JPS63268766A - Bituminous composition - Google Patents

Abstract

PURPOSE:To obtain a composition outstanding in softening point, rate of penetration, strength and elongation, suitable for road-paving asphalts, waterproof sheets, etc., by blending a conjugated diene-vinyl aromatic hydrocarbon block copolymer and bituminous material. CONSTITUTION:The objective composition can be obtained by blending (A) a block copolymer (or hydrogenated product therefrom) constituted of (i) polymer segments consisting mainly of at least one vinyl aromatic hydrocarbon (A1) and (ii) other polymer segments consisting mainly of at least one conjugated diene (A2) so that the weight ratio A1/A2=10/90-60/40 (pref. 15/85-55/45) and a component containing said hydrocarbon A1 more than that corresponding to the main peak (determined by composition analysis through high-performance liquid chromatography) by >=5wt.% and a second component containing said hydrocarbon A1 less than that corresponding to said main peak by >=5wt.% totals 20-80(pref. 30-70)wt.% and (B) a bituminous material so as to be 0.5-500(pref. 3-70)pts.wt. per 100pts.wt. of the component B, of the component A.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a composition that has excellent softening point, penetration, elongation, and strength, and is suitable for road paving asphalt, waterproof sheets, sound insulation sheets, roof inks, etc. [Prior Art] Conventionally, natural rubber Alternatively, by mixing synthetic rubber such as styrene-butadiene rubber or nitrile rubber, the properties of bituminous material, which are brittle at low temperatures and prone to impact fracture, and properties that are prone to plastic deformation at high temperatures, are improved. It is known that durability increases, and it is already used in Japan and other countries for road applications, civil engineering, architecture, industrial applications, etc. There are two methods: mixing rubber with bituminous material in advance on an oven roll to create a master patch with a high rubber part, heating and melting this, and then pouring it into the bituminous material and dissolving it; A method in which block copolymer pellets, crumbs, or bacter consisting of a conjugated diene and a vinyl aromatic hydrocarbon are poured into a heated and molten bituminous material and dissolved therein. There is. Particularly recently, it has superior solubility during mixing compared to conventionally used bituminous compositions containing natural rubber or synthetic rubber.
There is a tendency for block copolymer-containing bituminous compositions having relatively low viscosity at high temperatures to be used favorably. For example, Japanese Patent Publication No. 47-17319, Japanese Patent Publication No. 47-33058
The publication discloses a bituminous material composition using a block copolymer of a vinyl aromatic compound and a conjugated diene compound, or a hydrogenated product thereof, as a rubbery material.
[Problems to be Solved by the Invention] However, the above-mentioned block copolymer-containing bituminous compositions have poor balance performance among softening point, penetration, elongation, and strength, and improvement thereof is desired.

Attempts have been made to improve these problems by increasing the molecular weight of the block copolymer and increasing the content of nine divinyl aromatic compounds, but the former results in higher melt viscosity and significantly worse processability. However, the latter poses problems such as decreased penetration and elongation.

[Means and effects for solving the problems] In view of the current situation, the present inventors have conducted extensive studies on improving the softening point, penetration, elongation, etc. of the composition of bituminous material and block copolymer. As a result, in compositional analysis using high-performance liquid lithography, it was discovered that the objective could be achieved by using a block copolymer having a specific compositional distribution, and the present invention was completed. That is, the present invention provides (a
) has at least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, and the weight ratio of the vinyl aromatic hydrocarbon to the conjugated diene is 10/ In a block copolymer or its hydrogenated product having a molecular weight of 90 or more and 60,740 or less, component A (vinyl aromatic hydrocarbon content is the main peak of vinyl aromatic hydrocarbon content) determined from composition analysis by high performance liquid chromatography. component B (where the vinyl aromatic hydrocarbon content is lower than the vinyl aromatic hydrocarbon content of the main peak,
and the difference between them is 5% by weight or more) and the total amount is 2
A block copolymer having a content of 0 to 80%. (b) Bituminous material.

A bituminous composition comprising:

The present invention will be explained in detail below.

The block copolymer of component (a) used in the present invention is a polymer segment mainly composed of at least one, preferably two or more vinyl aromatic hydrocarbons. segment, the weight ratio of vinyl aromatic hydrocarbon and conjugated diene is 10/90 or more, 6
It is a block copolymer of 0/40 or less, preferably 15/85 to 55/45.

If the vinyl aromatic hydrocarbon content is less than 10/9G, the softening point and strength will be poor, and if it exceeds 60/40, the penetration and elongation will be poor, which is not preferable. In the present invention, a polymer segment containing mainly vinyl aromatic hydrocarbons means that the content of vinyl aromatic hydrocarbons is 50% by weight.
The above polymer segment is composed of a copolymer part of a conjugated diene and a vinyl aromatic hydrocarbon and/or a vinyl aromatic hydrocarbon superposition part. In addition, the polymer segment mainly composed of conjugated diene refers to a polymer segment in which the content of vinyl aromatic hydrocarbon is less than 50 i, a copolymer portion of conjugated diene and vinyl aromatic hydrocarbon, and/or a polymer segment containing a vinyl aromatic hydrocarbon. Or composed of a conjugated diene polymer moiety. Even though the vinyl aromatic hydrocarbon in the copolymer portion of the conjugated diene and vinyl aromatic hydrocarbon is uniformly distributed in the polymer chain,
Also tapered.

It may be distributed evenly. Further, the copolymer portion may include a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and/or a plurality of portions in which vinyl aromatic hydrocarbons are distributed in a tapered manner. In such a case, the proportions of conjugated diene and vinyl aromatic hydrocarbon in each copolymerization portion may be the same or different.

The greatest feature of the block copolymer of component (a) used in the present invention is that the components determined from the composition analysis by liquid chromatography (detected at a wavelength of 254n!n using an ultraviolet absorption photometer as a detector) A (component whose vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak and the difference is 5% by weight or more) and component B (component whose vinyl aromatic hydrocarbon content is higher than the main peak's vinyl aromatic hydrocarbon content). The total amount of the vinyl aromatic hydrocarbon content is 20 to 8096, preferably 30 to
It is 70 inches. If the total amount of component A and component B is outside the above range, it is not preferable because a product with excellent balance of softening point, penetration, elongation and strength cannot be obtained.

In the present invention, the composition analysis by high-performance liquid chromatography is the method developed by Professor Naka of the University of Agriculture and Technology (M.
akromol, Chem-* Rapid Com
mun, 5.719-722 (1984) and Proceedings of the Society of Polymer Science, Vol. 32, No. 9, 2227-2230 (1983)
acrylinitrile dimethacrylate copolymer gel (particle size 2.5-5).
．． This is a method for separating and analyzing polymers based on differences in composition by using a gradient method (hexane/chloroform) of eluent in a column packed with 0 μm). An ultraviolet absorption photometer is used as a detector, and detection is performed at a wavelength of 254 nm. The composition of the eluted component is determined using a calibration curve prepared using a standard sample prepared by the method described in the above-mentioned literature. In the present invention, the vinyl aromatic hydrocarbon content of the main peak is the vinyl aromatic hydrocarbon content (wt%) corresponding to the portion where the absorbance at a wavelength of 254 nm is maximum in the high performance liquid chromatogram obtained by the above method. . In addition, in the high performance liquid chromatogram, 254 nm
If there are two or more parts with maximum absorbance at the wavelength of
The main peak is the one with higher vinyl aromatic hydrocarbon content. The proportion of component A in the present invention is determined by calculating the area of the part corresponding to the component whose vinyl aromatic hydrocarbon content is 5% by weight or more higher than the vinyl aromatic hydrocarbon content of the main peak in a high-performance liquid chromatogram. It is found by dividing by the area of . Similarly, the proportion of component B is determined by dividing the area of the portion corresponding to the component whose vinyl aromatic hydrocarbon content is 5% or more by weight less than the vinyl aromatic hydrocarbon content of the main peak by the area of all components. It is determined by

In the present invention, when the vinyl aromatic hydrocarbon content of the main peak is equal to or less than the vinyl aromatic hydrocarbon content of the entire block copolymer, the former is preferably smaller than the latter, and the difference is preferably 1 When the content is more than % by weight, the penetration and elongation properties are particularly excellent.On the other hand, when the vinyl aromatic hydrocarbon content of the main peak exceeds the vinyl aromatic hydrocarbon content of the entire block copolymer, the former is preferable. is larger than the latter and the difference is 1 weight or more, the softening point is particularly excellent, and it can be used for various purposes depending on the state of the composition distribution.

The block copolymer of component (a) used in the present invention has a weight average molecular weight (hereinafter referred to as Mw) and a number average molecular weight (hereinafter referred to as Mn) of the vinyl aromatic hydrocarbon polymer block in the block copolymer. ) in the range of 1.2 to 3.0, preferably 1.3 to 2.0, is recommended from the viewpoint of processability, processability of the various diseases described above, and stability of the various performances described above.

Mw/Mn of the vinyl aromatic hydrocarbon polymer block can be measured as follows. A vinyl aromatic hydrocarbon polymer component (
L-M-KOLTHOFF.

et &1. ．． J, Po17m, aci, 1.42
9 (1946) method described in K) by gel permeation chromatography (GPC) and calculated according to a conventional method (for example, the method described in "Gel Chromatography Basics" published by Kodansha) Nine calibration curves for 0GPC were prepared using standard polystyrene commercially available for GPC.

The block copolymer of component (a) used in the present invention can be obtained by polymerization in a hydrocarbon solvent using an organolithium compound as an initiator.

Hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, hexane, impentane, heptane, octane, isooctane, didiclopentane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, Alternatively, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene can be used. Organolithium compounds have 1 in the molecule.
It is an organic lithium compound in which more than one lithium atoms are combined, such as ethyllithium, n-tetrapyrulithium 1
Inpropyl lithium, n-butyl lithium, 8eC-
Examples include butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, imprenyl dilithium, and the like.

In the present invention, vinyl aromatic hydrocarbons include styrene, 0-methylstyrene, p-methylstyrene, p-
Examples include tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanto-2cene, and styrene is particularly common. These may be used not only alone, but also as a mixture of two or more. The conjugated diene may be a diolefin 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, 1#3-hexadief, etc., but particularly common ones are 1,3-butadiene,
Isoprene is mentioned. These may be used not only alone, but also as a mixture of two or more.

When producing the block copolymer of component (a) used in the present invention, the method for forming a copolymer portion of vinyl aromatic hydrocarbon and conjugated diene includes (1) vinyl aromatic hydrocarbon and conjugated diene. Methods include continuously supplying a mixture with a diene to a polymerization system for polymerization, and/or (1) copolymerizing a vinyl aromatic hydrocarbon and a conjugated diene using a polar compound acid or a randomizing agent. Can be adopted. As polar compounds and randomizing agents, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether a)+7-! : Ethylmine, Nato2
Examples include aions such as methylethylenediamine, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, potassium and sodium alkoxides, and the like.

The bonding state of the vinyl aromatic hydrocarbon copolymerized into the copolymer portion of the vinyl aromatic hydrocarbon and conjugated diene by the above method is determined by the method developed by the professor at the University of Agriculture and Technology (Japan). Rubber Association Journal, 54 (9)
, 564 (1981)), it can be determined by dioscine decomposition that the proportion of the component corresponding to 9 methylene monomer to the component corresponding to styrene tetramer measured by this method is the proportion of the block copolymer. If the total amount of vinyl aromatic hydrocarbons in the total amount is less than 51i, a bituminous composition with a relatively good softening point can be obtained, and if it is 5 to 40% by weight, it will have relatively low penetration and elongation. A good bituminous composition is obtained.

The block copolymer of component (a) used in the present invention has a polymer structure of the general formula % formula %) (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a conjugated It is a polymer block mainly composed of diene. The boundary between the A block and the B block does not necessarily need to be clearly distinguished. n is an integer of 1 or more, and generally an integer of 1 to 5.) Or the general formula, ni) ((B-A 睩□X (e) 〒i Indicates the residue of an initiator such as a compound. m and n are integers of 1 or more. Generally, they are integers of 1 to 5.) or any mixture thereof. Particularly preferred is a block copolymer in which both ends of the polymer chain are formed of polymer blocks containing mainly vinyl aromatic hydrocarbons.

The method for producing the block copolymer of component (&) used in the present invention includes adding a catalyst to Shinku during production, adding a deactivator such as alcohol or carboxylic acid during production, etc. By deactivating some of the active sites, by adding chain transfer agents such as toluene, arenes, vinyl acetylenes, and secondary amines to cause a chain transfer reaction, and by adjusting the miscibility within the polymerization system, Examples of method b include, but are not limited to, methods in which these methods are used in combination. Any method may be used as long as the ratio of component A and component B falls within the range defined by the present invention.

The molecular weight of the block copolymer of component (&) used in the present invention is IQ, preferably 0001 to 000 NLOO2.
0,000~! , 000,000. In addition, block copolymers may be hydrogenated, halogenated, or
Modifications such as hydrogenation, or introduction of functional groups such as hydroxyl groups, thiol groups, nitrile groups, sulfonic acid groups, and amine groups by chemical reaction may be performed.

In particular, a hydrogenated block copolymer is a preferable improvement method because it improves heat aging resistance and weather resistance. It is recommended that the block copolymer before hydrogenation has a 1,2-hinyl bond amount based on the conjugated diene of 20 to 60%, preferably Vi of 25 to 50%. Catalysts used in the hydrogenation reaction include (1) Ni + Pt
, PcL Ru and other metals are supported on a carrier such as carbon, silica, alumina, diatomaceous earth, etc., and (2) Ni + Co, organic acid salts such as eFe, Cr, etc. are combined with acetylacetone salts and organic The so-called Ziegler type catalyst using a reducing agent such as Ru, Rh
Homogeneous catalysts such as so-called organic acid catalysts, such as organometallic compounds such as
Hydrogenated in the presence of a hydrogenation catalyst in an inert solvent according to the second son method described in Publication No. 3203 to obtain a hydrogenated product,
Hydrogenated block copolymers for use in the present invention can be synthesized. At that time, at least 80 atoms of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is transformed into an olefin. The compound can be converted into a polymer block. In addition, hydrogenation of aromatic double bonds based on the vinyl aromatic compound copolymerized into the polymer block A mainly composed of a vinyl aromatic compound and the polymer block B mainly composed of a conjugated diene compound as necessary. There are no particular restrictions on the hydrogenation rate, but it is preferable to keep the hydrogenation rate at 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like.

The bituminous material used as component (b) in the present invention includes those obtained as by-products during petroleum refining (petroleum asphalt), natural products (natural asphalt), or mixtures of these and petroleum. The main component is bitumen. Specifically, straight asphalt, semi-prone asphalt, flown asphalt, cutback asphalt containing tar, pitch, and oil, asphalt emulsion, and the like can be used. These may be used in combination.

The bituminous material preferred in the present invention has a penetration degree of 30-1.
30. More preferred is 45#120 straight asphalt. When a material having a penetration degree within this range is used, a composition having excellent softening point, elongation, and strength can be obtained.

The amount of the block copolymer (component (a)) in the bituminous composition of the present invention varies depending on the type and use of the bituminous material to be improved. , generally 0.5 to 5 parts by weight, preferably 1 to 10 parts by weight of component (b) bituminous material.
0 parts by weight, more preferably 3 to 70 parts by weight. In addition, in the present invention, for the purpose of improving the properties of component (a), 1 part by weight or more and 20. i (less than 5, preferably 5
~15! It is also possible to incorporate a certain amount of component (b).

The composition of the present invention may contain any additive in any amount as required. The types of additives are:
Inorganic fillers such as clay, talc, calcium carbonate, zinc oxide and glass peas, aggregates such as crushed stone, gravel and sand, fibrous reinforcements such as glass fiber and asbestos, organic reinforcements such as carbon black, coumaron indene resins, tackifier resins such as terpene resins, softeners such as paraffinic, naphthenic and aromatic oils, polyolefin resins,
Examples include thermoplastic resins such as polystyrene resins and polyvinyl chloride resins, and synthetic rubbers such as natural rubber, polybutadiene rubber, styrene, butadiene rubber, and nitrile rubber.

In the present invention, the method of mixing component (a) and component (b)e is not particularly limited, but a particularly desirable method is to pelletize or powder component (a),
This is a method of adding and mixing the component (b) which has been heated and melted.

〔Effect of the invention〕

The composition of the present invention can be used for various purposes by taking advantage of its excellent balance of softening point, penetration, elongation, and strength.

That is, by appropriately selecting the amount of the component (&) in the composition, it is possible to use bituminous materials for road paving, waterproofing, rust prevention, automobile base coating, roof ink, pipe coating, and joint applications. It can be used for almost all purposes,
In each application, it can contribute to improved temperature sensing performance, improved resistance to plastic deformation, improved impact resistance, and improved durability.

Examples are shown below to explain the present invention in more detail, but these examples are intended to demonstrate the excellent effects obtained by the present invention, and are not intended to limit the scope of the present invention. isn't it.

The block copolymers used in the examples of the present invention are as follows:
Create it as follows:

[Block copolymer prisoner]

After the autoclave was internally purged with nitrogen gas, a purified and dried cyclohexane solution containing 3 parts by weight of styrene and an n-butyl lithium solution containing 0.026 parts by weight were prepared.
A hexane solution was added and polymerization was carried out at 70°C for 1 hour. Next, a cyclohexane solution containing 6 parts by weight of styrene and an n-hexane solution containing 0.026 parts by weight of n-butyllithium were added to the polymerization solution, and polymerization was carried out at 70°C for 1 hour. Furthermore, a cyclohexane solution containing 16 parts by weight of styrene and an n-hexane solution containing 0.053 parts by weight of n-butyllithium were added to the polymerization solution, and the mixture was heated at 70°C.
Time-polymerized friend. Thereafter, a cyclohexane solution containing 60 parts by weight of butadiene was added to the polymerization solution, and polymerization was carried out at 70°C for 2 hours, followed by further addition of a cyclohexane solution containing 2,715 parts by weight of Ste, and polymerization was carried out at 70°C for 1 hour. The styrene content of the obtained block copolymer was 40% by weight, and fc,o' [Block copolymer support (B)] A cyclohexane solution containing 10 parts by weight of styrene and n-butyllithium were placed in the same autoclave as above. 0.0
Add a n-hexane solution containing 7 parts by weight and heat to 70°C.
Polymerization was carried out for 1 hour. Next, a cyclohexane solution containing 15 parts by weight of styrene and an n-hexane solution containing 0.035 parts by weight of n-butyllithium were added to the polymerization solution, and polymerization was carried out at 70° C. for 1 hour. Thereafter, a cyclohexane solution containing 60 parts by weight of butadiene and 3 parts by weight of styrene was added to the polymerization solution, and polymerization was carried out at 70°C for 2 hours.
Furthermore, a cyclohexane solution containing 15 parts by weight of styrene was added, and polymerization was carried out at 70° C. for 1 hour.

The styrene content of the obtained block copolymer was 40% by weight.

[Block copolymer (C)]

In an autoclave similar to the above, a cyclohexane solution containing 5 M parts of methylene ref and 0.08 m of n-butyllithium was added.
Part by weight of n-hexane solution was added and polymerized at 70°C for 1 hour. Next, a cyclohexane solution containing 20 parts by weight of styrene and an n-hexane solution containing 0.08 parts by weight of n-butyllithium were added to the polymerization solution, and polymerization was carried out at 70° C. for 1 hour. Thereafter, 35 parts by weight of butadiene and 2.5 parts by weight of styrene were added to the polymerization solution to give 70%
After polymerizing for 1 hour at 70°C, 35 parts by weight of butadiene and 2.5 parts by weight of styrene were further added and polymerization was carried out for 1 hour at 70°C. Then, 0.074 silicon tetrachloride was added to this polymer solution.
Parts by weight were added and reacted at 70°C for 30 minutes. The styrene content of the obtained next block copolymer was 3011%.

[Block copolymer Φ)]

A cyclohexane solution containing 15 parts by weight of styrene and 5 parts by weight of butadiene was placed in the same autoclave as above.
An n-hexane solution containing 0.2 parts by weight of butyllithium was added and polymerized at 70°C for 1 hour. Next, a cyclohexane solution containing 2.5 parts by weight of styrene and 20 parts by weight of butadiene was added to the polymerization solution, and after polymerization at 70°C for 1 hour, cyclohexane solution containing 2.5 parts by weight of styrene and 20 parts by weight of butadiene was added. 1 at 70°C by adding the solution.
Polymerized for hours. Thereafter, a cyclohexane solution containing 10'i parts of styrene and 5 parts by weight of butadiene was added and polymerized at 70°C for 1 hour, and then 0.025 parts by weight of methanol was added. Furthermore, a cyclohexane solution containing 9 parts by weight of styrene was added and polymerized at 70°C for 30 minutes, and then 0.025 parts by weight of methanol was added.

Thereafter, a cyclohexane solution containing 6 parts by weight of styrene was added and polymerized at 70°C for 30 minutes, and then 0.025 parts by weight of methanol was added. Finally, a cyclohexane solution containing 5 parts by weight of styrene was added and heated to 70°C for 30 minutes.
Then polymerize for a minute. The obtained block copolymer had a styrene content of 50% by weight. (Comparative example block copolymer (g))] A cyclohexane solution containing 25 parts by weight of styrene and n-butyl were placed in the same autoclave as above. lithium 0.1
70 by adding n-hexane solution containing 0.5 parts by weight.
7'Co was polymerized for 1 hour at 70° C. Next, a cyclohexane solution containing 60 parts by weight of butadiene was added to the polymerization solution, and polymerization was performed at 70° C. for 2 hours. Furthermore, a cyclohexane solution containing 15 parts by weight of styrene was added and the mixture was heated at 70°C.
Polymerized for hours. The styrene content of the resulting block copolymer was 40% by weight.

[Comparative example block copolymer (g)]

A cyclohexane solution containing 70 parts by weight of styrene and 0.1 part of n-butyllithium were placed in the same autoclave as above.
Add a n-hexane solution containing 6 parts by weight and heat to 70°C.
Polymerize for 1 hour and then. Next, add butadiene 30 to the polymerization solution.
Add a cyclohexane solution containing parts by weight to 70°C.
Polymerization was carried out for 2 hours. Thereafter, 0.106 parts by weight of silicon tetrachloride was added to this polymer solution, and the mixture was reacted at 70° C. for 30 minutes. The styrene content of the obtained secondary block copolymer was 30% by weight.

Each of the block copolymers obtained as described above contained 4-methyl-2,6-sheet-tert-butylphenoltodris-nonylphenyl 7-osphite as a stabilizer at 0% to 100 parts by weight of the block copolymer. After adding .5 parts by weight, the solvent was distilled off under heating.

Next, compositional analysis of each block copolymer was conducted based on the above-mentioned method developed by Tanaka et al. of the University of Technology. The analyzed high performance liquid chromatogram generally has 254 on the vertical axis.
The absorbance detected at a wavelength of nm is displayed, and the horizontal axis shows the vinyl aromatic hydrocarbon content of the eluted component (obtained using calibration a prepared in advance according to the amount of elution). An example of this is shown in FIG.

In the gt diagram, 1.2 represents the block copolymer (4) and CB) ft specified in the present invention, and 3 represents the block copolymer (g) of the comparative example.

Examples 1 to 3 and Comparative Examples 1 to 4 A composition was prepared by blending 5 parts by weight of the block copolymers shown in Table 1 with 100 parts by weight of straight asphalt (Stoas 60/80, Maruzen Sekiyu G). The following performance evaluations were performed.

Penetration is according to JISK 2207K, 2 in a constant temperature water bath.
The length that a specified needle enters into a sample kept at 5° C. in 5 seconds was measured. The softening point is determined according to JIS K 2207, by filling a specified ring with a sample, supporting it horizontally in a water bath, placing a 3.5f ball T device in the center of the sample, and increasing the bath temperature at a rate of 5℃/-. Next, measure the temperature when the sample touches the bottom plate using the weight of the ball.9. The elongation is determined according to JIS K2207. After pouring the sample neatly and shaping it into a specified shape, the sample is kept at 15°C in a constant temperature water bath, and then the sample is stretched at a speed of 5 cm/-. The distance it stretched before it broke was measured.

Toughness and tenacity are measured according to the method stipulated by the Japan Road Association.
R, depth of 2.7 cm in an aluminum container and pulled out at a temperature of 25 °C at a speed of 50 ay'm. The vertical axis is the load applied to the hemisphere, and the horizontal axis is the displacement. , the total energy was measured as toughness, and the energy at the hem was measured as tenacity.0 These results are shown in Table 1 and show that the composition using the block copolymer specified in the present invention has excellent penetration. It can be seen that the temperature, softening point, elongation and strength are shown.

In addition, block copolymers G and H of comparative examples were produced in the same manner as block copolymer A except that the fjk of styrene used was changed. In addition, the block copolymer weight of the comparative example is
It was created by mixing block copolymers with different styrene contents produced in the same manner as block copolymer A.

The following margin Examples 4 to 6 and Comparative Example 5.6 Straight asphalt (Stoas 60/80)
Block copolymer shown in the table? An asphalt composition was prepared and its performance was evaluated.

The results are shown in Table 2.

Table 2 below is a blank space Examples 7 to 1
A block copolymer was used in which the styrene content in the main peak in compositional analysis was 24% by weight, and the total ratio of component (4) and component (B) was 50%, as shown in Table 3. An asphalt composition was prepared according to the formulation described below, its performance was evaluated, and the fF-o results are shown in Table 3. ! ! A composition containing fibrous material was prepared and the following was prepared: 0 620/30 prone asphalt) 15 parts by weight O in the block copolymer) 15 parts by weight O heavy calcium carbonate 60 parts by weight O finely powdered silica
The tensile strength of the composition obtained in 10 parts by weight is 12 K4/d.
The tensile elongation was 200 inches, and the tear strength was 9 breasts/-.

Example 12 About 20 parts by weight of the composition of Example 4 and 95 parts by weight of aggregate
An asphalt mixture for road paving was prepared by mixing at 0°C. The obtained composite material had excellent heat resistance, stability, low-temperature properties, and abrasion resistance, and was suitable for road paving.

Example 13 Block copolymer (4) was produced in the same manner as block copolymer (4) except that the total amount of styrene used was 30% by weight and tetrahydrofuran was used as the vinylizing agent. A block copolymer having a styrene content of 30% by weight and a polybutashev portion of 1.2-JtrlL of 35% was obtained.

A block copolymer (J) with a hydrogenation rate of 98 was obtained by hydrogenating the block copolymer with the method described in JP-A-59-133203. In this block copolymer, the total amount of component A and component B in the composition analysis was 55%.

Next, a composition was prepared by blending 15 parts by weight of the block copolymer and 100 parts by weight of straight asphalt (Stoas 60/8G).The softening point of the resulting composition was 65.
℃, the penetration was 551/1 Gm, and the elongation was 45.

[Brief explanation of drawings]

Figure 1 shows block copolymers GA), 1, (B) of the present invention.
, 2 and comparative example block copolymers (g) and 3, the relationship between absorbance and styrene content (wt%) is shown. Patent applicant: Asahi Kasei Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] (a) It has at least one polymer segment mainly composed of vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of conjugated diene, which is conjugated with vinyl aromatic hydrocarbon. Weight ratio with diene is 10/90 or more, 60/40
In the following block copolymers or hydrogenated products thereof,
Component A (component whose vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak and the difference is 5% by weight or more) and component B (component) determined from composition analysis by high performance liquid chromatography. block copolymer (b ) a bituminous material composition consisting of a bituminous material;