DE102019107726A1 - Additive for bituminous waterproofing membrane, process for the production of a bituminous waterproofing membrane, bitumen composition and bituminous waterproofing membrane - Google Patents

Abstract

It is intended to provide an additive for bitumen-containing geomembranes, whereby a bitumen composition which achieves a low mixing temperature during production, has a high softening point, is excellent in low viscosity, high tack in a low temperature region up to a high temperature, causes less bleeding of oil and has excellent bending ability at low temperatures. The present invention provides an additive for bitumen-containing geomembranes comprising an additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less.

Description

FIELD OF THE INVENTION

The present invention relates to an additive for bitumen-containing geomembranes or bitumen layered sealing products, a method for producing a bitumen-containing geomembrane, a bitumen composition and a bitumen-containing geomembrane.

Description of the Related Art

So far, bitumen compositions have been widely used in applications such as pavements, geomembranes, sound barriers and roofing.

To use the bitumen compositions for various applications, many attempts have been made to improve the properties of bitumen by adding various polymers.

As polymers, for example, block copolymers having a conjugated diene monomer unit and a vinyl aromatic monomer unit are used.

In the production of bituminous roof sheets or bitumen waterproofing sheets, in recent years, a cold application method for bonding a roofing material having an auto-adhesion layer on the back side to a substrate has been frequently employed from the viewpoint of energy saving, environmental pollution reduction, work environment improvement and so on.

As the above-mentioned bitumen-containing bitumen compositions containing bitumen with added block copolymers, there have heretofore been disclosed bitumen compositions to which block copolymers having various specific structures have been added (see, for example, Japanese Patent Laid-Open Nos. 1-101371, 2006-299024 and 2001-164081).

The in the Japanese Patent Laid-Open Nos. 1-101371, 2006-299024 and 2001-164081 However, disclosed technologies are still insufficient from the viewpoint of balance of properties such as high softening point, excellent low viscosity and high tackiness in a range from low temperature to high temperature. Therefore, there is a need for further improvements.

Unfortunately, conventional prior art bitumen compositions, when mixed with other blending agents such as oils, also cause bleeding over time, leading to a deterioration in tackiness.

The construction of bitumen-containing geomembranes during the winter season can lead to cracks in the geomembranes during the unrolling of bent geomembranes during the bonding of the geomembranes.

Accordingly, to improve the low-temperature bendability of bitumen-containing liner sheets, it has been attempted to increase the amount of oil added to a bitumen composition or to add to the bitumen a styrene-butadiene-styrene copolymer having a degree of hydrogenation of 0%. Unfortunately, these attempts facilitate bleeding of the oil, etc., and sufficient physical property balance properties are not obtained. Therefore, there is a need for further improvements.

Accordingly, it is an object of the present invention to provide an additive for bitumen-containing geomembranes, whereby a bitumen composition can be obtained which achieves a low mixing temperature in manufacture, has a high softening point, is excellent in low viscosity, high tackiness in a range from a low temperature to a high temperature, causes less oil bleeding, and has excellent low temperature bendability.

SUMMARY OF THE INVENTION

The present inventors have made meticulous researches to solve the problems of the above-mentioned conventional techniques, and have subsequently completed the present invention by finding that an additive for bitumen-containing geomembranes containing a given polymer having a certain molecular structure is capable of giving a bitumen composition which gives a low mixing temperature during production, has a high softening point, is excellent in low viscosity, has high tack in a range from a low temperature to a high temperature, causes less bleeding of oil and has excellent bending ability at low temperatures.

More specifically, the present invention is as follows:

[1] An additive for bitumen-containing waterproof sheets comprising an additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less.

[2] Additive for bituminous membranes according to [1], where
the content of the vinyl aromatic monomer unit in the additive (A) is 20% by mass or more and 45% by mass or less.

• das Blockcopolymer (a) ein Blockcopolymer ist, das einen Polymerblock enthält, der hauptsächlich aus einer vinylaromatischen Monomereinheit aufgebaut ist, und einen Polymerblock, der hauptsächlich aus einer konjugierten Dienmonomereinheit aufgebaut ist, und das ein Peak-Molekulargewicht von 30000 oder größer und 150000 oder kleiner aufweist;
• das Blockcopolymer (b) ein Blockcopolymer ist, das einen Polymerblock enthält, der hauptsächlich aus einer vinylaromatischen Monomereinheit aufgebaut ist, und einen Polymerblock, der hauptsächlich aus einer konjugierten Dienmonomereinheit aufgebaut ist; und
• das Verhältnis des Peak-Molekulargewichts des Blockcopolymers (b) zum Peak-Molekulargewicht des Blockcopolymers (a) 1,5 oder mehr und weniger als 6,0 ist.

[3] An additive for bitumen-containing geomembranes according to [1] or [2], wherein the additive (A) has 30 mass% or more and 95 mass% or less of a block copolymer (a) and 5 mass% or more and 70 mass% % or less of a block copolymer (b), wherein:

• the block copolymer (a) is a block copolymer containing a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit and having a peak molecular weight of 30,000 or greater and 150,000 or smaller having;
• the block copolymer (b) is a block copolymer containing a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit; and
• 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.

[4] Additive for bituminous membranes according to [3], where
the block copolymer (b) comprises a block copolymer (b-2), wherein
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.

[5] Additive for bituminous membranes according to [3] or [4], where
the block copolymer (b) comprises a block copolymer (b-3), wherein
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.

[6] additive for bitumen-containing geomembranes according to any one of items [1] to [5], further comprising
an additive (B) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the degree of hydrogenation of double bonds contained in the conjugated diene monomer unit is 0 mol%.

[7] Additive for bituminous membranes according to any one of items [1] to [6], wherein
the addition (A)
has at least one functional group selected from the group consisting of a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group.

[8] Additive for bituminous membranes according to [6] or [7], where
the addition (B)
has at least one functional group selected from the group consisting of a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group.

• 5 Massen-% oder mehr und 30 Massen-% oder weniger eines Zusatzes für bitumenhaltige Dichtungsbahnen nach einem der Punkte [1] bis [8],
• 3 Massen-% oder mehr und 30 Massen-% oder weniger eines Klebrigmachers,
• 2 Massen-% oder mehr und 25 Massen-% oder weniger eines Weichmachers und
• 30 Massen-% oder mehr und 90 Massen-% oder weniger Bitumen.

[9] A process for producing a bitumen-containing geomembrane comprising the step
forming a layer of a bitumen composition comprising:

• 5 mass% or more and 30 mass% or less of an additive for bitumen-containing geomembranes according to any one of items [1] to [8],
• 3 mass% or more and 30 mass% or less of a tackifier,
• 2 mass% or more and 25 mass% or less of a plasticizer and
• 30 mass% or more and 90 mass% or less bitumen.

• 5 Massen-% oder mehr und 30 Massen-% oder weniger eines Zusatzes für bitumenhaltige Dichtungsbahnen nach einem der Punkte [1] bis [8];
• 3 Massen-% oder mehr und 30 Massen-% oder weniger eines Klebrigmachers;
• 2 Massen-% oder mehr und 25 Massen-% oder weniger eines Weichmachers; und
• 30 Massen-% oder mehr und 90 Massen-% oder weniger Bitumen.

[10] bitumen composition comprising:

• 5 mass% or more and 30 mass% or less of an additive for bitumen-containing geomembranes according to any one of items [1] to [8];
• 3 mass% or more and 30 mass% or less of a tackifier;
• 2 mass% or more and 25 mass% or less of a plasticizer; and
• 30 mass% or more and 90 mass% or less bitumen.

[11] The bitumen composition according to item [10], further comprising a rubber component and / or a resin component other than the additive for bitumen-containing waterproofing sheets according to any of [1] to [8].

[12] A bitumen-containing geomembrane comprising a bitumen composition according to [10] or [11].

The present invention can provide an additive for bituminous waterproofing sheets which can provide a bitumen composition which achieves a low mixing temperature during production, has a high softening point, has excellent low viscosity, high tackiness a range from a low temperature to a high temperature, causes less bleeding oil and has excellent bending ability at low temperatures.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Hereinafter, embodiments of the present invention (hereinafter referred to as "present embodiment") are described in detail.

The embodiments described below serve to illustrate the present invention and are not intended to limit the present invention to the content described below. Various changes or modifications may be made to the present invention without departing from the spirit of the present invention.

[Additive for bituminous waterproofing membrane]

The additive for bituminous waterproofing sheets of the present embodiment comprises:
an additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less.

In this context, the additive (A) consists of a block copolymer. A block copolymer forming unit is referred to as "a monomer unit" and is referred to simply as "a monomer", with "unit" omitted when describing it as a material for a polymer.

In this specification, the term "mainly composed of" 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, more preferably 90% by mass or more, and further preferably 95% by mass. % or more.

The upper limit is not particularly limited, and is preferably 100% by mass or less, or preferably 99% by mass or less.

(Structure of Addendum (A))

In the present embodiment, from the viewpoint of the high tackiness of a bitumen-containing geomembrane in a range from a low temperature to a high temperature, the additive (A) preferably comprises block copolymer (a) and block copolymer (b) which will be described later.

The block copolymer (a) is a low molecular weight component, and the block copolymer (b) is a high molecular weight component. The balance between the adhesiveness of a bitumen composition to an adhesive surface and the elasticity after bonding is important for the application of tackiness. A preferred embodiment contains the block copolymers (a) and (b) from the viewpoint that the combination of the low molecular weight component and the high molecular weight component enables the additive to be adjusted to the desired performance.

As the proportion of the block copolymer (a) as the low molecular weight component increases, the adhesiveness tends to be improved but the elasticity is lowered. On the other hand, as the proportion of the block copolymer (b) as the high molecular weight component increases, the adhesiveness tends to be lowered but the elasticity is improved. In particular, the bondability has a strong influence in the range of low temperatures, while the elasticity in the range of high temperatures has a strong influence.

The block copolymer (b) which is a high molecular weight component comprises a predetermined block copolymer (b-2), and 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 preferable 2.4 or more and less than 3.5, more preferably 2.5 or more and less than 3.4, and even more preferably 2.6 or more and less than 3.3.

The content of the block copolymer (b-2) is preferably in the range of 15 to 80% by mass in the block copolymer (b).

The block copolymer (b) containing the block copolymer (b-2) makes it possible to obtain an excellent balance between high-softening point properties and low viscosity of a bitumen composition.

The block copolymer (b) which is a high molecular weight component comprises a predetermined block copolymer (b-3), and 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 preferable 3.4 or more and less than 4.5, more preferably 3.4 or more and less than 4.4, more preferably 3.4 or more and less than 4.3.

The content of the block copolymer (b-3) is preferably in the range of 15 to 80% by mass in the block copolymer (b).

The block copolymer (b) containing the block copolymer (b-3) causes an excellent balance between high softening point properties and low viscosity of a bitumen composition to be obtained.

The block copolymer (a), which is a low molecular weight component contained in the additive (A), is a block copolymer containing a polymer block composed mainly of a vinyl aromatic compound Monomer unit, and a polymer block composed mainly of a conjugated diene monomer unit and having a peak molecular weight of 30,000 or greater and 150,000 or less. The block copolymer (b), which is a high molecular weight component contained in the additive (A), contains a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit.

The peak molecular weight of the block copolymer (b) is preferably 1.5 times or more and less than 6.0 times, more preferably 1.6 times, from the viewpoint of a high softening point and a low viscosity of the bitumen composition of the present embodiment. times or more and 5.8 times or less, more preferably 1.7 times or more, and 5.6 times or less the peak molecular weight of the block copolymer (a).

The peak molecular weights of the block copolymer (a) and the block copolymer (b) can be controlled by adjusting the amounts of monomers with respect to an initiator during the polymerization and / or adjusting the rate of the coupling reaction. Furthermore, the ratio between them can be set to the above-described numerical range.

The peak molecular weights of the block copolymers can be determined by a method described in the examples below.

The block copolymer (a) preferably has a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block composed mainly of a conjugated diene monomer unit from the viewpoint of the productivity of the block copolymer, the softening point of the bitumen composition and the viscosity of the bitumen composition.

The block copolymer (b) preferably has two or more polymer blocks composed mainly of a vinyl aromatic monomer unit and one or more polymer blocks mainly from the viewpoint of the productivity of the block copolymer, the softening point of the bitumen composition and the viscosity of the bitumen composition are constructed of a conjugated diene monomer unit.

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

$${\left(\text{S}-\text{B}\right)}_{\text{n}}$$

$$\text{B}-{\left(\text{S}-\text{B}\right)}_{\text{n}}$$

$$\text{S}-{\left(\text{B}-\text{S}\right)}_{\text{n}}$$

$$\text{S}-{\left(\text{B}-\text{S}\right)}_{\text{n}}-\text{X}$$

$${\left[{\left(\text{B}-\text{S}\right)}_{\text{k}}\right]}_{\text{m}}-\text{X}$$

$${\left[{\left(\text{S}-\text{B}\right)}_{\text{k}}-\text{S}\right]}_{\text{m}}-\text{X}$$

In the S-B and the formulas (i) to (vi), S represents a polymer block composed mainly of a vinyl aromatic monomer unit, and B represents a polymer block mainly composed of a conjugated diene monomer unit.

X represents a residue of a coupling agent or a residue of a polymerization initiator such as e.g. 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 the formulas (i) to (vi) may be the same or different.

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

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

Examples of the coupling agent include silicon tetrachloride, tin tetrachloride, epoxy compounds, polyhalogenated hydrocarbon compounds, carboxylic acid ester compounds, polyvinyl compounds, alkoxysilane compounds, halogenated silane compounds and ester compounds.

The block copolymer (b) may be a mixture of a coupled form in which X is a residue of a coupling agent and a block copolymer without X.

X is preferably a residue of a coupling agent consisting of an alkoxysilane compound or an epoxy compound from the viewpoint of thermal decomposition resistance of the block copolymer during production of the bitumen composition.

• Tetraalkoxysilanverbindungen wie Tetramethoxysilan und
• gleiche Typen von Verbindungen wie dieses;
• Tetraaryloxysilanverbindungen wie Tetraphenoxysilan und
• gleiche Typen von Verbindungen wie dieses;
• Alkylalkoxysilanverbindungen mit 2 oder 3 oder mehr Alkoxygruppen, wie Methyltriethoxysilan und gleiche Typen von Verbindungen wie dieses; Alkylaryloxysilanverbindungen mit 2 oder 3 oder mehr Aryloxygruppen, wie Methyltriphenoxysilan und gleiche Typen von Verbindungen wie diese;
• Alkenylalkoxysilanverbindungen mit 2 oder 3 oder mehr Alkoxygruppen, wie Vinyltrimethoxysilan und gleiche Typen von Verbindungen wie diese; und Halogenalkoxysilanverbindungen, wie Trimethoxychlorosilan und gleiche Typen von Verbindungen wie diese.

Examples of the alkoxysilane compound serving as a coupling agent include:

• Tetraalkoxysilane compounds such as tetramethoxysilane and
• same types of compounds as this one;
• Tetraaryloxysilane compounds such as tetraphenoxysilane and
• same types of compounds as this one;
• Alkylalkoxysilane compounds having 2 or 3 or more alkoxy groups such as methyltriethoxysilane and like types of compounds such as this; Alkylaryloxysilane compounds having 2 or 3 or more aryloxy groups such as methyltriphenoxysilane and like types of compounds such as these;
• Alkenylalkoxysilane compounds having 2 or 3 or more alkoxy groups such as vinyltrimethoxysilane and like types of compounds such as these; and haloalkoxysilane compounds such as trimethoxychlorosilane and like types of compounds such as these.

Among them, alkylalkoxysilane having 2 to 4 alkylalkoxy groups is preferable in view of the resistance to heat decomposition and the productivity of the block copolymer.

Examples of the epoxide compound serving as the coupling agent include polyepoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, epoxidized polybutadiene and epoxidized tetraallyl ether pentaerythritol.

Among them, an epoxy compound having a phenyl group is preferable from the viewpoint of the resistance to heat decomposition and the productivity of the block copolymer.

The number of the alkoxysilyl groups or epoxy groups in the alkoxysilane compound or the epoxy compound is preferably 2 to 5, more preferably 2 to 4, from the viewpoint of a low mixing temperature for the bitumen composition of the present embodiment, the low viscosity of the bitumen composition and a smaller degradation of a polymer in the bitumen composition. more preferably 3 to 4, more preferably 4, per molecule.

It is not necessarily that the boundary between the blocks or the most distant points of each block in the block copolymer are clearly visible.

For example, a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit may be present. Also, a plurality of the copolymer blocks may coexist with each other. The polymer block (S) composed mainly of a vinyl aromatic monomer unit may contain a plurality of segments differing in the content of the vinyl aromatic monomer unit.

The block copolymer (b) which is a high molecular weight component contained in the additive (A) preferably contains a block copolymer represented by (SB) _m -X (wherein m is a whole Number from 2 to 4, S is a polymer block composed mainly of a vinyl aromatic monomer unit, B is a polymer block composed mainly of a conjugated diene monomer unit, and X is a residue of a coupling agent or a residue of a polymerization initiator), and More preferably, a block copolymer represented by (SB) ₄ -X (wherein S is a polymer block mainly composed of a vinyl aromatic monomer unit, B is a polymer block composed mainly of a conjugated diene monomer unit, and X is a residue of a Coupling agent), from the viewpoint of a low mixing temperature during the production of the bitumen composition of the present embodiment, the low viscosity of the bitumen composition, the lower degradation of a polymer in the bitumen composition, and the high softening point of the bitumen composition.

The block copolymer (b) further preferably contains (SB) ₃ -X and (SB) ₄ -X from the viewpoint of low viscosity of the bitumen composition of the present embodiment and a high softening point of the bitumen composition.

The proportion of the block copolymer (a) relative to the total amount of the block copolymer (a) and the block copolymer (b) is preferably 30 mass% or from the viewpoint of a low mixing temperature for the bitumen composition, a low viscosity of the bitumen composition and a high tackiness of the bitumen composition more, more preferably 40% by mass or more, further preferably 50% by mass or more, still more preferably 60% by mass or more.

The content of the block copolymer (a) is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass from the viewpoint of high recovery after elongation of the bitumen composition and a high softening point of the bitumen composition. or less, more preferably 80 mass% or less.

In the present specification, the "recovery after expansion of the bitumen composition" refers to the property (elastic recovery) determined by molding the bitumen composition with a dumbbell-shaped shape, then cutting the central portion of the molded product, the molded product is stretched / stretched and then examined to see if the cut product restores the original length.

1. (1) Eine geschmolzene Bitumenzusammensetzung wird in eine Form mit Hantel-Form eingespritzt (z.B. Länge x Breite x Dicke = ca. 12 cm ×5 cm 5 cm ×1 cm).
2. (2) Eine kalte Bitumenzusammensetzung (mit beiden Enden an Spannvorrichtungen für die Hantel befestigt) wird in ein Wasserbad von 25°C gestellt.
3. (3) Beide Enden der Hantel werden von den Spannvorrichtungen gehalten und mit einer bestimmten Geschwindigkeit gezogen.
4. (4) Die Hantel wird auf 20 cm gestreckt, es wird gestoppt und dann wird ca. 5 Minuten lang gehalten.
5. (5) Während beide Enden der Hantel gehalten werden, wird die Hantel in der Mitte geschnitten.
6. (6) Die geschnittene Hantel versucht, ihre Länge (ca. 12 cm) von vor dem Strecken der Hantel (von der Länge von 20 cm - α einschließlich der beiden geschnittenen Teile unmittelbar nach dem Schneiden) wiederherzustellen, wenn die Kautschukelastizität erhalten bleibt. Daher wird der Grad der Wiederherstellung nach Ablauf der vorgegebenen Zeit gemessen. α stellt die bereits wiederhergestellte Länge der Hantel zum Zeitpunkt der Messung nach Ablauf der vorgegebenen Zeit dar.

Specifically, the recovery after elongation of the bitumen composition is determined by measurement according to the following process steps (1) to (6).

1. (1) A molten bitumen composition is injected into a dumbbell-shaped mold (eg, length x width x thickness = about 12 cm x 5 cm 5 cm x 1 cm).
2. (2) Place a cold bitumen composition (with both ends attached to dumbbell fixtures) in a 25 ° C water bath.
3. (3) Both ends of the dumbbell are held by the tensioners and pulled at a certain speed.
4. (4) The dumbbell is stretched to 20 cm, it is stopped and then held for about 5 minutes.
5. (5) While holding both ends of the dumbbell, the dumbbell is cut in the middle.
6. (6) The cut dumbbell tries to restore its length (about 12 cm) from before stretching the dumbbell (from the length of 20 cm - α including the two cut parts immediately after cutting), if the rubber elasticity is maintained. Therefore, the degree of restoration is measured after the lapse of the given time. α represents the already restored length of the dumbbell at the time of measurement after the predetermined time has elapsed.

The ratio of the block copolymer (b) to the total amount of the block copolymer (a) and the block copolymer (b) is preferably 5 mass% from the viewpoint of high recovery after elongation of the bitumen composition of the present embodiment, a high softening point of the bitumen composition, and excellent low temperature bendability of the bitumen composition. % or more, more preferably 10% by mass or more, further preferably 15% by mass or more, still more preferably 20% by mass or more.

The content of the block copolymer (b) is preferably 70 from the viewpoint of a low mixing temperature for the bitumen composition and a low viscosity of the bitumen composition Mass% or less, more preferably 65% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less. The higher molecular weight block copolymer (b) than the block copolymer (a) has higher rubber elasticity. It can therefore be considered that a relatively high proportion of the block copolymer (b) has a positive influence on characteristics such as the softening point and the low-temperature bendability of the bitumen composition to which the rubber elasticity contributes.

The peak molecular weight of the block copolymer (a) is 30000 or greater, preferably 40,000 or greater, preferably 45,000 or greater, from the viewpoint of a high softening point of the bitumen composition. The peak molecular weight of the block copolymer (a) is more preferable from the viewpoint of a low mixing temperature for the bitumen composition, a low viscosity of the bitumen composition, and a smaller degradation of a polymer in the bitumen composition of 150000 or smaller, preferably 130,000 or smaller, more preferably 120,000 or smaller 110,000 or smaller, more preferably 100,000 or smaller.

The peak molecular weight of the block copolymer (b) is 1.5 times to less than 6.0 times, preferably 1.7 to 5 times, from the viewpoint of a high softening point of the bitumen composition and a low viscosity of the bitumen composition and more preferably 1.8 to 4.5 times the peak molecular weight of the above-mentioned block copolymer (a).

When the block copolymer (b) (SB) _{m is} -X, the peak molecular weight of (SB) _m -X is preferably m times the peak molecular weight of the bitumen composition from the viewpoint of high softening point and high tensile recovery of the bitumen composition SB or SBX block copolymer (a). The peak molecular weight of each polymer can be determined by a method described in the examples mentioned later.

The content of the vinyl aromatic monomer unit in the additive (A) is preferably 20% by weight or more, more preferably 22% by weight or more, further preferably 24% by weight or more, still more preferably 26% by weight or more in view of a high softening point of the bitumen composition of the present embodiment and less degradation of a polymer in the bitumen composition.

The content of the vinyl aromatic monomer unit in the additive (A) is preferably 45% by weight or less, more preferably 42% by weight or less, more preferably 40% by weight or less, still more preferably 38% by weight or less from the viewpoint of excellent low-temperature bendability of the bitumen composition, excellent stickiness of the bitumen composition in a low-temperature region, low viscosity of the bitumen composition, and lower oil bleeding of the bitumen composition. The content of the vinyl aromatic monomer unit slightly influences the hardness of the additive (A) and is therefore considered to have a positive influence on the properties such as e.g. the low temperature bendability required for softness is set by setting the upper limit to a low value.

In this connection, the content of the vinyl aromatic monomer unit in the additive (A) is not the value of each component but the content of vinyl aromatic monomer units in the entire additive (A), i. the average content of the respective vinylaromatic monomer units of the components.

In the present embodiment, the content of the vinyl aromatic monomer unit in the additive (A) can be measured by a method described in the examples mentioned later.

The proportion of the vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units (block content) in the additive (A) is preferably 90% or higher, more preferably 93% or higher, further preferably 95% or higher, still more preferably 96% or higher in view of a high softening point of the bitumen composition and a high recovery after elongation of the bitumen composition.

The block content is preferably 99% or lower, more preferably 98% or lower, from the viewpoint of less degradation of a polymer in the bitumen composition and the elasticity of the bitumen composition.

The content of a vinyl aromatic monomer block content relative to the total content of vinyl aromatic monomer units (block portion) in the additive (A) can be determined according to (vinyl aromatic monomer block content in the additive) / (total content of vinyl aromatic monomer units in the additive) × 100.

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

The vinyl aromatic monomer block content in the additive (A) and the total content of the vinyl aromatic monomer units in the additive (A) can be determined by a method described in the examples mentioned later.

The content of the vinyl aromatic monomer block content relative to the total content of vinyl aromatic monomer units in the additive (A) can be made polar, for example, by adjusting the molecular weight, the polymerization temperature, the monomer addition rate, the time interval of addition between a monomer added first and a monomer added next Compound, a randomizing agent, the stirring rate of a polymerization reactor, etc are controlled.

Specifically, the block content can be set to 90% or higher and 99% or lower by a conjugated diene monomer unit after 1 minute or more and less than 21 minutes from the time point of reaching a peak temperature after completion of the polymerization of a vinyl aromatic monomer unit , and after a drop of 1 ° C or more from the peak temperature is added.

In this connection, the proportion of the vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units in the additive (A) is not the value of each component but a value of all the block copolymers contained therein, i. the average value of the components.

The melt flow rate (MFR, 200 ° C., 5 kgf) of the additive (A) is preferably 0.5 g / 10 min or more from the viewpoint of productivity, more preferably 0.75 g / 10 min or more, further preferably 1 g / 10 minutes or more.

The melt flow rate (MFR, 200 ° C, 5 kgf) of the additive (A) is, from the viewpoint of a small amount of a polymer added to the asphalt, i. a reduction in the amount of a polymer added to the asphalt, and from the viewpoint of tensile recovery, preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less, more preferably 30 g / 10 minutes or less.

In the additive (A), at least a part of the double bonds contained in the conjugated diene monomer unit in the polymer is from the viewpoint of a high softening point of the bitumen composition of the present embodiment, a high resistance of the polymer to thermal decomposition and a smaller oil bleeding of the bitumen composition hydrogenated.

In the above (A), the degree of hydrogenation of double bonds contained in the conjugated diene monomer unit is 10 mol% or more, preferably 20 mol% or more, more preferably 25 mol% or more, further preferably 35 mol% or more in view to a high softening point of the bitumen composition and a high resistance of the polymer to thermal decomposition.

In the above (A), the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 85 mol% or less, preferably 60 mol% or less from the viewpoint of excellent low-temperature bendability of the bitumen composition and excellent stickiness of a bituminous waterproof sheet in a low-temperature region. more preferably 55 mol% or less, more preferably 50 mol% or less. The hydrogenation shifts the glass transition temperature to a high temperature side in a low temperature region, and it is therefore believed that the low temperature bending ability required for softness in the low temperature region is lowered. However, the hydrogenation degree of 85% in mol or less is a problem-free value for practical use.

In the present specification, whether before or after hydrogenation, the conjugated diene monomer unit is referred to as a "conjugated diene monomer unit".

In particular, as a result of the polymerization of a conjugated diene monomer prior to hydrogenation, unsaturated bonds are present, while unsaturated bonds derived from the conjugated diene no longer exist after hydrogenation. However, a component derived from a conjugated diene monomer unit is also referred to as a "conjugated diene monomer unit" after hydrogenation.

The hydrogenation degree of double bonds can be controlled in the above-mentioned numerical range by adjusting the amount of added hydrogen or the hydrogenation reaction time in the hydrogenation step. In the present embodiment, the degree of hydrogenation can be determined by a method described in the later-mentioned Examples.

The vinyl content in the conjugated diene monomer unit before hydrogenation in the additive (A) contained in the bitumen-containing waterproofing agent additive of the present embodiment is preferably 8 mol% or more, more preferably 10 mol% or more, more preferably 12 mol% or more, more preferably 20 mol% or more, from the viewpoint of high compatibility with bitumen and a low viscosity of the bitumen composition. The vinyl content in the conjugated diene monomer unit before hydrogenation is preferably 50 mol% or less, more preferably 45 mol% or less, more preferably 42 mol% or less, still more preferably 38 mol, from the viewpoint of less degradation of a polymer in the bitumen composition. % Or less.

(Addition (B))

The bitumen-containing waterproof sheet additive of the present embodiment may contain an additive (B) in addition to the above-mentioned additive (A).

The additive (B) comprises a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 0 mol%.

The bitumen-containing waterproofing layer additive of the present embodiment preferably includes the additive (B) from the viewpoint of low viscosity of the bitumen composition of the present embodiment.

When using a later-mentioned tackifier, the bitumen-containing waterproof sheet additive of the present embodiment preferably includes (B) from the viewpoint of compatibility with the highly polar tackifier.

The additive (B) preferably comprises a block copolymer (c) and a block copolymer (d), which are derived from a low mixing temperature during production of the bitumen composition, a low viscosity of the bitumen composition, a high softening point of the bitumen composition and a high tack of a bitumen adhesive sheet differ from each other as described below.

The block copolymer (c) has a polymer block mainly composed of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit. The peak molecular weight of the block copolymer (c) is preferably 50,000 or more and 150,000 or less.

The block copolymer (d) has a polymer block mainly composed of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit.

The peak molecular weight of the block copolymer (d) is 1.5 times to less than 6 times the peak molecular weight of the block copolymer from the viewpoint of a low mixing temperature during production, a high softening point of the bitumen composition and a low viscosity of the bitumen composition (c).

The block copolymer (c) preferably has a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block composed mainly of a conjugated diene monomer unit, and the block copolymer (d) preferably has two or more Polymer blocks mainly composed of a vinyl aromatic monomer unit and one or more polymer blocks composed mainly of a conjugated diene monomer unit from the viewpoint of a low viscosity and a high softening point of the bitumen composition.

Examples of the structure of the block copolymer (c) may include structures of S-B and the formulas (i) to (iii) as in the above-mentioned block copolymer (a).

Examples of the structure of the block copolymer (d) may include structures of the formulas (i) to (vi) as in the above-mentioned block copolymer (b).

The additive (B) preferably contains block copolymers represented by SBS, (SB) ₂ -X and (SB) ₄ -X from the viewpoint of a high softening point of the bitumen composition and the tensile strength of the bitumen composition.

When the additive (B) comprises the block copolymer (c) and the block copolymer (d), the content of the block copolymer (c) with respect to the total mass of the additive (B) is from the viewpoint of a high softening point of the bitumen composition and an excellent low-temperature flexibility The bitumen composition is preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 85 mass% or less, still more preferably 80 mass% or less. The content of the block copolymer (c) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably from the viewpoint of high tackiness of the bitumen composition and a low viscosity of the bitumen composition 60 mass% or more.

The content of the block copolymer (d) relative to the total mass of the additive (B) is preferably 95% by mass or less, more preferably 80% by mass or less, more preferably from the viewpoint of low bitumen composition viscosity and high bitumen composition stickiness 60 mass% or less, still more preferably 40 mass% or less.

The content of the block copolymer (d) is preferably 5% by weight or more, more preferably 15% by weight or more, further preferably 40% by weight or more, from the viewpoint of high softening point of the bitumen composition and excellent low-temperature bending ability of the bitumen composition. even more preferably, 70% by weight or more.

The higher molecular weight block copolymer (d) than the block copolymer (c) has higher rubber elasticity. Therefore, it is considered that a relatively high proportion of the block copolymer (d) has a positive influence on characteristics such as e.g. the softening point and the low-temperature bendability of the bitumen composition to which the rubber elasticity contributes.

The additive (B) is preferably a mixture of SBS, (SB) ₂ -X (block copolymer (d)) and SB (block copolymer (c)), a mixture of (SB) ₃ -X (block copolymer (d)) and SB (Block copolymer (c)) or a mixture of (SB) ₄ -X (block copolymer (d)) and SB (block copolymer (c)). The additive (B) is more preferably a mixture of (SB) ₄ -X (block copolymer (d)) and SB (block copolymer (c), from the viewpoint of a high softening point of the bitumen composition, a low viscosity of the bitumen composition and the tackiness of the bitumen composition in a high temperature range )).

The peak molecular weight of the block copolymer (c) is preferably 50,000 or more, more preferably 60,000 or more, more preferably 70,000 or more, still more preferably 80,000 or more from the viewpoint of a high softening point. The peak molecular weight of the block copolymer (c) is preferably 150,000 or smaller, more preferably 130,000 or smaller, more preferably 120,000 or smaller, still more preferably 110,000 or smaller, from the viewpoint of a low mixing temperature during production and a low viscosity.

The peak molecular weight of the block copolymer (d) is 1.5 times to less than 6.0 times, preferably 1, from the viewpoint of a low mixing temperature during production, a high softening point of the bitumen composition and a low viscosity of the bitumen composition 7 to 5.0 times, more preferably 1.8 to 4.5 times, the peak molecular weight of the block copolymer (c).

The mass ratio between the block copolymer (c) and the block copolymer (d) is preferably 60 to 95/40 to 5, more preferably 65 to 95/35 to 5, from the viewpoint of viscosity and stickiness of the bitumen composition, particularly (c) / (d) , more preferably 70 to 90/30 to 10.

The content of the vinyl aromatic monomer unit in the additive (B) is preferably 8% by mass or more, more preferably 10% by mass or more, more preferably 12% by mass from the viewpoint of high softening point of the bitumen composition and less degradation of a polymer in the bitumen composition. % or more, more preferably 15 mass% or more.

The content of the vinyl aromatic monomer unit in the additive (B) is preferably 50 mass% or less, more preferably 46 mass% or less, more preferably 42 mass, from the viewpoint of excellent low-temperature bendability of the bitumen composition and excellent stickiness of a bitumen-containing geomembrane % or less, more preferably 35% by mass or less. The content of the vinyl aromatic monomer unit in the additive (B) slightly influences the hardness of the additive (B) and is therefore considered to have a positive influence on the property such as the content of (B). the low temperature bendability required for softness is set by setting the upper limit to a low value.

In this connection, the content of the vinyl aromatic monomer unit in the additive (B) is not the value of each component but the content of vinyl aromatic monomer units in the entire additive (B), i. the average content of the respective vinylaromatic monomer units of the components.

The content of the vinyl aromatic monomer unit in the additive (B) can be measured by a method described in the examples mentioned later.

The ratio of a vinyl aromatic monomer block content to the total vinyl aromatic monomer unit content (block ratio) in the additive (B) is preferably 90% or higher, more preferably 93% or higher, further preferably 95% or higher, still more preferably 96% or higher. in view of a high softening point of the bitumen composition and a high recovery after elongation of the bitumen composition.

The block fraction is preferably 99% or lower, more preferably 98% or lower, from the viewpoint of a low mixing temperature for the bitumen composition, a low viscosity of the bitumen composition, a smaller degradation of a polymer in the bitumen composition, and the flexibility of the bitumen composition.

The proportion of a vinyl aromatic monomer block content to the total content of vinyl aromatic monomer units (block ratio) in the additive (B) can be determined by (vinyl aromatic monomer block content in the additive (B)) / (total vinyl aromatic monomer content in the additive (B)) × 100.

In this connection, the vinyl aromatic monomer block means a polymer block mainly composed of a vinyl aromatic monomer unit.

In the present embodiment, the vinyl aromatic monomer block content in the additive (B) and the total content of the vinyl aromatic monomeric units in the additive (B) can be determined by a method described in the examples mentioned later.

The ratio of a vinyl aromatic monomer block content to the total vinyl aromatic monomer unit content in the additive (B) can be determined, for example, by adjusting the molecular weight, the polymerization temperature, the monomer addition rate, the time of addition between a monomer added first and a monomer added next, a polar compound Randomisierungsmittels, the stirring rate of a polymerization reactor, etc. are controlled.

Specifically, the block content can be set to, for example, 90% or higher and 99% or lower by adding a conjugated diene monomer unit after lapse of 1 minute or more and less than 21 minutes from the time of reaching a peak temperature after completion of the polymerization a vinyl aromatic monomer unit, and after decrease by 1 ° C or more from the peak temperature.

In this connection, the proportion of a vinylaromatic monomer block content to the total content of vinylaromatic monomer units in the addition (B) is not the value of each component but a value with respect to the additive (B) as a whole, ie, the average value of components.

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, more preferably 1 g / 10 min or more from a productivity point of view more.

The melt flow rate (MFR, 200 ° C., 5 kgf) of the additive (B) is preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less, further preferably 30 g / 10 minutes or less from the viewpoint of small amount of a polymer added to the bitumen, ie a reduction in the amount of a polymer added to the bitumen, and from the point of view of recovery from tensile stress.

The ratio / proportion of the above additive (A) to the total mass of the additive (A) and the additive (B) is preferably 8% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more even more preferably 20% by mass or more in terms of additive (A) / (additive (A) + additive (B)) × 100 (% by mass), from the viewpoint of less oil bleeding of bitumen composition and excellent tackiness Bitumen composition in a low temperature range. The proportion of the additive (A) is preferably 55% by mass or less, more preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably in view of a low viscosity of the bitumen composition and an excellent low-temperature flexibility of the bitumen composition 30 mass% or less.

The hydrogenation of the additive (A) shifts the glass transition temperature in a low-temperature region toward a high temperature. It is believed that a higher proportion of additive (A) tends to reduce softness in the low temperature range. In the case of blending additive (A) and additive (B) with equivalent polymer structures, it is therefore considered that a higher proportion of additive (B) produces better low-temperature bendability.

(Addition (A) and Addition (B))

The copolymer constituting the additive (A) and / or the additive (B) preferably has at least one functional group selected from the group consisting of from the standpoint of excellent stickiness of the bitumen composition of the present embodiment in a high temperature region and less oil bleeding of the bitumen composition a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group.

Among these functional groups, a functional group having a nitrogen atom is more preferable, and a functional group having a nitrogen atom and an oxygen atom is more preferable.

The additive (A) or (B) having the functional group interacts with a polar component in the bitumen and is thereby finely dispersed in the bitumen. This tends to prevent a low molecular weight component and a plasticizer in the bitumen composition from bleeding to the surface of the bitumen composition.

The functional group of the additive interacts with a polar group on the surface of an object to be bonded with a bitumen-containing geomembrane. This tends to result in excellent tack in a range from a low temperature to a high temperature.

Thus, the functional group of the additive (A) or (B) tends to preferably have a strong electronegative nitrogen atom and an oxygen atom. It is believed that the effect described above is as the number of functional groups increases. Both the additive (A) and the additive (B) preferably have the functional group.

Examples of the method for adding at least one functional group selected from the group consisting of a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group to which the additive (A) or (B) is added Copolymer, are methods using a polymerization initiator, a monomer or a final modifier having the functional group.

Among them, a method using an end modifier having the functional group is preferable from the viewpoint of easy production.

Examples of the monomer used for adding the predetermined functional group and the additive-forming copolymer are compounds having a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group or an alkoxysilane group in the monomer and are useful for the polymerization.

Among them, a monomer having an N group is preferable. Examples of these are N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-dibutylvinylbenzylamine, N, N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis (trimethylsilyl) aminoethylstyrene, 1- (4-N, N-dimethylaminophenyl) -1-phenylethylene, N, N -dimethyl-2- (4-vinylbenzyloxy) ethylamine, 4- (2-pyrrolidinoethyl) styrene, 4- (2- piperidinoethyl) styrene, 4- (2-hexamethyleneiminoethyl) styrene, 4- (2-morpholinoethyl) styrene, 4- (2-thiazinoethyl) styrene, 4- (2-N-methylpiperazinoethyl) styrene, 1 - ((4-vinylphenoxy) methyl) pyrrolidine and 1- (4-vinylbenzyloxymethyl) pyrrolidine.

Examples of the final modifier used for adding the predetermined functional group to the additive-forming copolymer include tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bisamino-methylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline , γ-caprolactone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, y-Glycidoxypropyltriphenoxysilan, y-glycidoxypropylmethyldimethoxysilane, γ-Glycidoxypropyldiethylethoxysilan, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane , β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β - (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethylpropyleneurea and N-methylpyrrolidone.

The amount of the end modifier used is preferably 0.5 to 5 equivalents per 1 equivalent of the living end of a base polymer.

[Method for producing an additive for bitumen-containing geomembranes]

The additive for bitumen-containing waterproofing sheets of the present embodiment can be prepared, for example, by, in order, a polymerization step of polymerizing at least one conjugated diene monomer and a vinyl aromatic monomer with a lithium compound as a polymerization initiator in a hydrocarbon solvent to obtain a polymer Hydrogenation step for hydrogenating, if necessary, double bonds in the conjugated diene monomer unit of the obtained polymer and a solvent removal step for removing a solvent from a solution containing the polymer.

The additive for bitumen-containing geomembranes of the present embodiment can also be prepared by preparing the above-mentioned additive (A) and additive (B), and mixing these additives.

(Polymerization)

In the polymerization step, monomers containing at least a conjugated diene monomer and a vinyl aromatic monomer are polymerized with a lithium compound as a polymerization initiator in a hydrocarbon solvent to obtain a polymer.

(Hydrocarbon solvent)

Examples of the hydrocarbon solvent for use in the polymerization step include: aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane and octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene. Only one of these solvents may be used alone, or two or more of them may be used as a mixture.

(Polymerization)

Examples of the lithium compound for use as the polymerization initiator in the polymerization step include compounds containing one or more lithium atoms bonded in the molecule, such as organic monolithium compounds, organic dilithium compounds and organic polylithium compounds.

Examples of such an organolithium compound include ethyllithium, n-propyllithium, isopropanol lithium, n-butyllithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium and isoprenyl dilithium. One of these organolithium compounds may be used singly or two or more of them may be used in combination.

(Monomer for use in polymerization)

Examples of the conjugated diene monomer include diolefins having a pair of conjugated double bonds such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3 Pentadiene, 2-methyl-1,3-pentadiene and 1,3-hexadiene. Among them, 1,3-butadiene or isoprene is preferable from the viewpoint of economy.

1,3-butadiene is more preferable from the viewpoint of mechanical strength. One of these diolefins may be used singly or two or more of them may be used in combination.

Examples of the vinyl aromatic monomer include vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethyl-styrene , Among them, styrene is preferable from the viewpoint of economy. One of these compounds may be used singly or two or more of them may be used in combination.

Besides the conjugated diene monomer and the vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer may be used as the polymerization monomers.

In the polymerization step, a predetermined polar compound or randomizing agent may be used to adjust, for example, the rate of polymerization, adjust the microstructure (ratios of cis, trans and vinyl) of a polymerized conjugated diene monomer unit, or adjust the reaction rate between the conjugated diene monomer and the vinyl aromatic monomer.

Examples of the polar compound or the randomizing agent include: ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; Amines such as triethylamine and tetramethylethylenediamine; and thioethers, phosphines, phosphoramides, alkylbenzenesulfonate and alkoxides of potassium or sodium.

The polymerization process carried out in the polymerization step is not particularly limited, and a method known in the art can be used therefor. Examples of methods known in the art include those disclosed in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. WO 00/19845 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 56-28925, Japanese Patent Publication No. 59-166518 and Japanese Patent Publication No. 60-186577.

(Deactivation step)

The active end of the polymer is preferably deactivated by a deactivation step. The method of deactivating the active end of the polymer can be achieved by reacting the active end with a compound having active hydrogen. The compound having active hydrogen is not particularly limited and is preferably an alcohol or water from the viewpoint of economy.

(Hydrogenation)

The hydrogenation step is the step in which a part of the double bonds in the conjugated diene monomer unit of the polymer obtained in the polymerization step is subjected to a hydrogenation reaction.

This step is carried out in the process for preparing the additive (A).

Examples of the hydrogenation catalyst for use in the hydrogenation reaction include: carrier type heterogeneous catalysts composed of a metal such as Ni, Pt, Pd or Ru and carried by a carrier such as carbon, silica, alumina or diatomaceous earth; so-called Ziegler catalysts in which an organic salt such as Ni, Co, Fe or Cr or acetylacetone salt and a reducing agent such as organic Al are used; so-called organic complex catalysts such as organometallic (e.g., Ru and Rh) compounds or homogeneous catalysts in which a reducing agent such as organic Li, organic Al or organic Mg is combined with a titanocene compound.

Among them, a homogeneous catalyst system having a reducing agent such as organic Li, organic Al or organic Mg together with a titanocene compound is preferable from the viewpoint of economy and heat aging resistance or weatherability of the polymer.

Examples of the hydrogenation process include those in the Japanese Patent Publication Nos. 42-8704 and 43-6636 described methods, preferably the method described in Japanese Patent Publication Nos. 63-4841 and 63-5401.

In particular, a hydrogenated block copolymer solution is obtained by hydrogenating in the presence of a hydrogenation catalyst in an inert solvent.

The hydrogenation reaction may be carried out using a batch process, a continuous process, and a combination thereof.

The hydrogenation reaction is not particularly limited and is preferably carried out from the above step of deactivating the active end of the polymer from the viewpoint of high hydrogenation activity.

The polymer of interest is obtained by adding predetermined hydrogen using the above hydrogenation catalyst. The degree of hydrogenation in the additive (A) can be adjusted to 10 mol% or more and 85 mol% or less by adjusting the number of moles of hydrogen to be added to the reaction system.

In the hydrogenation step, conjugated bonds in the vinyl aromatic monomer unit may be hydrogenated. The degree of hydrogenation of the conjugated bonds in all vinyl aromatic monomer units is preferably 30 mol% or less, more preferably 10 mol% or less, more preferably 3 mol% or less. The lower limit of the degree of hydrogenation of the conjugated bonds in all the vinyl aromatic monomers is not particularly limited, and is preferably 0 mol% or more, preferably 1 mol% or more. When the degree of hydrogenation of the conjugated bonds in all the vinyl aromatic monomers falls within the above-described range, there is a tendency that the amount of a polymer added to the bitumen is reduced or the compatibility with bitumen is improved.

(Solvent removal step)

The solvent removal step is the step of removing solvent from a solution containing the polymer.

Examples of the solvent removal method 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 mass% or less, more preferably 0.5 mass% or less, further preferably 0.2 mass% or less, still more preferably 0.05 mass% or less, more preferably 0.01 mass% or less. The lower limit of the amount of residual solvent in the copolymer is not is particularly limited, and is preferably a smaller amount, preferably 0% by mass, but is usually in the range of 0.01% by mass or more and 0.1% by mass or less from the viewpoint of economy during solvent removal.

From the viewpoint of the heat aging resistance of the copolymer and the suppression of gelation, an antioxidant is preferably added to the copolymer.

Examples of the antioxidant include: phenol antioxidants such as radical scavengers and phosphorus antioxidants or sulfur antioxidants such as peroxide decomposers.

Alternatively, an antioxidant may be used which has the properties of these two antioxidants. Only one of these antioxidants can be used alone or two or more of them can be used in combination.

Among the antioxidants, at least one phenol antioxidant is preferably added from the viewpoint of the heat aging resistance of the additives (A) and (B) and the bitumen composition and the suppression of gelation.

The amount of the phenol antioxidant added is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, per 100 from the viewpoint of high low-temperature productivity and less decomposition of the polymer during mixing Bulk parts of additives (A) and (B).

The amount of the phenol antioxidant added is preferably 1.00 parts by mass or smaller, more preferably 0.5 parts by mass or smaller, more preferably 0.4 parts by mass or smaller, still more preferably 0.3, from the viewpoint of high peeling strength of an aggregate and economy Parts by mass or smaller, per 100 parts by mass of the additives (A) and (B).

Further, before the solvent removal step, from the viewpoint of the color protection of the polymer and the improvement of the mechanical strength, a decalcification step for removing a metal in the polymer or a neutralizing step for adjusting the pH of the polymer, for example, by adding an acid or adding carbon dioxide may be performed become.

[Bitumen composition]

The bitumen composition of the present embodiment contains bitumen.

In the present specification, "bitumen composition" refers to a composition comprising bitumen and an additive polymer, the composition being prepared in the process of making a bitumen-containing geomembrane. The composition typically contains all the components that make up the bitumen-containing geomembrane and is cured to the bitumen-containing geomembrane.

(Bitumen)

Examples of the bitumen usable in the present embodiment include bitumen obtained as a by-product of petroleum refining (petroleum bitumen) or a natural product (natural bitumen), and mixtures thereof with petroleum.

The main component of the bitumen is also called bituminous mass.

Specific examples thereof include straight asphalt, semi-blown bitumen, blown bitumen, solvent deasphalted bitumen, tar, pitch, oil-offset cutback bitumen, and emulsion bitumen. Only one of these components can be used alone or two or more of them can be used as a mixture.

Alternatively, to each bitumen, a solvent-extracted oil of petroleum or an aromatic heavy oil such as an aromatic hydrocarbon process oil or extract may be added.

The bitumen for use in the bitumen composition of the present embodiment is preferably road pavement (straight asphalt) having a penetration (measured according to JIS-K 2207) of 30 from the viewpoint of high temperature physical properties, low temperature physical properties and economy or more and 300 or less, more preferably 40 or more and 250 or less, more preferably 45 or more and 200 or less.

The content of the bituminous waterproofing membrane additive of the above-mentioned embodiment in the bitumen composition of the present embodiment is 5% by mass or more, preferably 8% by mass or more, from the viewpoints of high softening point, high tackiness, excellent low-temperature flexing ability, and lower oil bleeding of the bitumen composition more, more preferably 10% by mass or more, further preferably 12% by mass or more.

The content of the bitumen-containing waterproofing membrane additive of the present embodiment is 30 mass% or less, preferably 27 mass% or less, more preferably 25 mass% or less, more preferably 23 mass%, from the viewpoint of low bitumen composition viscosity and economy. % Or less.

The total content of the additive (A) and the additive (B) in the bitumen composition of the present embodiment is 5 mass% or more, more preferably 8 mass% or more, more preferably 15 mass% or more, further preferably 21 mass% or more, from the viewpoint of a high softening point of the bitumen composition, an excellent low-temperature bendability of the bitumen composition, a high stickiness of the bitumen composition, and a smaller oil bleeding of the bitumen composition.

The total content of the additive (A) and the additive (B) in the bitumen composition is 30 mass% or less, preferably 27 mass% or less, more preferably 25 mass% or less, further preferably 23 mass% or less, below the point of view of a low mixing temperature for the bitumen composition, a low viscosity of the bitumen composition, a lesser degradation of a polymer in the bitumen composition and the economy.

The content of the bitumen in the bitumen composition of the present embodiment is 90% by mass or less, preferably 88% by mass or less, more preferably 84%, from the viewpoint of a high softening point of the bitumen composition, recovery from elongation of the bitumen composition and excellent low-temperature flexibility of the bitumen composition % or less, more preferably 80% by mass or less.

The content of the bitumen in the bitumen composition is 30% by mass or more, preferably 35% by mass or more, from the viewpoint of a low mixing temperature for the bitumen composition, a low viscosity of the bitumen composition, a smaller degradation of a polymer in the bitumen composition, and economy. more preferably 40% by mass or more, more preferably 45% by mass or more.

(Tackifier)

The bitumen composition of the present embodiment may contain, if desired, any tackifier selected from a variety of tackifiers.

The addition of the tackifier improves the tackiness of the bitumen composition and can thus suppress the detachment of a bitumen-containing geomembrane.

Examples of the tackifier include: rosin compounds such as natural rosin, modified rosin, natural rosin glycerin ester, modified rosin glycerol ester, natural rosin pentaerythritol ester, modified rosin pentaerythritol ester, hydrogenated rosin, and hydrogenated rosin pentaerythritol ester; Terpene compounds such as natural terpene copolymers, terpene polymers of natural terpene, aromatically modified terpene resin, hydrogenated derivatives of aromatic modified terpene resin, terpene phenolic resin, hydrogenated derivatives of terpene phenolic resin, terpene resin (monoterpene, diterpene, triterpene, polyterpene, etc.), hydrogenated terpene resin and hydrogenated derivatives of hydrogenated terpene resin; and petroleum hydrocarbon compounds or aromatic group-containing resins such as aliphatic petroleum hydrocarbon resin (C5 resin), hydrogenated derivatives of aliphatic petroleum hydrocarbon resin, aromatic petroleum hydrocarbon resin (C9 resin), hydrogenated derivatives of aromatic petroleum hydrocarbon resin, dicyclopentadiene resin, hydrogenated derivatives of dicyclopentadiene resin, C5 / C9 copolymer resin, hydrogenated derivatives of C5 / C9 copolymer resin, cyclic aliphatic petroleum hydrocarbon resin and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resin.

One of these tackifiers may be used singly or two or more of them may be used in combination. The C5 / C9 copolymer resin is a copolymerized petroleum resin obtained by polymerizing a mixture of a C5 fraction and a C9 fraction as a raw material.

<Aliphatic Tackifier>

The bitumen composition of the present embodiment preferably contains an aliphatic tackifier as a tackifier from the viewpoint of excellent stickiness of the bitumen composition and economy.

Examples of the aliphatic tackifier include aliphatic petroleum hydrocarbon resin (C5 resin), hydrogenated derivatives of aliphatic petroleum hydrocarbon resin (C5 resin), C5 / C9 copolymer resin and hydrogenated derivatives of C5 / C9 copolymer resin.

The aliphatic tackifier refers to a tackifier containing aliphatic hydrocarbon groups of preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 88% by mass or more, and still more preferably 95% by mass or more. When the content of aliphatic hydrocarbon groups falls within the above-described range, the excellent adhesion of the bitumen composition and the economy tend to be further improved.

The aliphatic tackifier can be prepared by homopolymerizing or copolymerizing a monomer having an aliphatic group and a polymerizable unsaturated group. Examples of the monomer having an aliphatic group and a polymerizable unsaturated group include natural or synthetic terpenes having a C5 or C6 cyclopentyl or cyclohexyl group.

Examples of other monomers that can be used in the copolymerization include 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2- Methyl 2-butene, cyclopentadiene, dicyclopentadiene, terpene and terpene phenolic resin.

<Aromatic tackifier>

In the bitumen composition of the present embodiment, it is preferable to use an aromatic tackifier as a tackifier from the viewpoint of excellent stickiness of the bitumen composition and economy.

Examples of the aromatic tackifier include aromatic petroleum hydrocarbon resin (C9 resin) and C5 / C9 copolymer resin.

The aromatic tackifier refers to a tackifier having an aromatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 88% by mass or more, and more preferably 95% by mass or more. When the content of aromatic hydrocarbon groups falls within the above-described range, the excellent adhesion of the bitumen composition and the economy tend to be further improved.

The aromatic tackifier can be prepared by homopolymerizing or copolymerizing a monomer having an aromatic group and a polymerizable unsaturated group. Examples of the monomer having an aromatic group and a polymerizable unsaturated group include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, tert-butylstyrene, chlorostyrene and indene monomers (including methylindene). Examples of other monomers that can be used in the copolymerization include 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2- Methyl 2-butene, cyclopentadiene, dicyclopentadiene, terpene and terpene phenolic resin.

The amount of the tackifier added is not particularly limited and is preferably 3.3 parts by mass or greater, more preferably 8 parts by mass or greater, more preferably 12 parts by mass or greater, still more preferably 15 parts by mass or greater, per 100 from the viewpoint of excellent stickiness of the bitumen composition Bulk parts of the bitumen.

The amount of the tackifier added is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, from the viewpoint of excellent stickiness of the bitumen composition in a low temperature range.

(Blend Component)

The bitumen composition of the present embodiment may be added with any mixture component if necessary.

The kind of the compounding ingredient is not particularly limited as long as the compounding ingredient is generally used for admixing with a thermoplastic resin or a rubbery polymer.

Examples thereof are: inorganic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titania, magnesia, zinc oxide, slag wool and glass fibers; Pigments such as carbon black and iron oxide; Lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate and ethylenebisstearamide; Plasticizers and pasting agents such as release agents, paraffin softener oil, naphthenic softening oil, aromatic process oil, paraffin, organic polysiloxane, and mineral oil; Antioxidants such as synthetic liquid oligomers, hindered phenol antioxidants and phosphorus heat stabilizers; hindered amine light stabilizers and benzotriazole ultraviolet absorbers; and flame retardants, antistatic agents, reinforcing agents such as organic fibers, glass fibers, carbon fibers and metal needles and dyes, and other blend ingredients, mixtures thereof, and the blend ingredients described in "Compounding Ingredients for Rubber and Plastics" (issued by Rubber Digest, Japan). The amount of the compounding ingredient added is not particularly limited, and is usually 85 parts by mass or less per 100 parts by mass of the bitumen.

(Plasticizer)

Among the above-mentioned compounding components, a plasticizer is preferably used from the viewpoint of low viscosity of the bitumen composition of the present embodiment and excellent tackiness of the bitumen composition in the low-temperature and the ordinary-temperature region. Examples of the plasticizer include oils, plasticizers, synthetic liquid oligomers, and mixtures thereof.

Among them, paraffin-type softening oil, naphthenic softening oil or aromatic process oil are preferably contained from the viewpoint of a low viscosity of the bitumen composition, an excellent stickiness of the bitumen composition in the low and normal temperature range, and economy.

The amount of the plasticizer added is not particularly limited, and is preferably 2.2 parts by mass or larger, more preferably 4 parts by mass or larger, further preferably 6 parts by mass or larger, from the viewpoint of a low viscosity of the bitumen composition and an excellent stickiness of the bitumen composition in the low-temperature and ordinary-temperature regions , even more preferably 8 parts by mass or greater, per 100 parts by mass of the bitumen.

The amount of the plasticizer added is preferably 83 parts by mass or smaller, more preferably 60 parts by mass or smaller, further preferably 40 parts by mass or smaller, still more preferably 25 parts by mass or smaller, from the viewpoint of high softening point of the bitumen composition, excellent stickiness of the bitumen composition in a high-temperature range , a lower oil bleeding of bitumen composition and economy.

The bitumen composition of the present embodiment preferably has the following composition from the viewpoint of a high softening point, a low viscosity, a high tack in a range from a low temperature to a high temperature, and the resistance of the bitumen composition to oil bleeding.

Addition for bituminous waterproofing membrane: 5 mass% or more and 30 mass% or less

Tackifier: 3 mass% or more and 30 mass% or less

Plasticizer: 2 mass% or more and 25 mass% or less.

Bitumen: 30 mass% or more and 90 mass% or less.

The content of the tackifier in the bitumen composition of the present embodiment is 3% by mass or more, preferably 6% by mass, from the viewpoint of softening point, tackiness at 5 ° C, tackiness at 23 ° C and tackiness at 50 ° C more, more preferably 10% by mass or more, further preferably 14% by mass or more. The content of the tackifier is 30% by mass or less, preferably 28% by mass or less, more preferably from the viewpoint of tackiness at 5 ° C, tackiness at 23 ° C, tackiness at 50 ° C, and low temperature flexing ability 26 mass% or less, more preferably 26 mass% or less, further preferably 24 mass% or less ,.

The content of the plasticizer in the bitumen composition of the present embodiment is 2% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more, further preferably 6% by mass or more from the viewpoints of melt viscosity and low-temperature flexibility , The content of the plasticizer is 25% by mass or less, preferably 23% by mass or less, from the viewpoint of softening point, tackiness at 5 ° C, tackiness at 23 ° C, tackiness at 50 ° C and resistance to oil bleeding , more preferably 21% by mass or less, more preferably 18% by mass or less.

The content of the bitumen in the bitumen composition of the present embodiment is 30 mass% or more, preferably 35 mass% or more, more preferably 40 mass% or more, further preferably 45 mass% or more, from the viewpoint of melt viscosity and economy , The bitumen content is 90% by mass or less, preferably 88% by mass or less, more preferably 84% by mass or less, more preferably 80% by mass or less from the viewpoint of the softening point and the low-temperature bending ability.

The low temperature bendability required to process the bitumen composition into a waterproof sheeting and to carry out construction in a low temperature environment varies depending on the building temperature or environment and is generally about -10 ° C at winter in, depending on the required low temperature resistance Areas with warm temperatures etc., or rather -15 to -20 ° C or below during winters in colder environments, ie cold regions or cold zones, etc., adjustable.

(Other rubber component and / or resin component as additive (A) and additive (B))

The bitumen composition of the present embodiment may contain a rubber component and / or resin component other than the bitumen-containing waterproofing agent additive of the present embodiment and the above-mentioned additives (A) and (B).

Examples of the rubber component are natural rubber and synthetic rubber.

Examples of the synthetic rubber are 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, acrylics. Rubber, an ethylene-vinyl acetate copolymer (EVA) and an ethylene-ethyl acrylate copolymer (EEA).

Examples of the resin component include thermoplastic resins such as polyethylene (PE), low-density polyethylene (PE), polyvinyl chloride (PVC), polyamide (PA), polystyrene (PS), acrylic resin, polycarbonate (PC), polyethylene terephthalate (PET) , Polybutylene terephthalate (PBT), Polyvinylidene fluoride (PVDF), Teflon® (PTFE), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyimide (PI) and polyamide-imide (PAI).

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

(Other components)

The bitumen composition of the present embodiment preferably contains a crosslinking agent from the viewpoint of a high softening point and excellent compatibility of the bitumen composition. Examples of the crosslinking agent include sulfur, sulfur compounds, inorganic vulcanizing agents other than sulfur, oximes, nitroso compounds, polyamine, organic peroxide, resin crosslinking agents, isocyanate compounds, polyphosphoric acid and crosslinking aids.

The amount of the crosslinking agent added to the bitumen composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further preferably 0.03% by mass or more, still more preferably 0.05% by mass or more from the standpoint of excellent compatibility of the additive for bitumen-containing geomembranes with the bitumen and a high softening point of the bitumen composition. The amount of the crosslinking agent added is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, more preferably 0.4% by mass, from the viewpoint of high penetration of the bitumen composition, low viscosity of the bitumen composition, and economy. % or less, more preferably 0.2% by mass or less.

[Method for producing a bitumen composition]

The method for producing the bitumen composition of the present embodiment is not particularly limited. Preferably, a mixing step is carried out at a temperature of 120 ° C or higher and 200 ° C or lower. A stirring time is usually 30 minutes to 6 hours. A shorter stirring time is more preferable from the viewpoint of economy. The stirring speed can be appropriately selected depending on the equipment used, and is usually 100 rpm or higher and 8000 rpm or lower.

[Bituminous waterproofing sheet or bituminous waterproofing membrane]

The bitumen-containing waterproofing sheet of the present embodiment has the above-mentioned bitumen composition.

Examples of the bitumen-containing waterproofing sheet of the present embodiment include, among others, geomembranes for a heat application method, geomembranes for a welding application method, geomembranes for a cold application method, and roofing materials.

A waterproofing sheet for a cold application method or a roofing material is particularly preferable from the viewpoint of excellent stickiness of the bitumen composition.

In this specification, the bitumen-containing liner sheet includes products in all forms as long as the geomembrane has a bitumen-main layer, and also includes products in all forms of roofing-material-forming materials having a bitumen-main layer.

The bitumen-containing sealing sheet containing the additive of the present embodiment is preferably a sheet having an adhesive layer.

The sealing sheet for a cold application method and / or the roofing material has, for example, the following layer structure: an anti-blocking layer, a bitumen layer, a carrier layer, a bitumen layer, an adhesive layer and a release layer in this order from above. The bitumen composition of the present embodiment is particularly preferably usable in the adhesive layer from the viewpoint of excellent tackiness.

The thickness of the individual layers is, for example, 0.003 mm to 1 mm for the antiblocking layer, 0.05 mm to 5 mm for the bitumen layer, 0.01 mm to 10 mm for the carrier layer, 0.05 mm to 5 mm for the adhesive layer and 0.003 mm to 1 mm for the release layer.

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 particles.

A primer layer may be provided or corona discharge treatment may be performed to ensure adhesion between the antiblock layer and the bitumen layer.

A composition constituting the anti-blocking layer may contain a UV protecting agent, a stabilizer and / or a pigment from the viewpoint of improving the weather resistance of the anti-blocking layer, or the anti-blocking layer may have a multilayer structure having a weatherproof plastic layer as the surface layer.

The carrier layer may be reinforced with a predetermined reinforcing material.

The reinforcing material for the carrier layer is not particularly limited as long as the material has the function of reinforcing a sealing sheet. Examples include fabrics, nonwovens and films.

In this connection, the nonwoven fabric or the fabric is made of synthetic resin fibers or chemical fibers. In particular, a nonwoven fabric of synthetic resin fibers is preferable.

In this context, the synthetic resin can be selected according to the desired geomembrane. Examples include: polyesters such as aromatic polyesters such as polyethylene terephthalate; Polyamides such as nylon 6 and nylon 66; and polyolefins such as polyacrylonitrile, polyethylene and polypropylene.

Only one of these fibers can be used alone or two or more of them can be used in combination.

The basis weight of the fabric or the nonwoven fabric is not particularly limited and is preferably 30 to 300 g / m ² from a technical viewpoint.

The shape of the bitumen-containing waterproofing sheet of the present embodiment is preferably a backing sheet of a reinforcing material impregnated with the bitumen or the bitumen composition from the viewpoint of ensuring tightness / waterproofness.

Any release layer that has a sheeting generally may be used. Examples include release paper and release films. The material can be selected according to the desired geomembrane. Examples include release paper constructed of paper coated with a film of polyolefin such as low density polyethylene, high density polyethylene or polypropylene, and release paper made by further treating the release paper with silicone.

The bitumen-containing sealing sheet of the present embodiment may comprise other layer structures in addition to the above-mentioned structure.

Examples thereof are a configuration consisting of an anti-blocking layer, a backing layer, an adhesive layer and a release layer, a configuration consisting of an anti-blocking layer, a bitumen layer, a carrier layer, an adhesive layer and a release layer, and a configuration consisting of a release layer, a Adhesive layer, a bitumen layer, a support layer, a bituminous layer, an adhesive layer and a release layer, in this order from above.

The total width of the geomembrane is usually 1 to 3 m and its length 5 to 60 m.

Process for producing a bitumen-containing geomembrane

The method for producing a bitumen-containing geomembrane according to the present embodiment preferably comprises the step of forming a layer of a bitumen composition containing 5 mass% or more and 30 mass% or less of the additive for bitumen-containing geomembranes the above-mentioned embodiment contains 3 mass% or more and 30 mass% or less of a tackifier, 2 mass% or more and 25 mass% or less of a plasticizer and 30 mass% or more and 90 mass% or less bitumen.

Thus, a layer of a bitumen composition which is excellent in softening point, tackiness, low-temperature bendability, melt viscosity, and oil bleeding resistance can be formed.

[Use]

The bitumen-containing geomembrane of the present embodiment can be used in the areas of road surface, roofing membranes or geomembranes and seals and can preferably be used in particular in the region of roofing membranes or geomembranes.

Examples

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples. However, the present invention is by no means limited to the examples given below.

Method for measuring the physical properties of the additive for bitumen-containing geomembranes and the additive contained therein (A) and additive (B) (in this description, collectively also referred to as "additive") in the examples and comparative examples are listed below.

<Content of vinyl aromatic monomer units (styrene content) in the additive>

A given amount of the additive was dissolved in chloroform and examined with an ultraviolet spectrophotometer (manufactured by Shimadzu Corp., UV-2450). The content of the vinyl aromatic monomer unit (styrene) in the additive was calculated using a calibration curve from the peak intensity of an absorption wavelength (262 nm) ascribed to a vinyl aromatic compound (styrene).

<Vinyl aromatic monomer block content in the additive>

A polymer prior to hydrogenation, which was the additive in an unhydrogenated state, was used as the object of investigation. The vinyl aromatic monomer block content in the polymer was characterized by the in Kolthoff, et al., J. Polym. Sci. 1, p. 429 (1946) described Osmiumtetraoxidverfahren to obtain the vinyl aromatic monomer block content in the additive.

A solution of 0.1 g of osmium tetraoxide in 125 ml of tertiary butanol was used in the decomposition of the polymer.

<Vinyl content in the addition and hydrogenation degree of conjugated diene unsaturated groups>

The vinyl content in the additive and the degree of hydrogenation of a conjugated diene unsaturated group were determined by nuclear magnetic resonance spectral analysis (NMR) under the following conditions.

For the measurement, a reaction solution after hydrogenation reaction was added to a large amount of methanol, so that a block copolymer was precipitated and recovered. Subsequently, the block copolymer was extracted with acetone.

The extract was dried in vacuo and used as a sample for ¹ H-NMR measurement. The conditions of the ¹ H-NMR measurement are described below.

(Measurement Conditions)

• Measuring device: JNM-LA400 (manufactured by JEOL Ltd.)
• Solvent: deuterated chloroform
• Sample: Products taken from the polymer before and after hydrogenation.
• Sample concentration: 50 mg / ml
• Observation frequency: 400 MHz
• Chemical shift standard: TMS (tetramethylsilane)
• Pulse delay: 2.904 sec.
• Number of scans: 64
• Pulse width: 45 °
• Measuring temperature: 26 ° C

<Ratio of the vinyl aromatic monomer content to the total content of vinyl aromatic monomer units (block ratio) in the additive>.

The block ratio was calculated according to the following expression using the vinyl aromatic monomer block content and the content of the vinyl aromatic monomer units determined by the measuring methods described above. $$\begin{array}{l}\text{block ratio}=(\text{vinylaromatic monomer block content}\\ \text{in addition})/(\text{Total content of vinyl aromatic}\\ \text{Monomer units in the additive})\times 100\end{array}$$

<Peak molecular weight>

The peak molecular weight of a block copolymer in the additive was measured by GPC [apparatus: manufactured by Waters Corp.].

In the GPC measurement, tetrahydrofuran was used as the solvent and the temperature was adjusted to 35 ° C. The peak molecular weight (peak) of a chromatogram was determined from a calibration curve (established using the peak molecular weight of standard polystyrene) determined from the measurement of standard commercial polystyrene. This molecular weight was considered as the peak molecular weight (polystyrene-based molecular weight).

<Modification>

Utilizing the property of adsorbing a modified component to a GPC column packed with silica gel as a packing, both a chromatogram of a GPC of the standard polystyrene as described in the previous paragraph <Peak Molecular Weight> and a Silaca Column GPC ( Zorbax manufactured by EI du Pont de Nemours and Company) for a sample solution containing a sample and standard low molecular weight internal polystyrene. The amount of component adsorbed on the silica column was determined from the difference between them to measure the degree of modification of the additive.

<Mass ratio between the block copolymers (a) and (b) or the block copolymers (c) and (d)>

The mass ratio of each block copolymer was determined by dividing vertically at each intermediate peak inflection point on a curve obtained from the above-described GPC and calculating the ratio of each separated area to the total area as the area ratio of each block copolymer component.

Each intermediate peak inflection point was defined as the intersection between peaks obtained by performing peak splitting by Gaussian approximation fitting with the waveform splitting software EcoSEC.

In the following description, "additive (A)" includes a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less.

The "additive (B)" includes a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 0 mol%.

The block copolymer (a) and the block copolymer (b) are components constituting the additive (A). The block copolymer (a) is a block copolymer containing a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block composed mainly of a conjugated diene monomer unit, and has a peak molecular weight of 30,000 or greater and 150,000 or less on. The block copolymer (b) contains a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit. 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 components constituting the additive (B). The block copolymer (c) has a polymer block mainly composed of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit.

The peak molecular weight of the block copolymer (c) is 50,000 or more and 150,000 or less.

The block copolymer (d) has a polymer block mainly composed of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit.

The peak molecular weight of the block copolymer (d) is 1.5 times 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 K 7210 with a melt index determiner (L247, manufactured by Technolseven Co., Ltd.).

The test temperature was 200 ° C and the test load was 5.00 kgf. The unit of a measured value was given by g / 10 min.

[Production of Hydrogenation Catalyst]

In a nitrogen-purged reaction vessel, 1 liter of dried and purified cyclohexane was placed, then 100 mmol of bis (cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with thorough stirring, followed by reaction at room temperature for about 3 days for the preparation of a hydrogenation catalyst.

[Method for producing additive]

The process for the preparation of the additive is given below.

When each of the additives described below contains two or more block copolymers, the additive is a mixture of a low molecular weight block copolymer (a) (peak molecular weight: 30,000 or greater and 150,000 or smaller) and a high molecular weight block copolymer (b) (Peak molecular weight: 1.5 times or greater and less than 6.0 times the peak molecular weight of the block copolymer (a)). In particular, when each of the additives described below contains three or more polymers, only the lowest molecular weight block copolymer is the block copolymer (a).

(Addition 1)

In a jacket tank reactor, a predetermined amount of cyclohexane was placed. The internal temperature of the reactor was adjusted to 60 ° C.

Then, n-butyllithium containing 0.14 parts by mass of n-butyllithium per 100 parts by mass of all monomers (total amount of butadiene monomer and styrene monomer added to the reactor) was added from the bottom of the reactor. A cyclohexane solution of N, N, N ', N'-tetramethylethylenediamine (hereinafter also referred to as "TMEDA") was further added with 0.30 mol of TMEDA per 1 mol of n-butyllithium.

Subsequently, to the reactor for the polymerization reaction in the first step, a cyclohexane solution containing 32 parts by mass of a styrene monomer (styrene monomer concentration: 15 mass%) was supplied over about 10 minutes.

During the supply of the styrene monomer, the internal temperature of the reactor was adjusted to 60 ° C.

After completion of the feeding of the styrenic monomer, the reaction was continued for 15 minutes while the internal temperature of the reactor was adjusted to 70 ° C.

Then, to the reactor for the polymerization reaction in the second step, a cyclohexane solution containing 68 parts by mass of a butadiene monomer (butadiene monomer concentration: 15 mass%) was continuously fed at a constant rate over 50 minutes.

During the supply of the butadiene monomer, the internal temperature of the reactor was adjusted to 70 ° C.

After completion of the supply of the butadiene monomer, the reaction was continued for 10 minutes while the internal temperature of the reactor was adjusted to 70 ° C to obtain a polystyrene-polybutadiene block copolymer.

A part of the obtained polystyrene-polybutadiene block copolymer was sampled. Tetraethoxysilane was added as a coupling agent in a molar ratio of 0.07 relative to the total moles of n-butyl lithium. The coupling reaction was carried out for 10 minutes to obtain a coupled polymer.

Subsequently, the obtained coupled polymer was hydrogenated continuously at 80 ° C using the above-mentioned hydrogenation catalyst.

The amount of the catalyst was 50 ppm, the hydrogen internal pressure of the hydrogenation polymerization reactor was 0.8 MPa, and the average residence time was 30 minutes.

After completion of the hydrogenation reaction, 0.25 mass parts of a stabilizer (octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) was added per 100 mass parts of the coupled polymer to obtain the additive 1.

The resulting additive 1 had a vinyl aromatic monomer content of 32% by mass, a vinyl aromatic monomer block content of 31.5% by weight, a block content of 98.4% by mass, a vinyl content of 34% by mol in the conjugated diene monomer unit, a hydrogenation degree of 48 mol% and an MFR (200 ° C, 5 kgf) of 1.4 g / 10 min.

The structure and composition of the additive 1 are shown below.

• (S-B): 70 Massen-%, Peak-Molekulargewicht 73000
• (S-B) ₂-X: 2 Massen-%, Peak-Molekulargewicht 146000
• (S-B) ₃-X: 18 Massen-%, Peak-Molekulargewicht 205000
• (S-B) ₄-X: 10 Massen-%, Peak-Molekulargewicht 261000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b) .

S represents a styrene block and B represents a butadiene block.

• (SB): 70 mass%, peak molecular weight 73,000
• (SB) ₂ -X: 2 mass%, peak molecular weight 146,000
• (SB) ₃ -X: 18 mass%, peak molecular weight 205,000
• (SB) ₄ -X: 10 mass%, peak molecular weight 261,000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 70 mass% / 30 mass%.

(Addition 2)

A coupled polymer was obtained under the same conditions as for additive 1 except that: 0.16 parts by mass of n-butyllithium were used; 0.34 mol of TMEDA was used; in the first step, 35 parts by mass of the styrene monomer were polymerized; and in the second step, 65 parts by mass of the butadiene monomer were polymerized.

Subsequently, the hydrogenation was carried out in the same manner as in the addition 1, and the same amount of the stabilizer was added to obtain the additive 2.

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

• (S-B): 77 Massen-%, Peak-Molekulargewicht 72000
• (S-B) ₂-X: 2 Massen-%, Peak-Molekulargewicht 152000
• (S-B) ₃-X: 10 Massen-%, Peak-Molekulargewicht 217000
• (S-B) ₄-X: 11 Massen-%, Peak-Molekulargewicht 274000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X sind das Blockcopolymer (b) .

The structure and the composition of the additive 2 are given below.

• (SB): 77 mass%, peak molecular weight 72,000
• (SB) ₂ -X: 2 mass%, peak molecular weight 152,000
• (SB) ₃ -X: 10 mass%, peak molecular weight 217,000
• (SB) ₄ -X: 11 mass%, peak molecular weight 274,000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X are the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 77 mass% / 23 mass%.

(Addition 3)

Additive 3 was obtained under the same conditions as for Additive 1 except that a mixture of a modified diglycidyl etherified product of 2,2-bis (4-hydroxyphenyl) propane with epichlorohydrin and a modified diglycidyl etherified product of a phenol-formaldehyde Polycondensate with epichlorohydrin as coupling agent in a molar ratio of 0.13 to the total moles of n-butyllithium, defined as 1, was added.

The obtained additive 3 had a content of vinyl aromatic monomer units of 32.2 mass%, a vinyl aromatic monomer block content of 31.6 mass%, a block content of 98.1%, a vinyl content of 34 mol% in the conjugated diene monomer unit Hydrogenation degree of 46 mol% and MFR (200 ° C, 5 kgf) of 7.4 g / 10 min.

• (S-B): 70 Massen-%, Peak-Molekulargewicht 73000
• (S-B) ₂-X: 30 Massen-%, Peak-Molekulargewicht 146000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X ist das Blockcopolymer (b).

The structure and the composition of the additive 3 are shown below.

• (SB): 70 mass%, peak molecular weight 73,000
• (SB) ₂ -X: 30 mass%, peak molecular weight 146,000
• (SB) is the block copolymer (a).
• (SB) ₂ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 70 mass% / 30 mass%.

(Addition 4)

n-Butyllithium was used at 0.09 mass parts. TMEDA was used at 0.34 mol. In the first step, 17 parts by mass of the styrene monomer were polymerized. In the second step, 68 parts by mass of the butadiene monomer were polymerized. Subsequently, a cyclohexane solution containing 15 parts by mass of the styrene monomer was supplied over about 10 minutes while maintaining the internal temperature of the reactor at 70 ° C. After completion of the supply of the styrene monomer, the reaction was continued for 15 minutes while the internal temperature of the reactor was adjusted to 80 ° C. 1,3-Dimethyl-2-imidazolidinone was added in a molar ratio of 0.7 to the total moles of n-butyllithium, defined as 1. The Reaction was carried out for 15 minutes to obtain a polystyrene-polybutadiene-polystyrene block copolymer. Subsequently, hydrogenation was carried out in the same manner as in the addition 1, and the same amount of the stabilizer was added to obtain the additive 4.

The obtained additive 4 had a content of vinyl aromatic monomer units of 31.5 mass%, a vinyl aromatic monomer block content of 31.2 mass%, a block content of 99.0%, a vinyl content of 33 mol% in the conjugated diene monomer unit, a degree of hydrogenation of 49 mol%, a degree of modification of 45.2% and a MFR (200 ° C, 5 kgf) of 1.2 g / 10 min.

• (S-B-S): 100 Massen-%, Peak-Molekulargewicht 130000
• (S-B-S) ist das Blockcopolymer (a).

The structure and composition of Supplement 4 are shown below.

• (SBS): 100 mass%, peak molecular weight 130,000
• (SBS) is the block copolymer (a).

(Addition 5)

Add 5 was obtained under the same conditions as for Add 1 except that 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane was added as a coupling agent in a molar ratio of 0.07 to the total moles of n-butyllithium, defined as 1 ,

The obtained additive 5 had a vinyl aromatic monomer content of 32.5 mass%, a vinyl aromatic monomer block content of 32.0 mass%, a block content of 98.5%, a vinyl content of 33 mol% in the conjugated diene monomer unit Hydrogenation degree of 45 mol% and MFR (200 ° C, 5 kgf) of 1.2 g / 10 min.

• (S-B): 67 Massen-%, Peak-Molekulargewicht 72000
• (S-B) ₂-X: 4 Massen-%, Peak-Molekulargewicht 143000
• (S-B) ₃-X: 12 Massen-%, Peak-Molekulargewicht 208000
• (S-B) ₄-X: 17 Massen-%, Peak-Molekulargewicht 273000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b) .

The structure and composition of the additive 5 are shown below.

• (SB): 67 mass%, peak molecular weight 72,000
• (SB) ₂ -X: 4 mass%, peak molecular weight 143,000
• (SB) ₃ -X: 12 mass%, peak molecular weight 208,000
• (SB) ₄ -X: 17 mass%, peak molecular weight 273,000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 67 mass% / 33 mass%.

(Addition 6)

A coupled polymer was obtained under the same conditions as for additive 1 except that: n-butyl lithium was used at 0.11 mass parts; 0.35 mol of TMEDA was used; 15 parts by mass of the styrene monomer were polymerized in the first step; in the second step, 85 parts by mass of the butadiene monomer were polymerized; and the coupling agent was added in a molar ratio of 0.1 to the total moles of n-butyllithium, defined as 1. Then, the hydrogenation was carried out in the same manner as in the additive 1, and the same amount of the stabilizer was added to obtain the additive 6.

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

• (S-B): 65 Massen-%, Peak-Molekulargewicht 90000
• (S-B) ₂-X: 6 Massen-%, Peak-Molekulargewicht 180000
• (S-B) ₃-X: 12 Massen-%, Peak-Molekulargewicht 270000
• (S-B) ₄-X: 17 Massen-%, Peak-Molekulargewicht 360000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b) .

The structure and composition of the additive 6 are shown below.

• (SB): 65 mass%, peak molecular weight 90000
• (SB) ₂ -X: 6 mass%, peak molecular weight 180,000
• (SB) ₃ -X: 12 mass%, peak molecular weight 270000
• (SB) ₄ -X: 17 mass%, peak molecular weight 360000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 65 mass% / 35 mass%.

(Addition 7)

A coupled polymer was obtained under the same conditions as in the additive 1 except that: in the first step, 47 parts by mass of the styrenic monomer was polymerized; and in the second step, 53 parts by mass of the butadiene monomer were polymerized.

Then, hydrogenation was carried out in the same manner as in the additive 1, and it became the same amount of the stabilizer to obtain the additive 7.

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

• (S-B): 71 Massen-%, Peak-Molekulargewicht 70000
• (S-B) ₂-X: 3 Massen-%, Peak-Molekulargewicht 142000
• (S-B) ₃-X: 17 Massen-%, Peak-Molekulargewicht 209000
• (S-B) ₄-X: 9 Massen-%, Peak-Molekulargewicht 270000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b).

The structure and composition of Supplement 7 are shown below.

• (SB): 71 mass%, peak molecular weight 70000
• (SB) ₂ -X: 3 mass%, peak molecular weight 142,000
• (SB) ₃ -X: 17 mass%, peak molecular weight 209,000
• (SB) ₄ -X: 9 mass%, peak molecular weight 270000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 71 mass% / 29 mass%.

(Addition 8)

A coupled polymer was obtained under the same conditions as in Additive 1, except that in the second step, the coupling agent was added in a molar ratio of 0.465 to the total moles of n-butyllithium, defined as 1.

Subsequently, hydrogenation was carried out in the same manner as in the addition 1, and the same amount of the stabilizer was added to obtain the additive 8.

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

• (S-B): 20 Massen-%, Peak-Molekulargewicht 72000
• (S-B) ₂-X: 7 Massen-%, Peak-Molekulargewicht 145000
• (S-B) ₃-X: 42 Massen-%, Peak-Molekulargewicht 207000
• (S-B) ₄-X: 31 Massen-%, Peak-Molekulargewicht 268000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b).

The structure and composition of Supplement 8 are given below.

• (SB): 20 mass%, peak molecular weight 72,000
• (SB) ₂ -X: 7 mass%, peak molecular weight 145,000
• (SB) ₃ -X: 42 mass%, peak molecular weight 207,000
• (SB) ₄ -X: 31 mass%, peak molecular weight 268,000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 20 mass% / 80 mass%.

(Addition 9)

A polymer was obtained under the same conditions as for additive 1 except that in the second step the coupling agent was added in a molar ratio of 0.008 to the total moles of n-butyllithium, defined as 1.

Then, hydrogenation was carried out in the same manner as in the addition 1, and the same amount of the stabilizer was added to obtain the additive 9.

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

• (S-B): 96 Massen-%, Peak-Molekulargewicht 72000
• (S-B) ₂-X: 0,5 Massen-%, Peak-Molekulargewicht 143000
• (S-B) ₃-X: 2% Massen-%, Peak-Molekulargewicht 208000
• (S-B) ₄-X: 1,5 Massen-%, Peak-Molekulargewicht 269000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b).

The structure and composition of Supplement 9 are given below.

• (SB): 96 mass%, peak molecular weight 72,000
• (SB) ₂ -X: 0.5 mass%, peak molecular weight 143,000
• (SB) ₃ -X: 2% mass%, peak molecular weight 208,000
• (SB) ₄ -X: 1.5 mass%, peak molecular weight 269000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 96 mass% / 4 mass%.

(Addition 10)

n-Butyllithium was used at 0.139 mass parts. TMEDA was used at 0.02 mol. In the first step, 31.5 parts by mass of the styrene monomer were polymerized. In the second step, 68.5 parts by mass of the butadiene monomer was polymerized, and silicon tetrachloride was added as a coupling agent in a molar ratio of 0.045 to the total moles of n-butyllithium. The coupling reaction was carried out for 10 minutes.

After completion of the reaction, 0.25 mass parts of the stabilizer (octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and 0.1 mass parts (2-methyl-4,6-bis [( octylthio) methyl] phenol) per 100 parts by mass of the block copolymer after the coupling reaction to obtain the addition of 10.

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

• (S-B): 80 Massen-%, Peak-Molekulargewicht 90000
• (S-B) ₂-X: 20 Massen-%, Peak-Molekulargewicht 180000
• (S-B) ist das Blockcopolymer (c).
• (S-B) ₂-X ist das Blockcopolymer (d).

The structure and composition of the additive 10 are shown below.

• (SB): 80 mass%, peak molecular weight 90000
• (SB) ₂ -X: 20 mass%, peak molecular weight 180,000
• (SB) is the block copolymer (c).
• (SB) ₂ -X is the block copolymer (d).

Accordingly, block copolymer (c) / block copolymer (d) = 80 mass% / 20 mass%.

(Addition 11)

A coupled polymer was obtained in the same manner as in the additive 1.

The hydrogenation was carried out under the same conditions as in Supplement 1, except that the amount of the hydrogenation catalyst was subsequently changed to 80 ppm. The same amount of stabilizer was added to obtain additive 11.

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

• (S-B): 67 Massen-%, Peak-Molekulargewicht 71000
• (S-B) ₂-X: 2 Massen-%, Peak-Molekulargewicht 143000
• (S-B) ₃-X: 19 Massen-%, Peak-Molekulargewicht 206000
• (S-B) ₄-X: 12 Massen-%, Peak-Molekulargewicht 265000
• (S-B) ist das Blockcopolymer (a).
• (S-B) ₂-X, (S-B) ₃-X oder (S-B) ₄-X ist das Blockcopolymer (b).

The structure and composition of the additive 11 are shown below.

• (SB): 67 mass%, peak molecular weight 71,000
• (SB) ₂ -X: 2 mass%, peak molecular weight 143,000
• (SB) ₃ -X: 19 mass%, peak molecular weight 206,000
• (SB) ₄ -X: 12 mass%, peak molecular weight 265,000
• (SB) is the block copolymer (a).
• (SB) ₂ -X, (SB) ₃ -X or (SB) ₄ -X is the block copolymer (b).

Accordingly, block copolymer (a) / block copolymer (b) = 67 mass% / 33 mass%.

(Addition 12)

Asapren 1205 (styrene amount: 25%), SBR manufactured by Asahi Kasei Corp. was used.

(Tackifier 1)

T-REZ RB-100, C5 petroleum resin manufactured by JXTG Nippon Oil & Energy Corp. was used.

(Tackifier 2)

T-REZ RD-104, C5 / C9 petroleum resin manufactured by JXTG Nippon Oil & Energy Corp. was used.

(Plasticizer)

Diana Process Oil NS-90S, naphthen softening oil manufactured by Idemitsu Kosan Co., Ltd., was used.

[Examples 1 to 19] and [Comparative Examples 1 to 5]. <Process for producing bitumen compositions>

Into a 750 ml metal can was placed 500 g of road bitumen 150-200 (manufactured by JXTG Nippon Oil & Energy Corp.). The metal can was dipped sufficiently in an oil bath of 180 ° C.

Then, while the bitumen was being stirred in a molten state at a revolution speed of 5000 rpm, predetermined amounts of each additive, a tackifier and a plasticizer as shown in the following tables were added to the asphalt. After the addition, the mixture was stirred for 90 minutes to prepare a bitumen composition.

The units in the tables are in mass%.

<Evaluation of bitumen composition>

The physical properties of the bitumen compositions of Examples and Comparative Examples were measured by the following methods.

The measurement results are shown in the following tables.

(Softening point)

The softening point of each bitumen composition was measured by the Ring & Ball method according to JIS-K 2207. A prescribed ring was filled with a sample and held in a horizontal position in a glycerin solution. A 3.5 g ball was placed in the middle of the sample. The temperature of the solution was increased by 5 ° C / min. The temperature at which the sample touched the bottom plate of the ring table due to the weight of the ball was measured.

A bitumen composition having a higher softening point has better resistance to flow. The sample was scored in the order of "best" with ⊚, ◯, △ and × according to the criteria given below. A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: The softening point was 105 ° C or higher.
• ◯: The softening point was 95 ° C or higher.
• △: The softening point was 75 ° C or higher.
• ×: The softening point was lower than 75 ° C.

(Melt viscosity)

The melt viscosity of each bitumen composition at 180 ° C was measured with a Brookfield viscometer.

A bitumen composition having a lower melt viscosity has better productivity. This was rated in the order from "best" with ⊚, ◯, △ and × according to the criteria given below. A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: The melt viscosity was 850 mPa · s or less.
• ◯: The melt viscosity was 1500 mPa · s or less.
• △: The melt viscosity was 2200 mPa · s or less.
• ×: The melt viscosity exceeded 2200 mPa · s.

(Stickiness at 5 ° C)

An aluminum foil (thickness: 100 μm) was coated with each produced bitumen composition with a thickness of about 100 μm.

Then, the film was cut into a size of 120 mm × 25 mm and adhered to a slate plate with a pressure roller (speed: 5 cm / mm, 2 kg load, 1 change motion) to prepare a sample for measurement.

The bonded sample was cured for 30 minutes in a 5 ° C thermostatic bath and removed. Immediately thereafter, the peel strength was measured at 180 degrees at a peel rate of 300 mm / min.

A bitumen composition having a higher tack at 5 ° C has better tack in a low temperature region during the manufacture of a geomembrane using the bitumen composition. The sample was scored in the order of "best" with ⊚, ◯, △ and × according to the criteria given below. A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: The adhesive strength was 55 N / 25 mm or more.
• ◯: The adhesive strength was 40 N / 25 mm or more.
• △: The adhesive strength was 30 N / 25 mm or more.
• ×: The adhesive strength was smaller than 30 N / 25 mm.

(Stickiness at 23 ° C)

A sample for measurement was prepared as in the evaluation of tackiness at 5 ° C and cured at room temperature (23 ° C) for 30 minutes. Then, peel strength was measured at 180 degrees at a peel rate of 300 mm / min.

A bitumen composition with higher tack at 23 ° C has better tackiness in a normal temperature range at the time of manufacturing a geomembrane using the bitumen composition. The sample was scored in the order of "best" with ⊚, ◯, △ and × according to the criteria given below. A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: The adhesive strength was 45 N / 25 mm or more.
• ◯: The adhesive strength was 38 N / 25 mm or more.
• △: The adhesive strength was 30 N / 25 mm or more.
• ×: The adhesive strength was smaller than 30 N / 25 mm.

(Stickiness at 50 ° C)

A sample for the measurement was prepared as in the evaluation of tackiness at 5 ° C, cured for 30 minutes in a thermostatic bath of 50 ° C and removed. Immediately thereafter, the peel strength was measured at 180 degrees at a peel rate of 300 mm / min.

A bitumen composition having a higher tack at 50 ° C has better tackiness in a high temperature region during the manufacture of a geomembrane using the bitumen composition. The sample was scored in the order of "best" with ⊚, ◯, △ and × according to the criteria given below. A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: The adhesive strength was 25 N / 25 mm or more.
• ◯: The adhesive strength was 21 N / 25 mm or more.
• △: The adhesive strength was 17 N / 25 mm or more.
• ×: The adhesive strength was smaller than 17 N / 25 mm.

(Resistance to oil bleeding ΔL *)

Each produced bitumen composition was cooled at normal temperature and cut into 2 cm squares. The resulting test piece was placed on kraft paper. From above, a load of 250 g was exercised. The test piece was allowed to stand for 144 hours in a gear oven at 40 ° C.

Then, the brightness L * before and after the test was measured with a colorimeter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) and ΔL * was determined as the difference of these values.

The value of ΔL * correlates with oil that has leaked onto / into the kraft paper. As oil bleeding increases, the absolute value of ΔL * increases. As oil bleeds, the adhesive strength at the interface between the bitumen composition and an adherend decreases. In particular, a sample with less oil bleeding (smaller absolute value of ΔL *) has a better adhesive strength.

After gluing a waterproofing membrane, oil bleeding weakens the adhesive strength at the interface with an adhesive surface and facilitates peeling. A bitumen composition with higher oil bleeding resistance thus gives a geomembrane a better durability. The sample was scored in the order of "best" with ⊚, ◯, △ and × according to the criteria given below.

A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: -1.6 or more.
• ◯: -2.0 or more.
• △: -2.8 or more.
• ×: Less than -2.8.

(Low temperature bendability)

A 2 mm thick sheet was made by pressing at 150 ° C with each produced bitumen composition. The web was cut to a size of 20 mm x 100 mm and immersed in a temperature-adjusted dry ice-ethanol solution for 10 minutes or more. Then, the web was taken out and quickly wound around a metal bar of 20 mm in diameter so that the web was bent in its longitudinal direction. The lowest temperature was measured at which neither cracks nor breaks occurred in the web.

A bitumen composition attributed to a lower temperature in low-temperature bendability has better crack resistance. The sample was scored in the order of "best" with ⊚, ◯, △ and × according to the criteria given below. A sample awarded △ or better was considered sufficient in practice.

[Evaluation Criteria]

• ⊚: -30°C oder niedriger.
• ◯: -20°C oder niedriger.
• △: -10°C oder niedriger.
• ×: höher als -10°C.

[Tabelle 1] Beispiel 1 2 3 4 5 6 7 8 9 10 Zusatz 1 15 Zusatz 2 15 Zusatz 3 15 Zusatz 4 15 Zusatz 5 15 Zusatz 6 15 2.5 Zusatz 7 15 Zusatz 8 15 Zusatz 9 15 Zusatz 10 12.5 Zusatz 11 Zusatz 12 Klebrigmacher 1 15 15 15 15 15 15 15 15 15 15 Klebrigmacher 2 Weichmacher 8 8 8 8 8 8 8 8 8 8 Bitumen 150-200 62 62 62 62 62 62 62 62 62 62 Erweichungspunkt ⊚ ⊚ ○ ○ ⊚ △ ⊚ ⊚ △ O Schmelzviskosität bei 180°C ○ ⊚ ○ ○ ○ △ △ △ ⊚ O Klebrigkeit bei 5°C ⊚ ⊚ ⊚ ⊚ ⊚ ○ ○ △ △ △ Klebrigkeit bei 23°C ○ ⊚ ○ ○ ○ ⊚ ○ △ ○ ○ Klebrigkeit bei 50°C ⊚ ○ ○ ⊚ ⊚ ○ ⊚ ○ △ △ Beständigkeit gegen Ölausbluten ΔL* ⊚ ○ ⊚ ⊚ ⊚ ⊚ △ ⊚ △ △ Biegefähigkeit bei niedriger Temperatur ○ ○ △ ○ ○ ⊚ △ ⊚ △ ○ [Tabelle 2] Beispiel 11 12 13 14 15 16 17 18 19 Zusatz 1 15 10 10 25 15 15 25 Zusatz 2 15 Zusatz 3 Zusatz 4 Zusatz 5 Zusatz 6 15 Zusatz 7 Zusatz 8 Zusatz 9 Zusatz 10 5 Zusatz 11 Zusatz 12 Klebrigmacher 1 10 10 15 20 25 Klebrigmacher 2 15 15 15 15 Weichmacher 8 8 8 8 8 10 15 8 15 Bitumen 150-200 62 62 62 62 72 55 55 57 35 Erweichungspunkt ○ ○ △ ○ ○ ⊚ △ ⊚ ⊚ Schmelzviskosität bei 180°C ⊚ ⊚ △ ⊚ ⊚ △ ⊚ ○ △ Klebrigkeit bei 5°C ⊚ ⊚ △ ○ ○ ⊚ ○ △ ⊚ Klebrigkeit bei 23°C ○ ⊚ △ △ ○ △ △ △ ○ Klebrigkeit bei 50°C ⊚ ○ ⊚ ○ △ ⊚ △ △ ○ Beständigkeit gegen Ölausbluten zlL* ⊚ ⊚ ⊚ ○ ○ ⊚ △ △ △ Biegefähigkeit bei niedriger Temperatur ○ ○ ⊚ ○ △ ⊚ ○ △ ⊚ [Tabelle 3] Vergleichsbeispiel 1 2 3 4 5 Zusatz 1 Zusatz 2 Zusatz 3 Zusatz 4 Zusatz 5 Zusatz 6 Zusatz 7 Zusatz 8 Zusatz 9 Zusatz 10 15 11,5 15 Zusatz 11 15 15 Zusatz 12 3,5 Klebrigmacher 1 15 15 15 Klebrigmacher 2 15 15 Weichmacher 8 8 8 8 8 Bitumen 150-200 62 62 62 62 62 Erweichungspunkt ○ ○ ○ ⊚ ○ Schmelzviskosität bei 180°C ⊚ ⊚ ⊚ ○ ○ Klebrigkeit bei 5°C × △ × × × Klebrigkeit bei 23°C × ○ △ ○ △ Klebrigkeit bei 50°C × × △ ⊚ △ Beständigkeit gegen Ölausbluten ΔL* × × × ⊚ ⊚ Biegefähigkeit bei niedriger Temperatur ○ ○ ○ × ×

• ⊚: -30 ° C or lower.
• ◯: -20 ° C or lower.
• △: -10 ° C or lower.
• ×: higher than -10 ° C.

[Table 1] example 1 2 3 4 5 6 7 8th 9 10 Addition 1 15 Addition 2 15 Addition 3 15 Addition 4 15 Addition 5 15 Addition 6 15 2.5 Addition 7 15 Addition 8 15 Addition 9 15 Addition 10 12.5 Addition 11 Addition 12 Tackifier 1 15 15 15 15 15 15 15 15 15 15 Tackifier 2 softener 8th 8th 8th 8th 8th 8th 8th 8th 8th 8th Bitumen 150-200 62 62 62 62 62 62 62 62 62 62 softening ⊚ ⊚ ○ ○ ⊚ △ ⊚ ⊚ △ O Melt viscosity at 180 ° C ○ ⊚ ○ ○ ○ △ △ △ ⊚ O Tack at 5 ° C ⊚ ⊚ ⊚ ⊚ ⊚ ○ ○ △ △ △ Tack at 23 ° C ○ ⊚ ○ ○ ○ ⊚ ○ △ ○ ○ Tack at 50 ° C ⊚ ○ ○ ⊚ ⊚ ○ ⊚ ○ △ △ Resistance to oil bleeding ΔL * ⊚ ○ ⊚ ⊚ ⊚ ⊚ △ ⊚ △ △ Flexibility at low temperature ○ ○ △ ○ ○ ⊚ △ ⊚ △ ○ [Table 2] example 11 12 13 14 15 16 17 18 19 Addition 1 15 10 10 25 15 15 25 Addition 2 15 Addition 3 Addition 4 Addition 5 Addition 6 15 Addition 7 Addition 8 Addition 9 Addition 10 5 Addition 11 Addition 12 Tackifier 1 10 10 15 20 25 Tackifier 2 15 15 15 15 softener 8th 8th 8th 8th 8th 10 15 8th 15 Bitumen 150-200 62 62 62 62 72 55 55 57 35 softening ○ ○ △ ○ ○ ⊚ △ ⊚ ⊚ Melt viscosity at 180 ° C ⊚ ⊚ △ ⊚ ⊚ △ ⊚ ○ △ Tack at 5 ° C ⊚ ⊚ △ ○ ○ ⊚ ○ △ ⊚ Tack at 23 ° C ○ ⊚ △ △ ○ △ △ △ ○ Tack at 50 ° C ⊚ ○ ⊚ ○ △ ⊚ △ △ ○ Resistance to oil bleeding zlL * ⊚ ⊚ ⊚ ○ ○ ⊚ △ △ △ Flexibility at low temperature ○ ○ ⊚ ○ △ ⊚ ○ △ ⊚ [Table 3] Comparative example 1 2 3 4 5 Addition 1 Addition 2 Addition 3 Addition 4 Addition 5 Addition 6 Addition 7 Addition 8 Addition 9 Addition 10 15 11.5 15 Addition 11 15 15 Addition 12 3.5 Tackifier 1 15 15 15 Tackifier 2 15 15 softener 8th 8th 8th 8th 8th Bitumen 150-200 62 62 62 62 62 softening ○ ○ ○ ⊚ ○ Melt viscosity at 180 ° C ⊚ ⊚ ⊚ ○ ○ Tack at 5 ° C × △ × × × Tack at 23 ° C × ○ △ ○ △ Tack at 50 ° C × × △ ⊚ △ Resistance to oil bleeding ΔL * × × × ⊚ ⊚ Flexibility at low temperature ○ ○ ○ × ×

A bitumen composition to which the additive for bitumen-containing geomembranes of the present invention is added is industrially applicable in the fields of pavements, roofing or waterproofing membranes and waterproofing, in particular in the area of roofing membranes or watertight membranes.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• JP 1101371 [0007]
• JP 2001164081 [0007]
• JP 428704 [0161]
• JP 436636 [0161]

Cited non-patent literature

• IN THE. Kolthoff, et al., J. Polym. Sci. 1, p. 429 (1946) [0256]

Claims (12)

An additive for bitumen-containing geomembranes comprising an additive (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the degree of hydrogenation of the double bonds contained in the conjugated diene monomer unit is 10 mol% or more and 85 mol% or less. Additive for bituminous membranes after Claim 1 wherein the content of the vinyl aromatic monomer unit in the additive (A) is 20% by mass or more and 45% by mass or less. Additive for bituminous membranes after Claim 1 or 2 wherein the additive (A) comprises 30 mass% or more and 95 mass% or less of a block copolymer (a) and 5 mass% or more and 70 mass% or less of a block copolymer (b), wherein: the block copolymer (a) a block copolymer containing a polymer block composed mainly of a vinyl aromatic monomer unit and having a polymer block composed mainly of a conjugated diene monomer unit and having a peak molecular weight of 30,000 or greater and 150,000 or less; the block copolymer (b) is a block copolymer containing a polymer block composed mainly of a vinyl aromatic monomer unit and a polymer block mainly composed of a conjugated diene monomer unit; and 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. Additive for bituminous membranes after Claim 3 wherein the block copolymer (b) comprises a block copolymer (b-2), wherein 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 is. Additive for bituminous membranes after Claim 3 or 4 wherein the block copolymer (b) comprises a block copolymer (b-3) wherein 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 is. Additive for bituminous membranes according to one of Claims 1 to 5 compound further comprising an additive (B) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, wherein the degree of hydrogenation of double bonds contained in the conjugated diene monomer unit is 0 mol%. Additive for bituminous membranes according to one of Claims 1 to 6 wherein the additive (A) has at least one functional group selected from the group consisting of a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group. Additive for bituminous membranes after Claim 6 or 7 wherein the additive (B) has at least one functional group selected from the group consisting of a hydroxy group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group and an alkoxysilane group. A method of making a bitumen-containing geomembrane, comprising the step of forming a layer of bitumen composition containing: 5 mass% or more and 30 mass% or less of an additive for bitumen-containing geomembranes according to one of Claims 1 to 8th , 3 mass% or more and 30 mass% or less of a tackifier, 2 mass% or more and 25 mass% or less of a plasticizer and 30 mass% or more and 90 mass% or less of bitumen. A bitumen composition comprising: 5 mass% or more and 30 mass% or less of an additive for bitumen-containing geomembranes according to any one of Claims 1 to 8th ; 3 mass% or more and 30 mass% or less of a tackifier; 2 mass% or more and 25 mass% or less of a plasticizer; and 30 mass% or more and 90 mass% or less bitumen. Bitumen composition after Claim 10 , further comprising a rubber component and / or a resin component, which of the additive for bituminous membranes according to one of the Claims 1 to 8th is different. Bitumen-containing geomembranes comprising a bitumen composition Claim 10 or 11 ,