylene, etc. And polyolefins.
These fibers can be used alone or in combination of two or more.
Although the fabric weight of a woven fabric and a nonwoven fabric is not specifically limited, From a viewpoint of construction workability, 30-300 g / m < ² > is preferable.
Moreover, the asphalt containing waterproof sheet of this embodiment is mentioned as a preferable form from the viewpoint of ensuring waterproof property as a base sheet which impregnated the said reinforcing material with asphalt or an asphalt composition.

  As the release layer, any one possessed by a general waterproof sheet can be used. For example, a release paper, a release film and the like can be used, and the material can be appropriately selected according to the intended waterproof sheet. . For example, a release paper obtained by laminating a polyolefin film such as low density polyethylene, high density polyethylene, or polypropylene on papermaking, or a release paper obtained by further performing silicone treatment on the release paper can be used.

The asphalt-containing waterproof sheet of the present embodiment may be provided with other layer configurations in addition to the above-described configuration.
For example, in order from the top, an anti-blocking layer, a base material layer, an adhesive layer, a release layer, a anti-blocking layer, an asphalt layer, a base material layer, an adhesive layer, a release layer, a release layer, an adhesive layer, Examples include an asphalt layer, a base material layer, an asphalt layer, an adhesive layer, and a release layer.
The overall width of the waterproof sheet is usually 1 to 3 m, and the length is 5 to 60 m.

[Method for producing asphalt-containing waterproof sheet]
The method for producing the asphalt-containing waterproof sheet of the present embodiment includes the above-described additive for asphalt-containing waterproof sheet of the present embodiment of 5% by mass to 30% by mass, the tackifier of 3% by mass to 30% by mass, It is preferable to have a step of forming a layer of asphalt composition containing 2% by mass to 25% by mass of a softening agent and 30% by mass to 90% by mass of asphalt.
Thereby, the layer of the asphalt composition excellent in the softening point, adhesiveness, low temperature bendability, melt viscosity, and oil bleed resistance can be formed.

[Use]
The asphalt-containing waterproof sheet of the present embodiment can be used in the fields of road pavement, roofing / waterproof sheet, and sealant, and particularly preferably in the field of roofing / waterproof sheet.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
Physical properties of additives for asphalt-containing waterproof sheets, additives (A) and additives (B) contained therein (sometimes collectively referred to as “additives” in this specification) in Examples and Comparative Examples. The measuring method is shown below.

<Content of vinyl aromatic monomer unit in additive (styrene content)>
A certain amount of additive was dissolved in chloroform and measured with an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450), and a calibration curve was obtained from the peak intensity of the absorption wavelength (262 nm) attributed to the vinyl aromatic compound (styrene). Was used to calculate the content of vinyl aromatic monomer units (styrene) in the additive.

<Vinyl aromatic monomer block content in additive>
As a measurement target, a polymer before hydrogenation which is an additive in a state before hydrogenation is used. M. Kolthoff, etal. , J .; Polym. Sci. 1, p. 429 (1946), the vinyl aromatic monomer block content in the polymer was measured by the osmium tetroxide method, and the vinyl aromatic monomer block content in the additive was obtained.
For decomposition of the polymer, an osmic acid 0.1 g / 125 mL tertiary butanol solution was used.

<Vinyl content in additive, hydrogenation rate of unsaturated group in conjugated diene>
The vinyl content in the additive and the hydrogenation rate of the unsaturated group in the conjugated diene were measured under the following conditions by nuclear magnetic resonance spectrum analysis (NMR).

In the measurement, the reaction solution after the hydrogenation reaction was poured into a large amount of methanol to precipitate and collect the block copolymer. Next, the block copolymer was extracted with acetone, and the extract was vacuum-dried and used as a sample for ¹ H-NMR measurement. The conditions for ¹ H-NMR measurement are described below.
(Measurement condition)
Measuring instrument: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Measurement sample: Extracted sample before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

<Ratio of vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in the additive (block ratio)>
It calculated by the following formula using the value of vinyl aromatic monomer block content and content of vinyl aromatic monomer unit determined by the above measurement method.
Block ratio = (vinyl aromatic monomer block content in additive) / (total content of vinyl aromatic monomer unit in additive) × 100

<Peak molecular weight>
The peak molecular weight of the block copolymer in the additive was measured by GPC (apparatus manufactured by Waters).
In GPC measurement, tetrahydrofuran was used as the solvent, and the temperature was set to 35 ° C. The molecular weight of the peak of the chromatogram was determined using a calibration curve (created using the peak molecular weight of standard polystyrene) determined from measurement of commercially available standard polystyrene. The said molecular weight was made into the peak molecular weight (polystyrene conversion molecular weight).

<Modification rate>
Applying the property of adsorbing the modified component to a GPC column with silica gel as a filler, the sample solution containing the sample and the low molecular weight internal standard polystyrene GPC of the standard polystyrene of the above <peak molecular weight> and silica type Both chromatograms of column GPC (Zorbax manufactured by DuPont) were measured, and the amount of adsorption on the silica column was measured from the difference between them to determine the modification rate of the additive.

<Mass ratio of block copolymer (a) and block copolymer (b), or block copolymers (c) and (d)>
The inflection point of each peak-to-peak curve obtained from the GPC is vertically divided, and the ratio of each divided area to the total area is the area ratio of each block copolymer component, and the mass ratio of each block copolymer Asked.
For each inflection point between peaks, peak division was performed by fitting processing by Gaussian approximation using EcoSEC waveform separation software, and a point where each peak intersected was defined as an inflection point.
In the following, “additive (A)” includes a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the hydrogenation rate of double bonds contained in the conjugated diene monomer unit is 10 mol%. More than 85mol%.
The “additive (B)” includes a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the hydrogenation rate of double bonds contained in the conjugated diene monomer unit is 0 mol%. .
The block copolymer (a) and the block copolymer (b) are constituents of the additive (A), and the block copolymer (a) is a polymer mainly composed of vinyl aromatic monomer units. A block copolymer containing a block and a polymer block mainly composed of a conjugated diene monomer unit and having a peak molecular weight of 30,000 to 150,000. The block copolymer (b) contains a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units. The ratio of the peak molecular weight of the block copolymer (b) to the peak molecular weight of the block copolymer (a) is 1.5 or more and less than 6.0.
The block copolymer (c) and the block copolymer (d) are constituents of the additive (B), and the block copolymer (c) is a polymer mainly composed of vinyl aromatic monomer units. It has a polymer block mainly composed of a block and a conjugated diene monomer unit.
The peak molecular weight of the block copolymer (c) is 50,000 to 150,000.
The block copolymer (d) has a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units.
The peak molecular weight of the block copolymer (d) is 1.5 to less than 6.0 times the peak molecular weight of the block copolymer (c).

<MFR>
The MFR of the additive was calculated by a method according to JIS K7210 using a melt indexer (L247; manufactured by TECHNOLSEVEN CO., LTD).
The test temperature was 200 ° C., the test load was 5.00 kgf, and the unit of the measured value was expressed in g / 10 minutes.

[Production of hydrogenation catalyst]
Into a reaction vessel purged with nitrogen, 1 L of dried and purified cyclohexane was added, 100 mmol of bis (cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. A hydrogenation catalyst was produced by reacting at room temperature for about 3 days.

[Method for producing additive]
The manufacturing method of an additive is shown below.
When the following additive contains two or more types of block copolymers, the additive includes a low molecular weight block copolymer (a) (with a peak molecular weight of 30,000 to 150,000), a high molecular weight Of the block copolymer (b) (peak molecular weight is 1.5 times or more and less than 6.0 times that of the block copolymer (a)). When it contains a coalescence, only the lowest molecular weight block copolymer is the block copolymer (a).

(Additive 1)
A predetermined amount of cyclohexane was placed in a jacketed tank reactor, and the temperature in the reactor was adjusted to 60 ° 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). Added. Further, a cyclohexane solution of TMEDA was added so that N, N, N ′, N′-tetramethylethylenediamine (hereinafter also referred to as “TMEDA”) was 0.30 mol with respect to 1 mol of n-butyllithium.

Thereafter, as a polymerization reaction in the first step, a cyclohexane solution (styrene monomer concentration of 15% by mass) containing 32 parts by mass of styrene monomer was supplied over about 10 minutes.
While supplying the styrene monomer, the temperature in the reactor was adjusted to 60 ° C.
After stopping the supply of styrene monomer, the reaction was continued for 15 minutes while adjusting the temperature in the reactor to 70 ° C.

Next, as a second polymerization reaction, a cyclohexane solution containing 68 parts by mass of butadiene monomer (butadiene monomer concentration: 15% by mass) was continuously supplied to the reactor at a constant rate over 50 minutes.
While supplying the butadiene monomer, the temperature in the reactor was adjusted to 70 ° C.
After stopping the supply of the butadiene monomer, the reaction was continued for 10 minutes while adjusting the temperature in the reactor to 70 ° C. to obtain a polystyrene-polybutadiene block copolymer.

  A part of the obtained polystyrene-polybutadiene block copolymer was extracted, and tetraethoxysilane was added as a coupling agent so that the molar ratio with respect to the total number of moles of n-butyllithium was 0.07, followed by a coupling reaction for 10 minutes. To obtain a coupling polymer.

Thereafter, the obtained coupling polymer was continuously hydrogenated at 80 ° C. using the hydrogenation catalyst produced as described above.
The catalyst amount was 50 ppm, the hydrogen pressure in the hydrogenation polymerizer was 0.8 MPa, and the average residence time was 30 minutes.
After the hydrogenation reaction, 0.25 parts by mass of stabilizer (octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) is added to 100 parts by mass of the coupling polymer. Additive 1 was obtained.

  The obtained additive 1 has a vinyl aromatic monomer unit content of 32% by mass, a vinyl aromatic monomer block content of 31.5% by mass, and a block ratio of 98.4%. Yes, the vinyl content of the conjugated diene monomer unit was 34 mol%, the hydrogenation rate was 48 mol%, and the MFR (200 ° C., 5 kgf) was 1.4 g / 10 min.

The structure and composition of Additive 1 are shown below.
S represents a styrene block, and B represents a butadiene block.
(SB): 70 mass%, peak molecular weight 73000
(SB) ₂ -X: 2% by mass, peak molecular weight 146000
(SB) ₃ -X: 18% by mass, peak molecular weight 205000
(SB) ₄ -X: 10% by mass, peak molecular weight 261000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, block copolymer (a) / block copolymer (b) = 70 mass% / 30 mass%
It becomes.

(Additive 2)
0.16 parts by mass of n-butyllithium and 0.34 mol of TMEDA were used, 35 parts by mass of styrene monomer was polymerized in the first step, and 65 parts by mass of butadiene monomer was polymerized in the second step. Other conditions were the same as those of additive 1 to obtain a coupling polymer.
Thereafter, hydrogenation was performed in the same manner as additive 1, and the same amount of stabilizer was added to obtain additive 2.

  The obtained additive 2 has a vinyl aromatic monomer unit content of 35.4% by mass, a vinyl aromatic monomer block content of 33.6% by mass, and a block ratio of 95.0%. %, The vinyl content of the conjugated diene monomer unit was 33 mol%, the hydrogenation rate was 50 mol%, and the MFR (200 ° C., 5 kgf) was 10.3 g / 10 min.

The structure and composition of Additive 2 are shown below.
(SB): 77 mass%, peak molecular weight 72000
(SB) ₂ -X: 2% by mass, peak molecular weight 152000
(SB) ₃ -X: 10% by mass, peak molecular weight 217000
(SB) ₄ -X: 11% by mass, peak molecular weight 274000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, block copolymer (a) / block copolymer (b) = 77 mass% / 23 mass%
It becomes.

(Additive 3)
Mixture of diglycidyl etherification modified product of 2,2-bis (4-hydroxyphenyl) propane with epichlorohydrin and diglycidyl etherified modified product of phenol / formaldehyde polycondensate with epichlorohydrin as a coupling agent Was added so that the molar ratio was 0.13 with respect to the total number of moles of n-butyllithium being 1.
Other conditions were the same as those of additive 1, and additive 3 was obtained.

  The obtained additive 3 has a vinyl aromatic monomer unit content of 32.2% by mass, a vinyl aromatic monomer block content of 31.6% by mass, and a block rate of 98.1. %, The vinyl content of the conjugated diene monomer unit was 34 mol%, the hydrogenation rate was 46 mol%, and the MFR (200 ° C., 5 kgf) was 7.4 g / 10 min.

The structure and composition of additive 3 are shown below.
(SB): 70 mass%, peak molecular weight 73000
(SB) ₂ -X: 30% by mass, peak molecular weight 146000
(SB) is a block copolymer (a).
(SB) _2- X is a block copolymer (b).
Therefore, block copolymer (a) / block copolymer (b) = 70 mass% / 30 mass%
It becomes.

(Additive 4)
After 0.09 parts by mass of n-butyllithium and 0.34 mol of TMEDA, 17 parts by mass of styrene monomer was polymerized in the first step, and 68 parts by mass of butadiene monomer was polymerized in the second step. A cyclohexane solution containing 15 parts by mass of a styrene monomer was supplied over about 10 minutes while maintaining the temperature of 70 ° C. After stopping the supply of the styrene monomer, the reaction was carried out for 15 minutes while adjusting the temperature in the reactor to 80 ° C., and the total number of moles of n-butyllithium was set to 1 for 1,3-dimethyl-2-imidazolidinone. It added so that the molar ratio with respect to a case might be set to 0.7, and it was made to react for 15 minutes, and the polystyrene-polybutadiene-polystyrene block copolymer was obtained. Thereafter, hydrogenation was performed in the same manner as additive 1, and the same amount of stabilizer was added to obtain additive 4.

  The resulting additive 4 has a vinyl aromatic monomer unit content of 31.5% by mass, a vinyl aromatic monomer block content of 31.2% by mass, and a block ratio of 99.0. %, The vinyl content of the conjugated diene monomer unit is 33 mol%, the hydrogenation rate is 49 mol%, the modification rate is 45.2%, and the MFR (200 ° C., 5 kgf) is 1 .2 g / 10 min.

The structure and composition of additive 4 are shown below.
(SBS): 100% by mass, peak molecular weight 130,000
(SBS) is a block copolymer (a).

(Additive 5)
A coupling agent was added except that 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane was added so that the molar ratio with respect to the total number of moles of n-butyllithium being 1 was 0.07. In the same manner as Agent 1, Additive 5 was obtained.

  The obtained additive 5 has a vinyl aromatic monomer unit content of 32.5% by mass, a vinyl aromatic monomer block content of 32.0% by mass, and a block ratio of 98.5. %, The vinyl content of the conjugated diene monomer unit was 33 mol%, the hydrogenation rate was 45 mol%, and the MFR (200 ° C., 5 kgf) was 1.2 g / 10 min.

The structure and composition of the additive 5 are shown below.
(SB): 67 mass%, peak molecular weight 72000
(SB) ₂ -X: 4% by mass, peak molecular weight 143000
(SB) ₃ -X: 12% by mass, peak molecular weight 208000
(SB) ₄ -X: 17% by mass, peak molecular weight 273000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, it becomes block copolymer (a) / block copolymer (b) = 67 mass% / 33 mass%.

(Additive 6)
In the first step, 15 parts by mass of styrene monomer is polymerized in the first step, and 85 parts by mass of butadiene monomer is polymerized in the second step. It added so that mol ratio with respect to the case where the total mol number of n-butyllithium was set to 1 may be set to 0.1. Other conditions were the same as those of additive 1 to obtain a coupling polymer. Thereafter, hydrogenation was performed in the same manner as additive 1, and the same amount of stabilizer was added to obtain additive 6.

  The obtained additive 6 has a vinyl aromatic monomer unit content of 16% by mass, a vinyl aromatic monomer block content of 15.7% by mass, and a block rate of 98.1%. Yes, the vinyl content of the conjugated diene monomer unit was 32 mol%, the hydrogenation rate was 42 mol%, and the MFR (200 ° C., 5 kgf) was 4.0 g / 10 min.

The structure and composition of the additive 6 are shown below.
(SB): 65% by mass, peak molecular weight 90000
(SB) ₂ -X: 6% by mass, peak molecular weight 180000
(SB) ₃ -X: 12% by mass, peak molecular weight 270000
(SB) ₄ -X: 17% by mass, peak molecular weight 360000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, block copolymer (a) / block copolymer (b) = 65 mass% / 35 mass%
It becomes.

(Additive 7)
In the first step, 47 parts by mass of styrene monomer was polymerized, and in the second step, 53 parts by mass of butadiene monomer were polymerized. Other conditions were the same as those of additive 1 to obtain a coupling polymer.
Thereafter, hydrogenation was performed in the same manner as additive 1, and the same amount of stabilizer was added to obtain additive 7.

  The obtained additive 7 has a vinyl aromatic monomer unit content of 47% by mass, a vinyl aromatic monomer block content of 46% by mass, and a block rate of 97.8%. The vinyl content of the conjugated diene monomer unit was 33 mol%, the hydrogenation rate was 49 mol%, and the MFR (200 ° C., 5 kgf) was 0.4 g / 10 min.

The structure and composition of additive 7 are shown below.
(SB): 71% by mass, peak molecular weight 70000
(SB) ₂ -X: 3% by mass, peak molecular weight 142000
(SB) ₃ -X: 17% by mass, peak molecular weight 209000
(SB) ₄ -X: 9% by mass, peak molecular weight 270000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, block copolymer (a) / block copolymer (b) = 71 mass% / 29 mass%
It becomes.

(Additive 8)
In the second step, the coupling agent was added so that the molar ratio with respect to the case where the total number of moles of n-butyllithium was 1 was 0.465. Other conditions were the same as those of additive 1 to obtain a coupling polymer.
Thereafter, hydrogenation was performed in the same manner as additive 1, and the same amount of stabilizer was added to obtain additive 8.

  The obtained additive 8 has a vinyl aromatic monomer unit content of 31% by mass, a vinyl aromatic monomer block content of 30.5% by mass, and a block rate of 98.3%. Yes, the vinyl content of the conjugated diene monomer unit was 33 mol%, the hydrogenation rate was 46 mol%, and the MFR (200 ° C., 5 kgf) was 0.1 g / 10 min.

The structure and composition of the additive 8 are shown below.
(SB): 20 mass%, peak molecular weight 72000
(SB) ₂ -X: 7% by mass, peak molecular weight 145000
(SB) ₃ -X: 42% by mass, peak molecular weight 207000
(SB) ₄ -X: 31% by mass, peak molecular weight 268000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, block copolymer (a) / block copolymer (b) = 20 mass% / 80 mass%
It becomes.

(Additive 9)
In the second step, the coupling agent was added so that the molar ratio with respect to the case where the total number of moles of n-butyllithium was 1 was 0.008. The other conditions were the same as in Additive 1 to obtain a polymer.
Thereafter, hydrogenation was performed in the same manner as additive 1 and the same amount of stabilizer was added to obtain additive 9.

  The obtained additive 9 has a vinyl aromatic monomer unit content of 31% by mass, a vinyl aromatic monomer block content of 30.4% by mass, and a block rate of 98.0%. Yes, the vinyl content of the conjugated diene monomer unit was 34 mol%, the hydrogenation rate was 48 mol%, and the MFR (200 ° C., 5 kgf) was 40.0 g / 10 min.

The structure and composition of the additive 9 are shown below.
(SB): 96 mass%, peak molecular weight 72000
(SB) ₂ -X: 0.5% by mass, peak molecular weight 143000
(SB) ₃ -X: 2% by mass, peak molecular weight 208000
(SB) ₄ -X: 1.5% by mass, peak molecular weight 269000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, it becomes block copolymer (a) / block copolymer (b) = 96 mass% / 4 mass%.

(Additive 10)
0.139 parts by mass of n-butyllithium and 0.02 mol of TMEDA, 31.5 parts by mass of styrene monomer in the first step, 68.5 parts by mass of butadiene monomer in the second step, Silicon tetrachloride was added as a ring agent so that the molar ratio with respect to the total number of moles of n-butyllithium was 0.045, and a coupling reaction was performed for 10 minutes.
After completion of the reaction, the block copolymer after the coupling reaction is added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the stabilizer (octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate). And 0.1 part by mass of (2-methyl-4,6-bis [(octylthio) methyl] -phenol) was added to obtain additive 10.

  The obtained additive 10 has a vinyl aromatic monomer unit content of 31.3% by mass, a vinyl aromatic monomer block content of 30.4% by mass, and a block ratio of 97.0. %, The vinyl content of the conjugated diene monomer unit was 12 mol%, the hydrogenation rate was 0 mol%, and the MFR (200 ° C., 5 kgf) was 14 g / 10 min.

The structure and composition of the additive 10 are shown below.
(SB): 80% by mass, peak molecular weight 90000
(SB) ₂ -X: 20% by mass, peak molecular weight 180,000
(SB) is a block copolymer (c).
(SB) _2- X is a block copolymer (d).
Therefore, block copolymer (c) / block copolymer (d) = 80 mass% / 20 mass%
It becomes.

(Additive 11)
A coupling polymer was obtained in the same manner as Additive 1.
Thereafter, the catalyst amount for hydrogenation was changed to 80 ppm. The other conditions were the same as for additive 1, hydrogenation was performed, the same amount of stabilizer was added, and additive 11 was obtained.

  The obtained additive 11 has a vinyl aromatic monomer unit content of 32% by mass, a vinyl aromatic monomer block content of 31.4% by mass, and a block rate of 98.1%. Yes, the vinyl content of the conjugated diene monomer unit was 33 mol%, the hydrogenation rate was 90 mol%, and the MFR (200 ° C., 5 kgf) was 0.1 g / 10 min.

The structure and composition of the additive 11 are shown below.
(SB): 67 mass%, peak molecular weight 71000
(SB) ₂ -X: 2% by mass, peak molecular weight 143000
(SB) ₃ -X: 19% by mass, peak molecular weight 206000
(SB) ₄ -X: 12% by mass, peak molecular weight 265000
(SB) is a block copolymer (a).
(SB) _2- X, (SB) _3- X, and (SB) _4- X are block copolymers (b).
Therefore, it becomes block copolymer (a) / block copolymer (b) = 67 mass% / 33 mass%.

(Additive 12)
Asaprene 1205 (styrene content 25%) manufactured by Asahi Kasei Co., Ltd., which is SBR, was used.

(Tackifier 1)
T-REZ RB-100 manufactured by JXTG Energy Co., which is a C5 petroleum resin, was used.

(Tackifier 2)
T-REZ RD-104 manufactured by JXTG Energy Co., which is a C5 / C9 petroleum resin, was used.

(Softener)
Diana process oil NS-90S manufactured by Idemitsu Co., Ltd., which is a naphthenic process oil, was used.

[Examples 1 to 19], [Comparative Examples 1 to 5]
<Method for producing asphalt composition>
500 g of straight asphalt 150-200 (manufactured by JX Energy) was put into a 750 mL metal can, and the metal can was sufficiently immersed in an oil bath at 180 ° C.
Next, while stirring the molten asphalt at a rotational speed of 5000 rpm, as shown in the following table, a predetermined amount of each additive, tackifier, and softener is added to the asphalt and stirred for 90 minutes after the addition. Asphalt composition was prepared.
The unit in the table is mass%.

<Evaluation of asphalt composition>
The physical properties of the asphalt compositions of Examples and Comparative Examples were measured by the following methods.
The measurement results are shown in the following table.

(Softening point)
According to JIS-K2207, the softening point of the asphalt composition was measured by the ring and ball method. When the sample is filled in the specified ring, supported horizontally in the glycerin liquid, a 3.5 g sphere is placed in the center of the sample, and the liquid temperature is increased at a rate of 5 ° C./min. Measured the temperature when touching the bottom plate of the ring base.
The higher the softening point of the asphalt composition, the better the flow resistance. Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
Softening point is 105 ° C or higher: ◎
Softening point 95 ° C or higher: ○
Softening point is 75 ° C or higher: △
Softening point less than 75 ° C: ×

(Melt viscosity)
The melt viscosity of the asphalt composition at 180 ° C. was measured with a Brookfield viscometer.
The lower the melt viscosity of the asphalt composition, the better the manufacturability, and it was evaluated as ◎, ○, Δ, × in order from the following criteria. Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
Melt viscosity is 850 mPa · s or less: ◎
Melt viscosity is 1500 mPa · s or less: ○
Melt viscosity is 2200 mPa · s or less: Δ
Melt viscosity exceeds 2200 mPa · s: ×

(5 ° C adhesive)
The produced asphalt composition was applied on an aluminum sheet (thickness: 100 μm) so as to have a thickness of about 100 μm.
Then, it cut out to the size of 120 mm x 25 mm, it affixed on the slate board using the press roller (speed 5cm / mm, 2kg load, 1 reciprocation), and was set as the sample for a measurement.
The affixed sample was cured for 30 minutes in a 5 ° C. constant temperature bath, and immediately after removal, the 180 ° peel force was measured at a peel rate of 300 mm / min.
The higher the asphalt composition is, the better the adhesiveness in the low temperature region when a waterproof sheet is produced using the asphalt composition. evaluated. Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
Adhesive strength 55N / 25mm or more: ◎
Adhesive strength is 40 N / 25 mm or more: ○
Adhesive strength is 30 N / 25 mm or more: Δ
Adhesive strength is less than 30 N / 25 mm: ×

(23 ° C adhesive)
A sample for measurement was prepared in the same manner as the evaluation of 5 ° C. adhesiveness, cured at room temperature of 23 ° C. for 30 minutes, and then the 180 ° peeling force was measured at a peeling speed of 300 mm / min.
The asphalt composition having higher adhesiveness at 23 ° C. has better adhesiveness in the normal temperature region when a waterproof sheet is produced using the asphalt composition, and in order from the following criteria, ◎, ○, Δ, × evaluated. Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
Adhesive strength 45N / 25mm or more: ◎
Adhesive strength is 38 N / 25 mm or more: ○
Adhesive strength is 30 N / 25 mm or more: Δ
Adhesive strength is less than 30 N / 25 mm: ×

(50 ° C adhesive)
A sample for measurement was prepared in the same manner as the evaluation of 5 ° C. adhesiveness, cured in a thermostatic bath at 50 ° C. for 30 minutes, and immediately after removal, the 180 ° peeling force was measured at a peeling speed of 300 mm / min.
The asphalt composition having higher adhesiveness at 50 ° C. has better adhesiveness in the high temperature region when a waterproof sheet is produced using the asphalt composition. evaluated. Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
Adhesive strength is 25N / 25mm or more: ◎
Adhesive strength is 21 N / 25 mm or more: ○
Adhesive strength is 17 N / 25 mm or more: Δ
Adhesive strength is less than 17 N / 25 mm: ×

(Oil bleed resistance ΔL *)
After cooling the prepared asphalt composition at room temperature, a specimen cut into a 2 cm square was placed on kraft paper, and was allowed to stand in a gear oven at 40 ° C. for 144 hours under a load of 250 g from the upper side.
Thereafter, using a colorimetric color difference meter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the lightness L * before and after the test was measured, and ΔL * of the difference was obtained.
The value of ΔL * correlates with the oil that oozes out on the kraft paper. The larger the oil oozes, the larger the absolute value of ΔL *. When the oil oozes out, the adhesive strength at the interface between the asphalt composition and the adherend decreases. That is, the smaller the oil seepage (the smaller the absolute value of ΔL *), the better the adhesion.
If an oil bleed is performed after the waterproof sheet is applied, the adhesive strength at the interface with the adherend is weakened and is easily peeled off. Therefore, the asphalt composition having higher oil bleed resistance has better waterproof sheet long-term adhesion, and was evaluated as ◎, ○, Δ, × in order from the following criteria.
Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
-1.6 or more: ◎
-2.0 or more: ○
-2.8 or more: △
Less than −2.8: ×

(Low temperature bending)
Using the prepared asphalt composition, pressing at 150 ° C. to produce a sheet having a thickness of 2 mm, cutting the sheet into a size of 20 mm × 100 mm, and immersing it in a temperature-adjusted dry ice-ethanol solution for 10 minutes or more The sheet was taken out and quickly wound around a metal rod having a diameter of 20 mm so as to bend the longitudinal direction of the sheet, and the lowest temperature at which no cracks or cracks occurred was measured.
The asphalt composition had better crack resistance when the temperature by low-temperature bending was lower, and was evaluated as 、, ○, Δ, and × in order from the following criteria. Above Δ, it was assumed that the performance was practically sufficient.
[Evaluation criteria]
−30 ° C. or less: ◎
−20 ° C. or less: ○
−10 ° C. or lower: Δ
Over -10 ° C: ×

  The asphalt composition to which the additive for asphalt-containing waterproof sheets of the present invention is added has industrial applicability in the fields of road paving, roofing and waterproofing sheets, and sealants, particularly roofing and waterproofing sheets. is doing.

Claims (12)

An additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein a hydrogenation rate of a double bond contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less. contains,
Additive for asphalt-containing tarpaulin. In the additive (A), the content of the vinyl aromatic monomer unit is 20% by mass or more and 45% by mass or less.
The additive for asphalt-containing waterproof sheets according to claim 1. The additive (A) contains the block copolymer (a) in an amount of 30% by mass to 95% by mass, the block copolymer (b) in an amount of 5% by mass to 70% by mass,
The block copolymer (a) contains a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units, and has a peak molecular weight of 30,000. A block copolymer of 150,000 or less and
The block copolymer (b) is a block copolymer containing a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units. ,
The ratio of the peak molecular weight of the block copolymer (b) to the peak molecular weight of the block copolymer (a) is 1.5 or more and less than 6.0.
The additive for asphalt-containing waterproof sheets according to claim 1 or 2. The block copolymer (b) includes a block copolymer (b-2),
The ratio of the weight average molecular weight of the block copolymer (b-2) to the weight average molecular weight of the block copolymer (a) is 2.4 or more and less than 3.5.
The additive for asphalt-containing waterproof sheets according to claim 3. The block copolymer (b) includes a block copolymer (b-3),
The ratio of the weight average molecular weight of the block copolymer (b-3) to the weight average molecular weight of the block copolymer (a) is 3.4 or more and less than 4.5.
The additive for asphalt-containing waterproof sheets according to claim 3 or 4. An additive (B) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the hydrogenation rate of the double bond contained in the conjugated diene monomer unit is 0 mol%,
The additive for asphalt containing waterproof sheets as described in any one of Claims 1 thru | or 5. The additive (A) is
Having 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;
The additive for asphalt containing waterproof sheets as described in any one of Claims 1 thru | or 6. The additive (B) is
Having 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;
The additive for asphalt-containing waterproof sheets according to claim 6 or 7. The additive for asphalt-containing waterproof sheets according to any one of claims 1 to 8,
3 to 30% by mass of a tackifier,
The softener is 2% by mass or more and 25% by mass or less,
Having a step of forming a layer of asphalt composition containing asphalt in an amount of 30% by mass to 90% by mass,
Manufacturing method of asphalt-containing waterproof sheet. The additive for asphalt-containing waterproof sheets according to any one of claims 1 to 8,
3 to 30% by mass of a tackifier,
The softener is 2% by mass or more and 25% by mass or less,
And asphalt, 30% by mass or more and 90% by mass or less,
An asphalt composition containing.   The asphalt composition of Claim 10 which further contains rubber components and / or resin components other than the additive for asphalt containing waterproof sheets as described in any one of Claims 1-8.   An asphalt-containing waterproof sheet comprising the asphalt composition according to claim 10 or 11.