JPH09111095A - Binder composition for colored pavement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a binder composition for colored pavement having approximately the same water resistance, plastic fluidity resistance and adhesiveness to an aggregate as those of a binder for asphalt-based drainage pavement. SOLUTION: This composition comprises (A) 20-90wt.% of a petroleum-based solvent extracted oil, (2) 20-70wt.% of a petroleum-based, coal-based and/or natural resin, (3) 4-12wt.% of a thermoplastic rubber and (4) 0.3-5wt.% of a maleated polyolefin resin.

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, and more particularly to a colored pavement binder composition suitable for roadway pavement on heavy traffic routes.

[0002]

2. Description of the Related Art Binders used for conventional color pavement have been mainly used on sidewalks, bicycle paths, light traffic roads, etc., but these binders are paraffin-based, naphthene-based, aromatic-based derived from petroleum crude oil. A thermoplastic resin and rubber are added to the light-colored lubricating oil fraction to give properties equivalent to those of straight asphalt normally used in asphalt mixtures, and aggregates, fillers,
It is a mixture of pigments and the like. Therefore, this binder has only the same degree of deformation resistance as a mixture using straight asphalt, and therefore, for use in places with light loads such as sidewalks, bicycle paths and light traffic roadways, There is no problem, but when used for pavement in places where heavy loads are applied, such as heavy traffic lines and vehicle stops, deformation resistance is small and rutting is likely to occur.

Further, there is a problem that since the adhesiveness to the aggregate is insufficient, the binder is easily peeled from the aggregate and cracks are easily generated.

On the other hand, JP-A-4-359063 discloses a base material 100 in which a dicyclopentadiene petroleum resin is dissolved in an aromatic process oil to adjust the penetration.
2 to 6 parts by weight of a teleblock copolymer such as styrene-butadiene-styrene or styrene-isoprene-styrene, and ethylene ethyl having a molar content of ethyl acrylate or vinyl acetate in the range of 4 to 20%. There has been proposed an invention relating to a colored pavement binder composition in which acrylate or ethylene vinyl acetate alone or both of them are added in an addition ratio of 2 to 6 parts by weight and uniformly dissolved and mixed. This invention uses a specific base binder and a teleblock polymer to
The composition has an improved toughness / tenacity value.

Further, in JP-A-6-157917, an aromatic process oil is mainly used, and a tereblock copolymer such as styrene-butadiene-styrene or styrene-isoprene-styrene is added to the aromatic process oil. There has also been proposed a colored paving binder composition in which a dicyclopentadiene-based petroleum resin and a C ₅ -based petroleum resin, which increase the modification effect of the teleblock copolymer, are added to the colored paving binder.

However, all of these compositions are required to be further improved in water resistance, plastic flow resistance, adhesiveness with aggregates, and the like.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to obtain water resistance equivalent to that of an asphalt-based drainage pavement binder,
Another object of the present invention is to provide a novel pigmented pavement binder composition having plastic flow resistance and adhesiveness to aggregate.

[0008]

The present invention provides: (1) Petroleum-based solvent-extracted oil 20-90% by weight, preferably 40-70% by weight (2) Petroleum-based, coal-based and / or 20-70% by weight , Natural resin preferably 30 to 60% by weight (3) thermoplastic rubber 4 to 12% by weight, preferably 6 to 10% by weight (4) maleated polyolefin resin 0.3 to 5% by weight, preferably 1 to 4% by weight % Of the binder composition for colored paving.

The petroleum solvent-extracted oil is
March 30, published by the Petroleum Association of Japan "Petroleum products made" 10th
As shown in page 1, FIG. 6-1, “General lubricating oil production process”, it is an oily substance rich in aromatic and naphthene content obtained by solvent extraction in the process of producing lubricating oil from crude oil. , Generally boiling point (at atmospheric pressure) 35
0 ° C or higher, viscosity 5 to 100 cSt / 100 ° C, preferably 30 cSt to 100 cSt / 100 ° C, penetration (JI
S K 2207) 1000 or more, softening point (JIS K
2207) 20 ° C. or lower, particularly preferably a total of aromatic and naphthene content of 45 wt% or more (by ring analysis) and a flash point of 220 ° C. or more.

The petroleum-based, coal-based and / or natural-based resin is a solid resin starting from petroleum, coal and / or natural products, and is generally a polymer having a molecular weight of about 200 to 3000, and is an aliphatic or aromatic resin. And / or one of cyclic compounds
It is a terpolymer or terpolymer (co) polymer. Examples of the petroleum-based resin include C _{4 to} C ₉ petroleum resin, terpene and / or phenol resin, and examples of the coal-based resin include coumarone indene resin, xylene resin and the like, and natural type. Examples of the resin include various resin acid esters.

Among these, a particularly preferable petroleum resin is one using a C ₅ fraction or a C ₅ or C ₉ fraction as a raw material.

Petroleum resin using C ₅ fraction as a raw material is a polymer of C ₅ fraction which is a decomposition product when naphtha is thermally decomposed to produce ethylene, propylene and the like, and cyclopentadiene (CPD) And dicyclopentadiene (DCPD)
Those with a high content of have a high softening point. Molecular weight about 20
0-2000, generally 1000-1500, softening point 1
It is a colorless to pale yellow resin at 00 to 150 ° C.

Furthermore, C _5, C ₉ copolymer petroleum resin of C ₅ and C ₉ fraction as a raw material, generally a molecular weight of about 300-3
000 and a softening point of 100 to 180 ° C. Among these, those having a high transparency with a Gardner index of 6 or less and having a softening point of 120 ° C. or more are preferable.

The thermoplastic rubber can be used without vulcanization like a block polymer composed of a polymer chain of a vinyl monomer such as styrene and acrylonitrile and a polymer chain of a diene monomer such as butadiene and isoprene. Polymers that can be prepared, and typical ones include styrene-butadiene block copolymers and acrylonitrile-butadiene copolymers. In particular, they have polystyrene segments as terminal segments, and rubber component segments include, for example, polybutadiene. A chain or branched block copolymer having a segment, a polyisoprene segment, a polyethylene, a butylene segment, etc. is preferable. Typical examples are SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), SEBS.
(Styrene-ethylene / butylene-styrene block copolymer) and the like. The molecular weight is 5 × 10 ^4.
Above, polystyrene content 10 ~ 50wt%, specific gravity 0.9
The above are preferred.

Examples of the maleated polyolefin resin include the following thermoplastic resins modified with 0.1 to 7.0% of maleic anhydride. Maleated Ethylene-Ethyl Acrylate Copolymer (Maleized EEA Resin) Maleated Ethylene-Vinyl Acetate Copolymer (Maleized EVA Resin) Maleated Polypropylene Resin Maleated Polyethylene Resin A typical product is Chimie's "LO" in France.
TADER ", Sumitomo Chemical's bondine, etc. Of these, maleic anhydride 0.5 is preferable.
It is the above-mentioned thermoplastic resin modified by 5.0%.

[0016]

EXAMPLES AND COMPARATIVE EXAMPLES Examples and comparative examples of the present invention will be described below. The compositions of the binder compositions of Examples and Comparative Examples are shown in Tables 1 to 1.
2, the properties of the binder composition are shown in Tables 3 to 5, the performance of the mixture of the aggregate and the binder composition is shown in Tables 6 to 8, and the evaluation results are shown in Tables 9 to 1.
It is shown in FIG.

[0017]

[Table 1]

* 1 BFE is manufactured by Showa Yokkaichi Oil Co., Ltd., and its properties are 68 centistokes at a viscosity of 100 ° C.,
It has an aromatic content of 33% by weight, a naphthene content of 26% by weight, a paraffin content of 41% by weight, and a flash point of 254 ° C. * 2 HVI is manufactured by Showa Yokkaichi Sekiyu Co., Ltd., and its properties are 33 centistokes at 100 ° C, aromatic content 5% by weight, naphthene content 27% by weight, paraffin content 68% by weight, and flash point 324 ° C. Is. * 3 TR manufactured by JS R Elastomer Co., Ltd.
-1101 is a thermoplastic rubber of a styrene-butadiene-styrene block copolymer and has a specific gravity of 0.
94, hardness (Shore A) 72, 300% modulus 29
kg / cm ² , tensile strength 330 kg / cm ² , elongation 88
0%, solution viscosity (polymer concentration, 25 wt% toluene solution) 4000 cps. 25 ° C. * 4 Product name QTN-1325 manufactured by Nippon Zeon Co., Ltd.
The properties are hue 2 (Gardner No.), softening point 125 (° C.), bromine number 55 (g / 100 g), molecular weight 4
60, flash point 245 (° C). * 5 N-100 manufactured by Nippon Steel Chemical Co., Ltd., which has a hue of 15 (Gardner No.) and a softening point of 100.
(° C.), bromine number 14 (g / 100 g), and molecular weight 640. * 6 Yasuhara Chemical Co., Ltd. product name Z-115
The properties are those having a hue of 10 (Gardner No.), a softening point of 115 (° C.) and an acid value of 0.8. * 7 Bondyne AX-8060 manufactured by Sumitomo Chemical Co., Ltd.
The melt flow rate is 40 (g / 10
Min), density 0.95 (g / cm ³ ), picat softening point 4
0 (° C.), melting point DSC method 68 (° C.). * 8 Sanyo Kasei Kogyo Co., Ltd. Yumex 1001 with properties of specific gravity 0.95, molecular weight 15,000, melt viscosity (160 ° C) 16,000 cps, softening point 154
(° C) and acid value 26 (mgKOH / g). * 9 A-70 manufactured by Mitsui DuPont Polychemical Co., Ltd.
No. 7, its properties are 17% EA content, MFR (melt.
Flow rate) 25 (dg / min), and the Vicat softening point is 57 ° C.

[0019]

[Table 2]

[0020]

[Table 3]

* 10 to * 16 These evaluation tests were carried out in accordance with the asphalt test method introduced in "Handbook of Pavement Test Method", P316-456, published by Japan Road Association in November, 1988.

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

* 17 The mixture is a drainage paving mixture with a porosity of about 20%, a binder amount of 5.0% by weight, an aggregate composition of 76.0% by weight of crushed stone No. 6, 14.2% by weight of coarse sand, stone powder. It was evaluated at 4.8% by weight. * 18-20,23,25 These evaluation tests are the mixture tests introduced in "Handbook of Pavement Test Law" P505-568, published by the Japan Road Association in November 1988. * 18 Uniaxial compression test of asphalt mixture at 60 ℃. * 19 Carry out after soaking * 18 above in water at 60 ° C for 2 days or more. The water resistance is evaluated, and the higher the residual rate, the better the water resistance. * 20 In a test for indoor evaluation of the flow resistance of an asphalt mixture at 60 ° C, a small rubber wheel (loading pressure 6.4 kg with a ground pressure of 6.4 kg) with a load adjusted on a 30 × 30 × 5 cm thick specimen.
/ Cm ² ) at 42 times / minute, and the dynamic stability (DS value) is calculated from the deformation amount after 45 minutes (d ₄₅ ) and the deformation amount after 60 minutes (d ₆₀ ) by the following formula, The larger the DS value, the higher the flow resistance. Dynamic stability DS value (times / mm) = (15 × 42) ÷ (d
_60- d ₄₅ ) * 21 A type of test method for determining the minimum amount of binder that can stably maintain the aggregate of drainage asphalt mixture for paving. Loss after the test was performed for the Marshall stability test specimens with different binder amounts by using the Los Angeles tester (machine specified in the method for testing the coarse aggregate grinding), rotating the drum 300 times without using steel balls. Measure the quantity. Note: At the end of each test, completely remove the scattered aggregate in the tester. The mass of the test piece after the test is measured by removing the fine particles that have entered the voids of the test piece. * 22 A type of maximum binder amount determination test for drainage asphalt mixtures for paving. The asphalt mixture in which the amount of binder is changed is heat-cured for a required time in a drying oven at a constant temperature, and the mass of binder lost due to sagging or adhesion is measured. A bat is generally used as the curing device. Note: The curing temperature of the asphalt mixture depends on the properties of the binder used. Also, the thickness of the asphalt mixture to the vat should be uniform. * 23 A test to evaluate the resistance of the asphalt coating to peeling from the aggregate. A static peel test is generally performed in which an aggregate completely covered with asphalt is spread on a glass plate, dipped in a water bath at 80 ° C., and the peel state is visually observed. The peeled area of the asphalt coating from the aggregate is evaluated as a percentage (%). Note: The peeled area is evaluated visually, but it is evaluated by multiple people because individual differences tend to occur. * 24 This is based on the RIEDEL & WEBER TEST (proposed by the UK Road Research Institute), which is said to be the most severe test method and its test results are said to correspond to the results of actual road tests relatively well. The test was conducted in the following procedure. Particle size after cleaning and drying in a container for aggregates 13.2-9.5 m
About 100 g of the aggregate of m is weighed and heated for 1 hour in a dryer kept at a temperature higher by 5 ° C. than the mixing temperature determined from the temperature-viscosity relationship. On the other hand, about 5.5 g of asphalt is weighed in another container and heated at the same temperature as the aggregate for 15 minutes. After that, transfer the aggregate into a container containing asphalt,
Mix quickly with a spatula for 1-1.5 minutes to completely cover the aggregate. A 1 mol / l sodium carbonate solution and an appropriate amount of aggregate cooled to room temperature are put in an Erlenmeyer flask and boiled on a hot plate for 1 to 5 minutes. After washing the aggregate after boiling and drying, the peeled state is visually observed. * 25 A large difference is observed in the crush strength between the samples after 30 minutes at 80 ° C and after immersion in water for 24 hours. Further, as a result of visually evaluating the peeling ratio between the aggregate and the binder after the test, a large difference was observed in the peeling ratio. Therefore, this test is an effective evaluation method for evaluating peel resistance.

[0026]

[Table 7]

[0027]

[Table 8]

The data in Tables 1 to 8 were comprehensively examined, and the evaluation results are summarized in Tables 9 to 11.

[0029]

[Table 9] Evaluation criteria ◎ Very good. ○ Excellent. △ Somewhat inferior. × Inferior.

[0030]

[Table 10]

[0031]

[Table 11]

In Examples 1 to 5, since the maleated polyolefin resin was used in an appropriate amount of 3%, the mixture was very excellent in water resistance. However, Comparative Examples 1 to 3 have poor water resistance because they do not use the maleinized polyolefin resin or the addition amount thereof is small.

As is clear from Comparative Example 4, if the amount of the maleinized polyolefin resin added is too large, the viscosity at high temperature becomes too high, resulting in poor workability in preparing the mixture.

As is clear from Comparative Example 5, when the amount of the thermoplastic rubber added is small, the flow resistance, crack resistance, scatter resistance of aggregate, and sagging test are poor. Further, as is clear from Comparative Example 6, if the addition amount of the thermoplastic rubber is too large, the workability is poor because the viscosity at high temperature is high.

As is clear from Comparative Example 7, if the amount of resin added is too large, the penetration will be too small, and the low temperature elongation will be poor and cracks will easily occur. In addition, the amount of wear in the cantablow test is large, and aggregates are easily scattered.

The commercially available colored paving color binders tended to be inferior in water resistance as compared with Examples 1-5. Moreover, the low temperature elongation, tenacity, and cantablow tests also show a tendency to be slightly inferior.

Regarding Examples 1 to 5, even when compared with the high viscosity modified asphalt used for asphalt-based drainage pavement and having many construction results, Tables 9 to 11 are shown.
From the evaluation results shown in (1), it is understood that Examples 1 to 5 show very excellent performance as in the asphalt high viscosity modified asphalt.

[0038]

The mixture with the aggregate using the colored pavement binder composition of the present invention has excellent characteristics in water resistance, fluidity resistance, crack resistance, aggregate scattering resistance, and workability. Have Therefore, the composition of the present invention is used as a binder for color paving of dense grain type and open grain type such as drainage pavement in heavy traffic roads such as expressways in which large vehicles such as large trucks and buses are heavy, and in bus lanes. It is extremely useful as a binder for color pavement that clearly shows vehicle division zones such as vehicle stops at intersections and intersections.

Claims (1)

[Claims] (1) Petroleum-based solvent-extracted oil 20 to 90% by weight (2) Petroleum-based or coal-based 20 to 70% by weight and / or natural resin (3) Thermoplastic rubber 4 to 12% by weight (4 ) Maleinized polyolefin resin 0.3 to 5% by weight, which is a binder composition for colored pavement.