JPH11315187A - Block copolymer composition for modifying asphalt and asphalt composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent asphalt solubility, or the like, and used for providing asphalt compositions having high softening points, high elongations, or the like, by compounding two kinds of specific block copolymers and specifying bulk density, or the like. SOLUTION: This block copolymer composition for modifying asphalt comprises (A) 98-20 wt.% of a block copolymer comprising two or more of (a) polymer blocks consisting mainly of (i) a monoalkenyl aromatic compound and one or more of (b) polymer blocks consisting mainly of (ii) a dienic compound and (B) 2-80 wt.% of a block copolymer having a mol.wt. of 1/3 to 2/3 based on that of the component A and comprising one or more of the component (a) and one or more of the component (b). The components A and B have each a total component (i) content of 10-50 wt.% and a vinylic bond content of <=70 wt.% in the component (ii), and the block copolymer composition has an MI (G condition) of 0.3-15.0, a bulk density of 0.1-0.7, a particle distribution having a 5 mesh-nonpassing particle content of <=30 wt.% and a 20 mesh-passing particle content of <=30 wt.%, and a total pore volume of 100-2,000 mm<3> /g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a monoalkenyl aromatic compound-conjugated diene-block copolymer composition. In particular, the present invention has a high softening point and excellent elongation, further excellent balance between physical properties such as mechanical strength and workability, and further excellent storage stability asphalt composition, for example for drainage pavement Asphalt composition suitable for the asphalt, and a block copolymer composition for asphalt modification having extremely excellent solubility in asphalt having a specific structure and a specific shape as an asphalt modifier for providing the asphalt composition And provide.

[0002]

2. Description of the Related Art Hitherto, asphalt compositions have been widely used for applications such as road pavement, waterproof sheets, sound insulation sheets, and roofing. At that time, many attempts have been made to add various polymers to asphalt to improve its properties. Specific examples of the polymer include an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a rubber latex, a block copolymer composed of butadiene and a vinyl aromatic compound, and the like.

However, ethylene-vinyl acetate copolymers and ethylene-ethyl acrylate copolymers are not preferable because the low-temperature properties of the asphalt composition are inferior and cracks occur in winter. In addition, the elongation characteristics are inferior, and therefore the binding force (tenacity) is also inferior. In particular, in the case of road pavement, the characteristics of grasping the aggregate are inferior. In the case of rubber latex, there is an economical or process problem that extra heating is required to evaporate water in the latex.

[0004] In recent years, with the increase in the number of vehicles passing on the road or the increase in speed, there has been a demand for better strength and abrasion resistance for heavy traffic roads and highway roads, and further, drainage performance. The demand for high-performance asphalt compositions (asphalt binders for drainage pavement) for construction of high porosity pavement roads for the purpose of improvement and noise reduction has also increased, and machines with higher softening points, toughness, tenacity, etc. Target strength is needed.

[0005] Further, there are some new problems such as a decrease in the performance of the asphalt composition due to a decrease in the quality of the straight asphalt accompanying an improvement in the degree of refining in petroleum refining, and a stability during storage of the asphalt composition due to long-term storage. Has occurred. Stability during storage means that performance after storage at high temperature, for example, a phenomenon such as phase softening point, which is lowered as a whole, and a phase difference between the upper layer and the lower layer, which causes a difference in performance, is observed. Such a phenomenon has not been solved so far and has been a major problem.

[0006] In order to solve these problems, an attempt has been made to improve, for example, by increasing the molecular weight of the block copolymer. However, simply increasing the molecular weight improves mechanical strength, but increases the melt viscosity, resulting in problems such as remarkably sacrificing workability such as road pavement. As for the storage stability, when the molecular weight is increased, the stability is greatly reduced, and no improvement effect is observed.

[0007] As a higher performance asphalt composition having a higher softening point, an asphalt composition to which a block copolymer having a specific molecular structure is added has been proposed (Japanese Patent Application Laid-Open No. 6-041439). ). This composition was a composition having both a high softening point and penetration, elongation, excellent cold resistance, and workability, but the storage stability was not improved, and storage stability was required. Cannot be used for any purpose. As described above, the asphalt composition to which each conventional polymer is added simultaneously satisfies the high softening point, penetration, elongation, and the high balance required for the workability as its properties, and further has excellent storage stability. There is no one having such properties, and there is a strong demand for providing such asphalt compositions.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the problems of such conventional asphalt compositions, exhibits high softening points, physical properties such as elongation and mechanical strength, and has excellent storage stability. An asphalt composition having an asphalt composition, and a block copolymer composition as an asphalt modifier having excellent solubility in asphalt and excellent in subsequent processability for providing the asphalt composition. The purpose is to provide.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to develop an asphalt modifier having the above-mentioned performance and a modified asphalt composition using the same. By adding a block copolymer composition of an alkenyl aromatic compound having a structure and a shape limited to a conjugated diene in a specific range as an asphalt modifier, excellent solubility and further processability Excellent in softening point, elongation, and mechanical strength, and furthermore, exhibit excellent storage stability in which the performance is stably maintained even during storage, and found that the above object is achieved. Thus, the present invention has been completed.

That is, the present invention relates to a block copolymer (A) comprising at least two polymer blocks mainly composed of a monoalkenyl aromatic compound and at least one polymer block mainly composed of a co-projection diene compound. A polymer block mainly composed of at least one monoalkenyl aromatic compound and a block copolymer mainly composed of at least one conjugated diene compound, wherein the molecular weight is 1/3 of the molecular weight of the block copolymer (A). A block copolymer composition consisting of a block copolymer (B) corresponding to to 2/3, and 1) all of (a) in the block copolymer (A) and the block copolymer (B). The content of the bonded alkenyl aromatic compound is 10 to 50% by weight, (a) the content of the vinyl bond in the conjugated diene is 70% by weight or less, and 2) the block copolymer. The content of (c) (A) in the Narubutsu is 98-20 wt%, the content of (B) 2 to 80
(D) and M of the block copolymer composition
I (G condition) is 0.3 to 15.0, (e) the bulk density is 0.1 to 0.7, and (f) the particle size distribution is 30% by weight or less of the component remaining in the mesh, And 30% by weight or less of components passing through 20 mesh, and (g) the total volume of the pores is 1%.
An asphalt-modified block copolymer composition having a particle size of from 00 to 2000 mm ³ / g; and from ^{3 to} 15 parts by weight of the asphalt-reforming block copolymer composition and 85 to 97 parts by weight of asphalt. Asphalt composition for road paving.

Hereinafter, the present invention will be described in detail. The component (A) constituting the present invention is a block copolymer comprising at least two polymer blocks mainly composed of a monoalkenyl aromatic compound and at least one polymer block mainly composed of a conjugated diene. . The component (B) is
A block copolymer comprising at least one polymer block mainly composed of a monoalkenyl aromatic compound and at least one copolymer block mainly composed of a conjugated diene. A polymer block mainly composed of a monoalkenyl aromatic compound is a polymer block containing 50 monoalkenyl aromatic compounds.
It is a polymer block essentially containing a monoalkenyl aromatic compound as a main component and contained in an amount of at least% by weight. The polymer block mainly composed of a conjugated diene is a polymer block containing 50% by weight or more of a conjugated diene and substantially containing a conjugated diene as a main component.

The monoalkenyl aromatic compound in the block copolymer composition constituting the present invention includes, for example, styrene, P-methylstyrene, tertiary butylstyrene,
Monomers such as α-methylstyrene and 1,1-diphenylethylene are exemplified, and among them, styrene is preferred. These monomers may be used alone or in combination of two or more. On the other hand, as the conjugated diene, for example, 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene,
Examples include monomers such as piperylene, 3-butyl-1,3-octadiene, and phenyl-1,3-butadiene, and among them, 1,3-butadiene and isoprene are preferred. These monomers may be used alone or in combination of two or more.

The peak molecular weight of the component (B) constituting the present invention measured by gel permeation chromatography (GPC) is 1/3 of the peak molecular weight of the component (A) measured in the same manner. ~ 2/3. If it is less than 1/3, the melt viscosity is low and the processability is excellent, but the cohesive strength and the softening point are poor, and the elongation is also poor. On the other hand, if it exceeds 2/3, although the softening point increases, the melt viscosity of the asphalt composition increases, which is not preferable in terms of processability.

In the structure of the component (A), S is a monoal
A polymer block mainly composed of a kenyl aromatic compound, wherein B is
When a polymer block mainly composed of a conjugated diene is used, S
BS, SBSB, SBSBS, (SB)_TwoX, (SB)
_ThreeX, (SB)_FourX, (SBS)_TwoX, (SBS)
_ThreeX, (SBS)_FourX or the like (where X is
Coupling agent residue). Among them, (SB)_TwoX, SBS
It is preferable from the viewpoint of performance. Especially (SB)_TwoX is production on performance
Desirable from above. As the structure of the component (B), SB, S
BS, SBSB, SBSBS, (SB) _TwoX, (SB)
_ThreeX, (SB)_FourX, (SBS)_TwoX, (SBS)
_ThreeX, (SBS)_FourX, etc. (where X is
Coupling agent residue). Above all, SB, (SB)_TwoX, S
BS is preferred in terms of performance. Especially SB is performance and production
Desirable.

The content of the component (A) in the block copolymer composition of the present invention must be 98 to 20% by weight, and the content of the component (B) must be 2 to 80% by weight. Outside these ranges, a high balance of physical properties of melt viscosity, softening point and elongation is not exhibited. The preferred range is (B)
The content of the component is 5 to 60% by weight, more preferably 10 to 40% by weight.

The content of the monoalkenyl aromatic compound in the block copolymer composition of the present invention is 10 to 50% by weight. When the content of the monoalkenyl aromatic compound is 1
If the amount is less than 0% by weight, the cohesive force of the monoalkenyl aromatic compound polymer block is insufficient, and the mechanical strength such as toughness and tenacity is poor. If it exceeds 50% by weight,
The storage stability deteriorates significantly, which is not desirable. Further, when producing an asphalt composition, the dissolution and dispersion time in asphalt becomes long, and the processability is deteriorated, which is not preferable. Further, the low-temperature properties of the asphalt composition deteriorate, which is not preferable. The preferred range of the content of the monoalkenyl aromatic compound is 15 to 45% by weight, more preferably 20 to 40% by weight.

The content of the monoalkenyl aromatic compound polymer block in the block copolymer composition is desirably 10% by weight or more and less than 50% by weight. If it is less than 10% by weight, the cohesive force of the monoalkenyl aromatic compound polymer block cannot be sufficiently obtained, and the softening point, toughness and tenacity may be insufficient. When the content is 50% by weight or more, phase separation or a change with time of the softening point may occur when the asphalt composition is used. A more preferred range is 15 to
It is 45% by weight, even more preferably 20 to 40% by weight. The content of the monoalkenyl aromatic compound polymer block can be determined by an oxidative decomposition method described later.

The vinyl bond content derived from the conjugated diene compound in the conjugated diene polymer block in the block copolymer composition of the present invention is 70% by weight or less. If the vinyl bond content exceeds 70% by weight, the thermal stability of the block copolymer becomes extremely poor, which is not preferable.
In addition, the low-temperature characteristics of the asphalt composition become poor. A preferred range is a vinyl bond content of 5 to 60% by weight, more preferably 8 to 50% by weight.

The MI of the block copolymer composition of the present invention
Is from 0.3 to 0.3 g as measured under G conditions (200 ° C., 5 kgf).
15.0. When the MI is less than 0.3, the melt viscosity of the asphalt composition is too high, and the workability is poor. When the MI exceeds 15.0, the workability is excellent, but the softening point is low, and a high asphalt modifying effect of the components (A) and (B) is not exhibited. The preferred range is from 0.5 to 10.0, more preferably from 0.7 to 10.0.
5.0.

Further, the softening temperature of the block copolymer composition of the present invention measured by a static thermomechanical tester (TMA) is 8
It needs to be 0-130 ° C. Softening temperature 80
When the temperature is lower than ℃, the cohesive strength is poor, the high softening point of the asphalt composition is not exhibited, and the toughness and tenacity are poor. On the other hand, when the softening temperature exceeds 130 ° C., the melt viscosity of the asphalt composition becomes too high, and the dispersion compatibility with the asphalt becomes poor, so that desirable physical properties cannot be exhibited. The preferred range is 85-125 ° C, more preferably 90-120 ° C.

Further, the shape of the copolymer composition of the present invention needs to take the following shapes. The bulk density of the copolymer composition of the present invention needs to be in the range of 0.1 to 0.7. If the bulk density is lower than 0.1, it will float when it is dissolved in asphalt and will separate and have poor solubility. It is also inefficient during transportation. On the other hand, when it is larger than 0.7, it is highly aggregated, so it is difficult to dissolve, and it takes a long time to dissolve. Desirably 0.2 to 0.5, more preferably 0.1 to 0.5.
25 to 0.4.

It is necessary that the particle size distribution of the copolymer composition of the present invention is such that 30% by weight or less of components remaining in 5 meshes when sieved. 3 components remain in 5 mesh
When the content is more than 0% by weight, components having a large particle size increase, resulting in poor solubility. It is preferably at most 20% by weight, more preferably at most 10% by weight. Further, it is necessary that the component passing through the 20 mesh is not more than 30% by weight. If the amount of the component that passes through the 20 mesh is 30% by weight or less, there are too many components having a small particle size, and the component tends to be lump and takes a long time to dissolve. It is preferably at most 10% by weight, more preferably at most 2% by weight.

When the volume of the pores present in the copolymer composition of the present invention is measured, the total pore volume is 100 to 2000 m.
It needs to be in the range of m ³ / g. 100mm ³
If it is less than / g, the pores are so small that the components of the asphalt hardly enter and the dissolution time is long. Also, 2000m
If it exceeds m ³ / g, the voids become so large that they float on the upper surface of the asphalt at the time of melting, and it takes a long time to melt. It is preferably from 120 to 1500 mm ³ / g, more preferably from 130 to 1000 mm ³ / g.

Further, the copolymer composition of the present invention exhibits particularly excellent performance in the following modes. That is, the block copolymer composition of the present invention contains an alkenyl aromatic compound obtained by subtracting the content (BS) of the monoalkenyl aromatic compound polymer block from the content (TS) of the total bonded alkenyl aromatic compound. The amount (TS-BS) is desirably 2 to 30% by weight. If it is less than 2% by weight, a particularly excellent effect of storage stability, which is the object of the present invention, cannot be expected.
On the other hand, when the content is more than 40% by weight, performance such as softening point decreases. A desirable range is 3 to 25% by weight, more preferably 4 to 20% by weight.

The amount of (TS-BS) is determined by, for example, adding a conjugated diene to a reaction vessel and then gradually adding a monoalkenyl aromatic compound when polymerizing a block mainly composed of a conjugated diene. Alternatively, it can be adjusted by simultaneously charging a conjugated diene and an alkenyl aromatic compound in a reaction vessel in the presence of a randomizing agent, and optionally performing polymerization while further adding a conjugated diene.

At this time, the content of the monoalkenyl aromatic compound in the block copolymer composition of the present invention (T
S) is desirably 12 to 50% by weight. When the content of the monoalkenyl aromatic compound is less than 12% by weight, the cohesive force of the monoalkenyl aromatic compound polymer block is insufficient, and the mechanical strength such as toughness and tenacity is poor. On the other hand, when the content exceeds 50% by weight, the storage stability is significantly deteriorated, which is not desirable. In addition, when producing an asphalt composition, the time required for dissolution and dispersion in asphalt is prolonged, and workability becomes difficult, which is not preferable. Further, the low-temperature properties of the asphalt composition deteriorate, which is not preferable. The preferred range of the monoalkenyl aromatic compound is 1
It is 5 to 45% by weight, more preferably 20 to 40% by weight.

Similarly, the content (BS) of the monoalkenyl aromatic compound polymer block in the block copolymer composition is desirably from 10% by weight to 48% by weight. When the amount is less than 10% by weight, the cohesive force of the monoalkenyl aromatic compound block cannot be sufficiently obtained, and the softening point, toughness and tenacity are insufficient. 48% by weight
When the temperature exceeds the above range, phase separation and a change in softening point with time occur when the asphalt composition is formed. The preferred range is 15-4
It is 5% by weight, more preferably 20 to 40% by weight.

The present invention discloses a block copolymer composition for asphalt modification and a modified asphalt composition modified by using the same, wherein the components (A) and (B) When 2 to 15 parts by weight of the resulting asphalt modifying block copolymer composition and 85 to 97 parts by weight of asphalt are contained, the effect of the asphalt composition is effectively exhibited. If the amount of the copolymer composition in the modified asphalt composition is less than 2 parts by weight, a satisfactory asphalt modification effect cannot be obtained. Also, 1
If the amount is more than 5 parts by weight, the melt viscosity of the asphalt composition increases, and not only does the processability deteriorate,
It is economically disadvantageous. More preferably, 4 to 12 parts by weight of the copolymer composition and 88 to 96 parts by weight of asphalt are blended.

[0029] The asphalt used in the present invention is not particularly limited, and asphalt commonly used,
For example, straight asphalt, (semi) blown asphalt, a mixture thereof and the like can be mentioned. Preferably, straight asphalt having a penetration of 40 to 120,
Examples thereof include blown asphalt having a penetration of 10 to 30 and a mixture thereof.

The component (A) constituting the present invention is prepared, for example, by polymerizing styrene using an organolithium compound as a polymerization initiator in an inert hydrocarbon solvent and then polymerizing butadiene alone, or while polymerizing butadiene. Butadiene polymer by a method of gradually adding styrene and polymerizing, or a method of polymerizing a mixture of butadiene / styrene, optionally in the presence of a polar compound, and optionally in the presence of a conjugated diene. To form a block, or a styrene-butadiene copolymer block, and further polymerize styrene, optionally,
Further, it can be obtained by repeating the above operation. At this time, the amount of the organolithium compound is controlled so that the peak molecular weight in GPC is in the range of 5 × 10 ⁴ to 50 × 10 ⁴ in terms of standard polystyrene.

The component (B) constituting the present invention is prepared by, for example, polymerizing styrene in an inert hydrocarbon solvent using an organolithium compound as a polymerization initiator, and then subjecting it to any of the methods described above. Butadiene polymer block,
Alternatively, it can be obtained by forming a styrene-butadiene copolymer block and repeating the above-mentioned operation in some cases. The method of polymerization of component (A) and the method of component (B) need not be the same. At this time, the amount of the organic lithium compound is controlled such that the peak molecular weight in GPC is in the range of 1/3 to 2/3 times the peak molecular weight of the component (A). After the reaction, the components (A) and (B) are added with water, alcohol, acid or the like to deactivate the active species, and after blending a solution of each component with a predetermined composition, for example, steam stripping or the like. To obtain a copolymer composition.

Further, the block copolymer composition comprising the component (A) and the component (B) constituting the present invention comprises the component (B)
After polymerizing the components, a predetermined amount of an appropriate coupling agent is added to the organolithium compound in the polymerization system to cause a coupling reaction in the system, and the unreacted components are converted into component (B) (B). A) A predetermined composition containing the component obtained by the coupling reaction of the component as the component (A) is obtained.
This method is more industrially advantageous than the above method.
These components (A) and (B) are similarly reacted after completion of the reaction.
Add water, alcohol, acid, etc. to deactivate the active species,
For example, a copolymer composition can be obtained by performing steam stripping or the like.

As the coupling agent, a bifunctional coupling agent is preferably used. As such, for example, dichlorodimethylsilane, silicon halide compounds such as phenylmethyldichlorosilane, alkoxysilicon compounds such as dimethyldimethoxysilane, tin compounds such as dichlorodimethyltin, methyl benzoate Ester compounds, vinyl allenes such as divinylbenzene, and bifunctional epoxy compounds.

When polymerizing the block mainly composed of a conjugated diene in the block copolymers (A) and (B), a polar compound is added as a randomizing agent so that the monoalkenyl aromatic compound in the conjugated diene block is added. It is possible to adjust the randomness of the compound. For example, ethers and tertiary amines, specifically, ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran, N, N, N ′, N′-tetramethylethylenediamine, preferably tetrahydrofuran, N, N, N ', N'-tetramethylethylenediamine can be used. Such polar compounds are
For example, when a polymer is obtained using an organolithium compound as an initiator, it can be used by adding a small amount to an inert hydrocarbon solvent such as n-hexane, cyclohexane, benzene, toluene and octane. Instead of the butadiene / styrene mixture, it is also possible to adjust the randomness of butadiene and styrene by first charging styrene and gradually adding butadiene.

Further, the vinyl bond content may be determined by, for example, n-type when a polymer is obtained using an organolithium compound as an initiator.
Polar compounds such as ethers and tertiary amines, for example, ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran, N, N, N ′ in an inert hydrocarbon solvent such as hexane, cyclohexane, benzene, toluene and octane. , N′-tetramethylethylenediamine, preferably tetrahydrofuran or N, N, N ′, N′-tetramethylethylenediamine.

If necessary, stabilizers such as antioxidants and light stabilizers can be added to the composition of the present invention. Examples of the stabilizer include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3-.
(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-
Methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol),
2,4-bis [(octylthio) methyl] -0-cresol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylpentyl) -4-methylphenyl acrylate, 2,4- Di-t-amyl-6- [1-
(3,5-di-t-amyl-2-hydroxyphenyl)
Ethyl] phenyl acrylate and other hindered phenolic antioxidants; dilauryl thiodipropionate,
Sulfur-based antioxidants such as lauryl stearyl thiodipropionate pentaerythritol-tetrakis (β-lauryl thiopropionate); tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite And other phosphorus-based antioxidants.

As the light stabilizer, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ′, 5′-di-tert-butylphenyl)-
Examples include benzotriazole-based ultraviolet absorbers such as 5-chlorobenzotriazole, benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, and hindered amine light stabilizers.

Further, the composition of the present invention can be obtained by the following method after polymerization by the above method. For example,
The dehydrated polymer (hydrated crumb) obtained by steam stripping is extruded in a semi-molten state while dewatering using a screw-type squeezing machine, and squeezing is performed by adjusting the moisture, temperature, etc. so as to obtain a predetermined foaming degree. Foaming is performed at the outlet of the machine, and further adjusted by a cutter blade attached to the outlet so as to obtain a predetermined particle size, to obtain porous pellets. If necessary, the composition of the present invention can be obtained by evaporating the remaining water with a hot air dryer. In addition, after dehydrating the wet crumbs with a press-type dehydrator, the temperature and
The composition of the present invention can also be obtained by drying in a semi-molten state while adjusting the time and water content and foaming as needed, and then pulverizing with a pulverizer. Furthermore, the composition of the present invention can be obtained by crushing the wet crumb through a roll dehydrator, heating and dehydrating, and then crushing the hydrated crumb through a crusher adjusted to have a predetermined shape. As still another method, the composition of the present invention can be obtained by directly drying the wet crumb with a fluidized drier or the like. In this case, conditions such as the temperature, the number of stirring, and the stirring time are adjusted during steam stripping so that a predetermined shape can be obtained.

The method for mixing the asphalt composition of the present invention is not particularly limited, and the above-mentioned various additives may be optionally heated and melted by using, for example, a hot-melt pot, a roll, a kneader, a Banbury mixer, an extruder, or the like. It can be prepared by kneading. In the asphalt composition of the present invention, in addition to the stabilizer, if necessary, various additives conventionally used in asphalt compositions, for example, fillers and reinforcements such as silica, talc, calcium carbonate, mineral powder, glass fiber and the like. Agents, mineral aggregates, pigments or softeners such as paraffinic, naphthenic and aromatic process oils, tackifying resins such as coumarone indene resin and terpene resin, foaming agents such as azodicarbonamide, atactic Polyolefin-based or low-molecular-weight vinyl aromatic-based thermoplastic resins such as polypropylene and ethylene-ethyl acrylate copolymer; natural rubber; polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, and acrylic rubber , Isoprene-isobutylene rubber, Repeller antenna mer rubbers, and styrene-butadiene block copolymer other than the present invention, may be added to synthetic rubber such as styrene-isoprene block copolymer. In particular, when used for road pavement, the asphalt composition is usually used as a mixture with aggregates such as mineral stones, sand and slag.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but these examples do not limit the present invention in any way. In addition, various measurements followed the following method. A. Measurement of physical properties of block copolymer composition; 1) Total styrene content: UV spectrophotometer (Hitachi UV20)
Using 0), it was calculated from the absorption intensity at 262 nm. 2) Block styrene content: Determined according to an oxidative decomposition method using osmium tetroxide and t-butyl hydroperoxide (described in Journal of Polymer Science, Vol. 1, p. 429 (1946)). The weight of the styrene polymer block was measured using an ultraviolet spectrophotometer (Hitachi U.S.A.).
V200) using the absorption intensity at 262 nm.

3) Content of vinyl bond in butadiene part: Measured using an infrared spectrophotometer (Model 1710 manufactured by PerkinElmer) and measured by the Hampton method (“Analytical”).
Chem. , 21, 943 ('43) "). 4) Static thermomechanical analysis: Using a thermomechanical analyzer (manufactured by Shimadzu Corporation, TMA-40), the block copolymer was converted to 2 units.
Using a quartz rod with a pin diameter of 0.5φmm as the detection rod, a temperature change is measured by the penetration method, and the temperature at which the penetration changes sharply is softened. Temperature (load 10 g, heating rate 5 ° C./min).

5) Peak molecular weight and composition ratio: GPC [The equipment was manufactured by Waters, and the column was manufactured by DuPont.
It is a combination of two ZORBAXPSMIOO-S and three PSM60-S. Tetrahydrofuran was used as a solvent, and the measurement conditions were a temperature of 35 ° C., a flow rate of 0.7 ml / min, a sample concentration of 0.1% by weight, and an injection amount of 50 μl.]. The peak molecular weight is a value converted from the following standard polystyrene (manufactured by Waters) calibration curve. 1.75 × 10 ⁶ ,
4.1 × 10 ⁵ , 1.12 × 10 ⁵ , 3.5 × 10 ⁴ ,
8.5 × 10 ³ 6) MI: Measurement of MI is according to Method A of JIS-K7210, the test conditions are conditions 8 (test temperature 200 ° C. in Table 1,
The test load was 5 kgf (corresponding to the ASTM G condition).

B. Measurement of physical properties of asphalt composition: 1) Melt viscosity: Measured at 180 ° C. with a Brookfield viscometer. 2) Toughness and tenacity: Measured according to the test method for pavement work (edited by Japan Road Construction Industry Association). 3) Elongation, penetration and softening point: Measured according to JIS-K-2207. 4) Phase separation: After preparing the asphalt composition, 160 ° C. ×
After allowing to stand for 2 days, the softening points of the upper and lower layers were measured, and the difference was regarded as phase separation. 5) Solubility in asphalt: In the process of dissolving in asphalt, the presence or absence of undissolved matter was confirmed with a wire mesh, and the solubility when the undissolved matter disappeared was determined as the dissolution time in asphalt to determine the solubility.

C. Shape analysis of composition: 1) Bulk density A sufficiently dried polymer composition was weighed in a 100 cc container, and the bulk density was calculated from the weight of 100 cc. 2) Particle size distribution 500 g of a sufficiently dried polymer composition was 5 mesh
After passing through a sieve having meshes of 0 mesh, the weight passing through the sieve and the weight remaining on the sieve were measured and calculated. 3) Total volume of pores Mercury porosimeter [Porosimeter pa, manufactured by Amco Corporation]
[scal140 type] using a mercury intrusion method.

[0045]

Example 1 A 10-liter stainless steel reactor equipped with a jacket and a stirrer was sufficiently purged with nitrogen.
000 cc, 1.41 g of tetrahydrofuran, N, N,
0.6 g of N ′, N′-tetramethylethylenediamine,
300 g of styrene (referred to as first styrene) was charged, and warm water was passed through the jacket to set the content at about 70 ° C. Thereafter, an n-butyllithium cyclohexane solution (1.8 g in pure content) was added to initiate polymerization of the first styrene. After the first styrene was completely polymerized, 700 g of butadiene (1,3-butadiene) was added to continue the polymerization, and after the butadiene and styrene were almost completely polymerized, the coupling agent shown in Table 1-1 was added. Was added and a coupling reaction was performed. After adding the coupling agent, 0.5 g of water
Was added. Immediately after charging the first styrene,
The system was continuously stirred by a stirrer.

Thereafter, the solution of the block copolymer composition was withdrawn, and 1.9 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of tris (nonylphenyl) phosphite were added. The solution was subjected to steam stripping to remove the solvent to obtain a wet crumb.
Subsequently, the mixture was dehydrated and dried by a hot roll, and further adjusted by a pulverizer so as to have a predetermined particle size distribution to obtain a block copolymer composition. The conditions for this operation are summarized in Table 1-1. The block copolymer composition thus obtained was measured by GPC, and a low-molecular-weight main component was defined as (B) and a high-molecular-weight main component was defined as (A). The analytical values and physical properties are shown in Table 2-1. In addition, straight asphalt [Nippon Oil Co., Ltd.
Manufactured by STORUS 60/80] was added at a ratio of 6 g to 100 g and melt-kneaded at 180 ° C. to prepare an asphalt composition. Table 3-1 shows data of the characteristics, workability, and the like of the asphalt composition.

[0047]

Example 2 A 10-liter stainless steel reactor equipped with a jacket and a stirrer was sufficiently purged with nitrogen.
000 cc, 1.41 g of tetrahydrofuran, N, N,
0.6 g of N ′, N′-tetramethylethylenediamine,
200 g of styrene (referred to as first styrene) was charged, and warm water was passed through the jacket to set the content at about 70 ° C. Thereafter, an n-butyllithium cyclohexane solution (1.4 g in pure content) was added to initiate polymerization of the first styrene. After the first styrene is completely polymerized, 700 g of butadiene (1,3-butadiene) and styrene (second
100 g of styrene) was added, and the polymerization was continued. After butadiene was almost completely polymerized, a coupling agent was added to perform coupling.

After the addition of the coupling agent, 0.4 g of water was added. Immediately after charging the first styrene, the inside of the system was continuously stirred by a stirrer during this period. Thereafter, a solution of the block copolymer composition was extracted, and 1.9 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of tris (nonylphenyl) phosphite were added. Was subjected to steam stripping to remove the solvent to obtain a wet crumb. Subsequently, dehydration and drying were performed using a vented 30 mm extruder. At that time, the cutter was adjusted to have a predetermined particle size distribution. Furthermore, hot-air drying was performed to obtain a desired block copolymer composition. The conditions for this operation are summarized in Table 1-1. The block copolymer composition thus obtained was measured by GPC, and a low-molecular-weight main component was defined as (B) and a high-molecular-weight main component was defined as (A). The analytical values and physical properties are shown in Table 2-1. Also, straight asphalt [Nippon Oil Co., Ltd., Stores 60/80] 10
The polymer composition was added at a ratio of 6 g to 0 g,
The mixture was melt-kneaded at 0 ° C. to prepare an asphalt composition. Table 3 shows the data of the properties, processability, etc. of the asphalt composition.
-1.

[0049]

Example 3 A 10-liter stainless steel reactor equipped with a jacket and a stirrer was sufficiently purged with nitrogen.
000 cc, 1.41 g of tetrahydrofuran, N, N,
0.6 g of N ′, N′-tetramethylethylenediamine,
150 g of styrene (referred to as first styrene) was charged, and warm water was passed through the jacket to set the content at about 70 ° C. Thereafter, an n-butyllithium cyclohexane solution (pure content: 1.64 g) was added to initiate polymerization of the first styrene. After the first styrene was completely polymerized, 850 g of butadiene (1,3-butadiene) was added and the polymerization was continued, and after the butadiene was almost completely polymerized, a coupling agent was added and coupled.

After the addition of the coupling agent, 0.4 g of water was added. Immediately after charging the first styrene, the inside of the system was continuously stirred by a stirrer during this period. Thereafter, a solution of the block copolymer composition was extracted, and 1.9 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of tris (nonylphenyl) phosphite were added. Was subjected to steam stripping to remove the solvent to obtain a wet crumb. Subsequently, dehydration was performed using a press-type dehydrator, and then drying was performed using a dryer. The mixture was further adjusted to a predetermined particle size distribution by a pulverizer to obtain a block copolymer composition. The conditions for this operation are summarized in Table 1-1.

The block copolymer composition thus obtained was measured by GPC, and the main component of low molecular weight was (B) and the main component of high molecular weight was (A). The analytical values and physical properties are shown in Table 2-
1 is shown. Also, 6 g of the polymer composition was added to 100 g of straight asphalt (Storus 60/80, manufactured by Nippon Oil Co., Ltd.) and melt-kneaded at 180 ° C. to prepare an asphalt composition. Table 3-1 shows data of the characteristics, workability, and the like of the asphalt composition.

[0052]

Examples 4 to 17 and Comparative Examples 1 to 8 Examples 4 to 18 and Comparative Examples 1 to 7 were performed under the same conditions as in Example 1 except for the conditions described in Tables 1-1, 2, and 3. Was. As a result, the analysis values and physical properties of the obtained block copolymer composition are shown in Table 2-
1, 2, and 3. Asphalt composition evaluation was performed using the same asphalt as in Example 1, and the amount and method of asphalt blending were the same as in Example 1. The results are shown in Tables 3-1, 2 and 3.

[0053]

REFERENCE EXAMPLE 1 [Production method of block copolymer component (A)] After sufficiently replacing a 10-liter stainless steel reactor equipped with a jacket and a stirrer with nitrogen, a predetermined amount of cyclohexane, tetrahydrofuran, N, N, N ', N'-tetramethylethylenediamine and styrene (referred to as first styrene) were charged, and warm water was passed through the jacket.
Set to. Thereafter, a predetermined amount of an n-butyllithium cyclohexane solution was added to start polymerization of the first styrene. After the first styrene was completely polymerized, butadiene (1,3-butadiene) and styrene (referred to as second styrene) were added in predetermined amounts to continue the polymerization, and after the butadiene was completely polymerized, again Styrene (referred to as tertiary styrene) was added in a predetermined amount to continue the polymerization. After the tertiary styrene was completely polymerized, water was added to completely inactivate the active species. Thereafter, 2,6-di-t-butyl-4-methylphenol and tris (nonylphenol) phosphite (cyclohexane solution) were added. Table 1 shows the conditions for this operation.
-4.

[0054]

REFERENCE EXAMPLE 2 [Production method of block copolymer component (B)] After sufficiently replacing a 10-liter stainless steel reactor equipped with a jacket and a stirrer with nitrogen, a predetermined amount of cyclohexane, tetrahydrofuran, N, N, N ', N'-tetramethylethylenediamine and styrene (referred to as first styrene) were charged, and warm water was passed through the jacket.
Set to. Thereafter, a predetermined amount of an n-butyllithium cyclohexane solution was added to start polymerization of the first styrene. After the first styrene was completely polymerized, butadiene (1,3-butadiene) and styrene (second styrene) were added in predetermined amounts to continue the polymerization, and after the butadiene and the second styrene were completely polymerized, Water was added to completely inactivate the active species. Thereafter, 2,6-di-t-butyl-4-methylphenol and tris (nonylphenol) phosphite (cyclohexane solution) were added. The conditions for this operation are shown in Table 1-4.

[0055]

Example 18 The polymer solutions of the components (A) and (B) obtained in the above Reference Examples 1 and 2 were mixed with each other so as to have a predetermined composition ratio, and the obtained polymer solutions were obtained. The solvent was removed by steam stripping the solution to obtain a wet crumb. Subsequently, the mixture was dehydrated and dried by a hot roll, and further adjusted by a pulverizer so as to have a predetermined particle size distribution, thereby obtaining a block copolymer composition. The physical properties of this block copolymer composition are shown in Table 2-3. The block copolymer composition thus obtained was made into an asphalt composition in the same amount by using the same asphalt as in Example 1. The physical properties are shown in Table 3-3.

[0056]

Reference Example 3 A 10-liter stainless steel reactor equipped with a jacket and a stirrer was sufficiently purged with nitrogen.
000 cc, 1.41 g of tetrahydrofuran, N, N,
0.6 g of N ′, N′-tetramethylethylenediamine,
220 g of styrene (referred to as first styrene) was charged, and warm water was passed through the jacket to set the content at about 70 ° C. Thereafter, an n-butyllithium cyclohexane solution (1.4 g in pure content) was added to initiate polymerization of the first styrene. After the first styrene is completely polymerized, 680 g of butadiene (1,3-butadiene) and 10
0 g was added to continue the polymerization, and after the butadiene was almost completely polymerized, a coupling agent was added for coupling. After addition of the coupling agent, 0.5 g of water was added.
Immediately after charging the first styrene, the inside of the system was continuously stirred by a stirrer during this period. Thereafter, the solution of the block copolymer composition was extracted, and 2,6-di-t-butyl-4
1.9 g of methylphenol and 1.2 g of tris (nonylphenyl) phosphite were added.

[0057]

Example 19 The solution obtained in Reference Example 3 was subjected to steam stripping to remove the solvent to obtain a hydrated crumb, which was subsequently dehydrated and dried using a vented 30 mm extruder. At that time, the cutter was adjusted to have a predetermined particle size distribution. Furthermore, hot-air drying was performed to obtain a desired block copolymer composition. The block copolymer composition thus obtained was measured by GPC, and a low-molecular-weight main component was (B) and a high-molecular-weight main component was (A). The physical properties are shown in Table 2-3. Further, 6 g of the polymer composition and straight asphalt [manufactured by Nippon Oil Co., Ltd .;
/ 80] was melt-kneaded at 180 ° C. to prepare an asphalt composition. The characteristics of the asphalt composition are shown in Table 3-3.

[0058]

Examples 20 to 23, Comparative Examples 9 to 10 Examples 20 to 2
3 and Comparative Examples 9 to 10, the same as in Example 19, the solution obtained in Reference Example 3 was granulated by the method described in Table 1-5, and 6 g of the polymer composition and straight asphalt [ Nippon Oil Co., Ltd., Stores 60/80]
The mixture was melted and kneaded at ℃ to prepare an asphalt composition. The analysis values of the polymer composition are shown in Table 2-4, and the characteristics of the asphalt composition are shown in Table 3-4.

[0059]

Comparative Example 11 The solution of Reference Example 3 was subjected to steam stripping to remove the solvent, and the obtained water-containing crumb was dehydrated and dried with a hot air drier to substantially completely remove the water, thereby obtaining a dried crumb. Obtained. In addition, the dried crumbs
Melt extrusion was performed with a mm extruder to obtain pellets. The analytical values of the pellets are shown in Table 2-4. Also, straight asphalt [Nippon Oil Co., Ltd., Stores 60/80] 10
The polymer composition was added at a ratio of 6 g to 0 g,
The mixture was melt-kneaded at 0 ° C. to prepare an asphalt composition. Table 3 shows the data of the properties, processability, etc. of the asphalt composition.
-4.

[0060]

COMPARATIVE EXAMPLE 12 The solution of Reference Example 3 was subjected to steam stripping to remove the solvent, and the obtained water-containing crumb was dehydrated and dried with a hot air drier to obtain a dried crumb. The analytical values of the crumb are shown in Table 2-4. 6 g of polymer composition and straight asphalt [Stores, manufactured by Nippon Oil Co., Ltd.
60/80] was melt-kneaded at 180 ° C. to prepare an asphalt composition. The characteristics of the asphalt composition are shown in Table 3-4.

[0061]

Comparative Example 13 The sheet obtained in Comparative Example 10 was press-molded to obtain a sheet. The sheet was further cut to obtain a sample. The analysis values of the sample are shown in Table 2-4.
6 g of the sample and 100 g of straight asphalt (Storus 60/80, manufactured by Nippon Oil Co., Ltd.) were melt-kneaded at 180 ° C. to prepare an asphalt composition. The characteristics of the asphalt composition are shown in Table 3-4.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

[0068]

[Table 7]

[0069]

[Table 8]

[0070]

[Table 9]

[0071]

[Table 10]

[0072]

[Table 11]

[0073]

[Table 12]

[0074]

[Table 13]

[0075]

As can be seen from these tables, asphalt compositions modified with block copolymers having a specified range of structures have high softening points, high 60 ° C. melt viscosities, excellent elongation, and high toughness. , Tenacity and excellent storage stability. Further, it can be seen that the examples have excellent storage stability when the initial softening points are equal to those of the comparative examples, and that the examples have excellent initial softening points when the storage stability is equal. The asphalt composition of the present invention is excellent in physical properties such as mechanical strength, softening point, elongation, and the like, and has a high degree of balance excellent in workability, and is also excellent in storage stability. It can be used not only for road pavement, but also for applications such as waterproof sheets, sound insulation sheets, and waterproof materials, and its industrial significance is great.

Claims (5)

[Claims] 1. A block copolymer (A) comprising at least two polymer blocks mainly composed of a monoalkenyl aromatic compound and at least one polymer block mainly composed of a co-projected diene compound; And at least one block copolymer mainly composed of a conjugated diene compound, wherein the molecular weight is 1/3 to 2/2 of the molecular weight of the block copolymer (A). Block copolymer (B) corresponding to 3
1) The content of (a) the total bond alkenyl aromatic compound in the block copolymer (A) and the block copolymer (B) is 10 to 10.
(A) the vinyl bond content in the conjugated diene is 70% by weight or less; 2) the content of (c) (A) in the block copolymer composition is 98 to 20% by weight. , (B) is from 2 to 80% by weight, (D) and the MI (G condition) of the block copolymer composition is from 0.3 to 15.0, and (E) the bulk density is (F) 30% by weight or less of components whose particle size distribution remains in 5 meshes, 30% by weight or less of components passing through 20 meshes, and (g) the total volume of pores is 100%. A block copolymer composition for asphalt modification, characterized by having a particle size of ２０００2000 mm ³ / g. 2. The asphalt modifying block copolymer composition according to claim 1, wherein the softening temperature of the block copolymer mixture is 80 to 130 ° C. as measured by static thermomechanical analysis (TMA). 3. The monoalkenyl aromatic compound polymer block (BS) is at least 10% by weight and less than 48% by weight, and the monoalkenyl aromatic compound polymer block (TS) is determined based on the total content of alkenyl aromatic compound (TS). (BS)
Alkenyl aromatic compound content (TS-B
2. The composition according to claim 1, wherein S) is 2 to 30% by weight.
Or the block copolymer composition for asphalt modification according to 2. 4. The block for asphalt modification according to claim 1, wherein the component (A) is a coupling polymer obtained by a coupling reaction of the component (B). Polymer composition. 5. An asphalt composition comprising 3 to 15 parts by weight of the asphalt-modified block copolymer composition according to claim 1 and 85 to 97 parts by weight of asphalt.