JPH1121385A - Colored paving binder composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored paving binder composition that exhibits excellent flowability when applied and develops further improved strength properties. SOLUTION: This composition is prepared by mixing an isoprene hydrocarbon resin obtained by cationically polymerizing a monomer mixture comprising 25-70 wt.% isoprene, 25-70 wt.% aromatic monoolefin and 5-40 wt.% aliphatic monoolefin in the presence of an aluminum halide with a process oil and a thermoplastic rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored pavement binder composition comprising a specific isoprene-based hydrocarbon resin as a binder in place of asphalt or modified asphalt.

[0002]

2. Description of the Related Art Colored pavement binder compositions that do not use asphalt or modified asphalt are used for colored pavements and colored pavements such as roadways, sidewalks, amusement parks, playgrounds, parks and plazas. As such a colored pavement binder composition, for example, JP-B-3-35563 discloses a thermoplastic resin such as a petroleum resin, a coumarone indene resin, an alkylbenzene resin, a rosin and its modified resin, and a terpene resin; A composition comprising a petroleum-based process oil, a thermoplastic polymer compatible therewith, and a urethane prepolymer of a diene-based liquid rubber is disclosed in
The 00862 discloses a composition comprising petroleum resins C ₄ -C _9, petroleum resins such as terpene and / or phenolic resins, Kumaron'inde resins, coal resins and xylene resins, and petroleum-based solvent-extracted oil, and thermoplastic rubber Is disclosed.

[0003] The binder composition for colored pavement is mixed with an aggregate or a filler in a heated and molten state in the same manner as asphalt or modified asphalt, and is applied in a thin layer at a construction site. It is necessary that the flow characteristics such as low viscosity, good flowability and excellent workability are balanced with the strength characteristics to withstand use after paving. However, with the conventional colored pavement binder composition, those having excellent flow characteristics and good construction characteristics have inferior strength characteristics, while those having good strength characteristics have inferior workability. There is a need for such a composition that balances properties and strength.

[0004] It is an object of the present invention to provide a colored paving binder composition which maintains good fluidity during construction and has further improved strength properties. The present inventors have repeatedly studied to develop a hot-melt colored pavement binder composition having a balance between workability and strength properties, and as a result, the petroleum resin blended in the conventional composition is C9 petroleum oil. Resin or dicyclopentadiene-based petroleum resin.
Even petroleum-based resins do not contain isoprene as the main component, and it is judged that this is the cause of the inadequate balance between workability and strength, and specific isoprene is substituted for these petroleum resins. It has been found that it is effective to use a hydrocarbon resin, and the present invention has been completed.

[0005]

Thus, according to the present invention, (a) 25 to 70% by weight of isoprene, 25 to 70% by weight of aromatic monoolefin and 5 to 50% of aliphatic monoolefin
(B) process oil and (c) a thermoplastic rubber are blended with an isoprene-based hydrocarbon resin obtained by cationically polymerizing a monomer mixture consisting of ４０40% by weight in the presence of an aluminum halide-based catalyst. A colored paving binder composition is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in detail with reference to embodiments of the present invention. The isoprene-based hydrocarbon resin used in the present invention comprises a monomer mixture comprising 25 to 70% by weight of isoprene, 25 to 70% by weight of an aromatic monoolefin, and 5 to 40% by weight of an aliphatic monoolefin. Is a hydrocarbon resin obtained by cationic polymerization in the presence of

The use ratio of isoprene in the monomer mixture is as described above. If the use ratio is less than 25% by weight, a large amount of low-molecular liquid components are formed during the polymerization reaction, and the mechanical properties of the resin are significantly deteriorated. And the use ratio is 70% by weight.
When the ratio exceeds, a high molecular weight component which adversely affects the compatibility with the thermoplastic rubber is easily generated. The preferred use ratio is 30
~ 65% by weight.

On the other hand, examples of the aromatic monoolefin include styrene, α-methylstyrene, vinyltoluene, and isopropenyltoluene. Among them, those having 10 or less carbon atoms are awarded. The usage ratio in the monomer mixture is as described above, and if it is out of this range, the compatibility with the thermoplastic rubber is reduced. The preferred use ratio is 30 to
65% by weight.

Examples of the aliphatic monoolefin include isobutylene, butene-1, cis-butene-2, trans-butene-2, pentene-1, cis-pentene-2, trans-pentene-2, and 2-methyl-butene. Examples thereof include 1,2-methyl-butene-2, diisobutylene, cyclopentene, and cyclohexene, and particularly those having 4 to 8 carbon atoms are awarded. By using such an aliphatic monoolefin, the compatibility with the thermoplastic rubber is improved,
The strength characteristics of the resin are improved. When the use ratio in the monomer mixture is less than 5% by weight, the production of a liquid low molecular weight component increases, and the strength characteristics of the resin are remarkably reduced. When it exceeds 40% by weight, the yield of the resin is reduced. The preferred use ratio is 10
30% by weight.

As long as the effects of the present invention are not substantially impaired, 1,3-butadiene and 1,3-butadiene
It may contain other monomer components that can be copolymerized with the above monomers such as pentadiene, cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, indene, and methylindene, but the content ratio is as small as possible. It is preferably 10% by weight or less, preferably 5% by weight or less.

The isoprene-based hydrocarbon resin used in the present invention can be obtained by cationic polymerization of the above monomer mixture in the presence of an aluminum halide-based catalyst according to a conventional method. Examples of catalysts used include:
Examples include aluminum halides such as aluminum chloride and aluminum bromide, and complexes formed with these and ligands such as hydrochloric acid, halogenated hydrocarbons and aromatic hydrocarbons.

The cationic polymerization of the above monomer mixture is usually carried out without solvent or in a solvent inert to the reaction.
As the reaction solvent, aromatic hydrocarbon, aliphatic hydrocarbon,
Either alicyclic hydrocarbons or halogenated hydrocarbons can be used effectively, but among them, aromatic hydrocarbons are preferred. This solvent is generally used in an amount of 20 to 1000 parts by weight, preferably 50 to 500 parts by weight, per 100 parts by weight of the monomer mixture.
Used in parts by weight. The polymerization is usually carried out at 0 to 120.
C., preferably at a temperature of from 20 to 100 C., and the pressure of the reaction system may be above or below atmospheric pressure.
Reaction times generally can vary from seconds to 12 hours or more. After completion of the polymerization, the mixture is treated according to the information and dried to obtain a target isoprene-based hydrocarbon resin.

The process oil used in the present invention is an essential component for imparting appropriate fluidity to the composition and ensuring good workability. As the process oil, a petroleum-based process oil, a lubricating oil, a heavy mineral oil, a liquid obtained by polymerizing an unsaturated hydrocarbon of petroleum or a petroleum decomposition product, or the like can be used. Along with these, creosote oil, anthracene oil, pine oil, plasticizer, fats and oils (dry oil, semi-dry oil, non-dry oil and derivatives thereof) can also be used in combination.

Petroleum-based process oils are commonly used as auxiliary plasticizers such as vinyl chloride resins as compounding agents such as rubber softeners and processing aids. Depending on the ratio of components such as naphthenics and aromatics, they are classified into types such as paraffinic, naphthenic and aromatic process oils, and any of them can be used in the present invention.

A preferred petroleum-based process oil is “until petroleum products can be produced” published by the Petroleum Association of Japan on November 30, 1971.
Oily substance rich in aromatics and naphthenes obtained by solvent extraction in the process of producing a lubricating oil from crude oil, as described in "General Lubricating Oil Production Process" in FIG. And generally has a boiling point (atmospheric pressure) of 350
° C or higher, viscosity of 5 to 100 cst (at 100 ° C), penetration (according to JIS K2207) of 1000
As described above, the softening point (by the ring and ball method) is 20 ° C. or less.

The thermoplastic rubber used in the present invention includes:
Those which are compatible with the hydrocarbon resin and the process oil are preferable. For example, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, isoprene-
Butadiene copolymer rubber, polybutadiene rubber, polyisoprene rubber, natural rubber, butyl rubber, chlorinated or brominated butyl rubber, ethylene-propylene copolymer rubber (EP
M), ethylene-propylene-diene monomer terpolymer rubber (EPDM), chlorinated polyethylene, chloroprene rubber, chlorosulfonated polyethylene, and the like.

Particularly preferred thermoplastic rubbers are linear and branched block copolymers having a polystyrene segment (S) at both ends of a rubber component segment such as polybutadiene (B) or polyisoprene (I). Examples include SBS, SIS, and SEBS (polystyrene-polyethylene / butylene-polystyrene: hydrogenated butadiene units of SBS). As for the molecular weight, those having a weight average molecular weight of 8 × 10 ⁴ or more in terms of standard polystyrene measured by GPC, a styrene content of 10 to 50% by weight, and a specific gravity of 0.9 or more are preferable.

The colored pavement binder composition of the present invention contains the above-mentioned components, and usually contains 10 parts by weight of process oil per 100 parts by weight of isoprene-based hydrocarbon resin.
-100 parts by weight, preferably 30-80 parts by weight, and the thermoplastic rubber is 10-100 parts by weight, preferably 20-80 parts by weight. If the amount of the process oil is too small, the desired fluidity cannot be obtained, and the workability deteriorates. If the amount is too large, the workability decreases. In addition, when the amount of the thermoplastic rubber is too small, the bonding force (caking force) with the aggregate or filler decreases, and when the amount is too large, the melting temperature (softening temperature) of the composition increases, and the viscosity of the melt increases. And the fluidity is reduced.

The colored pavement binder composition of the present invention can be made into a colored pavement composition by blending an aggregate, a color pigment, a filler, and the like, similarly to the conventional colored pavement composition. it can. The composition of the present invention can improve the balance between workability and strength by using an isoprene-based hydrocarbon resin instead of the conventionally used C9-based or cyclopentadiene-based petroleum resin.

The colored paving binder composition of the present invention can be prepared by heating and mixing the above-mentioned isoprene-based hydrocarbon resin, process oil, thermoplastic rubber and the like at a predetermined ratio. The order of mixing the components is not particularly limited. For example, a method of mixing an isoprene-based hydrocarbon resin and a process oil, adding a thermoplastic rubber to the mixture, mixing the isoprene-based hydrocarbon resin, the process oil, and the thermoplastic oil Any method such as a method of simultaneously mixing the three rubbers can be employed. In addition, the binder composition prepared as described above may be mixed with heat by adding other additives such as aggregate, or when preparing a colored pavement mixture in a plant, the binder may be used. The components of the composition and the aggregate can be mixed simultaneously.

[0021]

Next, the present invention will be described specifically with reference to examples. In the following, parts and percentages are by weight unless otherwise specified.

Examples 1 to 5 and Comparative Examples 1 and 2 100 parts of benzene and aluminum chloride were placed in a reaction vessel.
After charging 2 parts, 100 parts of the monomer mixture shown in Table 1 was added and polymerized at 65 ° C. to obtain hydrocarbon resins having various compositions.

Next, a colored pavement binder composition was prepared according to the formulation shown in Table 2. The composition was prepared by putting each component in a container, heating to 180 ° C. in a nitrogen stream, melting and mixing for 30 minutes with stirring. The properties of each of the obtained compositions were evaluated according to the following test methods. Table 2 shows the evaluation results.

(1) Elongation (mm) Measured at 25 ° C. according to JIS K2530. (2) Softening point (° C.) of hydrocarbon resin Measured by a ring and ball method according to JIS K2531. (3) Penetration The value after applying a load of 100 g for 5 seconds at 25 ° C. in accordance with JIS K2530 was determined. (4) Tensile test According to JIS K6301, the elongation percentage (maximum point) when the strength shows the yield value, the elongation percentage at break (%), and the strength at break (tensile strength) (kgf / cm ² ) were determined. . (5) HB viscosity (ps) The melt viscosity at 160 ° C. and 180 ° C. was measured using a B-type viscometer.

[0025]

[Table 1]

[0026]

[Table 2]

(Note) (* 1) Naphthenic process oil manufactured by Shell Chemical Co., Ltd. (* 2) Aromatic process oil manufactured by Idemitsu Kosan Co., Ltd. (* 3) Styrene-butadiene (SBS) block copolymer (styrene content 43%) (* 4) Styrene-butadiene (SBS) block copolymer (styrene content 35%) (* 5) Phenolic antioxidant manufactured by Sumitomo Chemical Co., Ltd.

The results in Table 2 show that, in the compositions of Comparative Examples 1 and 2 using the conventional hydrocarbon resin, those having excellent strength properties have high viscosity (Comparative Example 1), and those having low viscosity have low viscosity. Poor strength characteristics (Comparative Example 2). On the other hand, in the compositions of the present invention using the isoprene-based hydrocarbon resin (Examples 1 to 5), the strength properties were all excellent, but the viscosity did not increase, indicating that both properties were balanced. ing.

[0029]

According to the present invention described above, there is provided a colored pavement binder excellent in workability in which strength characteristics and viscosity characteristics are balanced without using asphalt.

A preferred embodiment of the first embodiment will be described below. (1) Based on 100 parts by weight of the isoprene-based hydrocarbon resin, 10 to 100 parts by weight, preferably 30 to 80 parts by weight, of the process oil and 10 to 100 parts by weight, preferably 20 to 80 parts by weight of the thermoplastic rubber. Use in proportion. (2) The isoprene-based hydrocarbon resin is from 30 to 30 isoprene.
It is obtained by polymerizing a monomer mixture comprising 65% by weight, 30 to 65% by weight of an aromatic monoolefin and 10 to 30% by weight of an aliphatic monoolefin. (3) The process oil is at least one selected from petroleum-based process oils, lubricating oils, heavy mineral oils, and plasticizers. (4) The thermoplastic rubber is SBS having a weight average molecular weight of 8 × 10 ⁴ or more and a styrene content of 10 to 50% by weight;
It is at least one selected from SIS and SEBS.

Claims (1)

[Claims] 1. A monomer mixture comprising (a) 25 to 70% by weight of isoprene, 25 to 70% by weight of an aromatic monoolefin and 5 to 40% by weight of an aliphatic monoolefin in the presence of an aluminum halide catalyst. Isoprene-based hydrocarbon resin obtained by cationic polymerization,
A colored pavement binder composition comprising (b) a process oil and (c) a thermoplastic rubber.