JPH07278439A - Additive for highly durable hot bituminous material, highly durable asphalt pavement composition using the same, and its production - Google Patents

Abstract

PURPOSE:To obtain the subject additive which strengthens adhesion between a bituminous material and an aggregate to thereby cause the material to produce very excellent peeling-prevention effects. CONSTITUTION:This additive comprises a dicarboxylic acid of formula I and/or a dicarboxylic acid of formula II or its anhydride. The additive enables an advancement in pavement technology and is expected to have great environmental merits. In those formulas, R<1> to R<3> are each an 8-30C linear or branched satd. or unsatd. hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

This invention relates to a heated bituminous additive comprising a specific divalent carboxylic acid or an anhydride thereof.
The present invention relates to an asphalt pavement composition using the same, and a method for producing the same, and more specifically, strengthens the adhesiveness between the bituminous material and the aggregate, and as a result, exerts an extremely excellent anti-peeling agent effect on the bituminous material. The present invention relates to a heated bituminous additive that enables the above, an asphalt pavement composition using the same, and a method for producing the same.

[0002]

Bituminous substances such as asphalt, tar and pitch obtained from petroleum or coal are used for paving materials, roofing materials and waterproofing materials, and especially for paving materials. Is big. However, since the bituminous substance is non-polar, it does not sufficiently adhere to the aggregate and has a defect that the bituminous substance is separated from the aggregate due to the intervening action of water such as precipitation or groundwater.

Further, as the size and weight of vehicles increase, rutting and fluidization of asphalt pavement occur, impairing smooth traffic and running performance. As a countermeasure against this, a method of mixing thermoplastic resin or rubber into the bitumen has been devised.
However, a bituminous material mixed with a thermoplastic resin or rubber has a problem that the adhesiveness between the aggregate and the bituminous material is lower than that of the original bituminous material.

As described above, the technical problem of improving the adhesion between the bituminous material and the aggregate is a very important problem for improving the performance of the asphalt pavement, but various methods have been devised to solve the problem. . For example, according to Japanese Examined Patent Publication No. 55-38995, higher aliphatic polyamines and their derivatives are used as a countermeasure for this, but conventionally devised higher aliphatic polyamines and their derivatives have improved initial adhesion improving performance. However, the durability of the effect of preventing peeling is said to be about one year.

Further, Japanese Patent Application Laid-Open No. 57-51745 proposes a method of adding a silane compound to improve the adhesion performance. However, it is harmful when it is added to a heated bituminous material or during the production of a heated mixture. It emits various odors and steam and leaves a problem in terms of safety and hygiene, and it is neither economical nor practical.

Furthermore, a composition prepared by adding and mixing a phosphoric acid compound such as phosphorus pentoxide, polyphosphoric acid and phosphorus pentasulfide to asphalt is used as an additive for asphalt modification.
Although disclosed and proposed in Japanese Patent No. 3691, these phosphoric acid compounds are inorganic substances and their dispersion state in an organic substance is not always good, and the adhesion performance of asphalt to an aggregate is insufficient. Furthermore, in recent years, there is a concern that the quality of asphalt and aggregate will deteriorate, but in the recycling method that uses waste pavement material, asphalt of reduced quality is used, so strong adhesion cannot be expected, and asphalt cannot be modified. Although more and more strongly desired, a means for solving all of the above-mentioned problems and various performances required by the market has not been developed yet.

JP-A-60-188462 describes that an acidic organic phosphoric acid compound has a peeling-preventing effect, but under the present circumstances where the level for asphalt pavement is increasing due to the current heavy transportation, The performance is insufficient to satisfy these requirements, and the development of an additive having further peeling prevention performance is desired.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have made diligent efforts to obtain a bituminous composition which is further excellent in exfoliation prevention property, and as a result, a specific divalent carboxylic acid or anhydride thereof is particularly excellent in exfoliation prevention. The inventors have found that they have the ability to exert an effect on bitumen and have completed the present invention.

That is, the present invention provides the following general formula (I) and / or
Alternatively, the present invention relates to a highly durable additive for heated bituminous substances, which comprises a divalent carboxylic acid represented by (II) or an anhydride thereof.

[0010]

[Chemical 3]

(In the formula, R ^{1 to} R ³ are straight or branched chain, saturated or unsaturated hydrocarbon groups having 8 to 30 carbon atoms.) Further, the present invention provides 100 parts by weight of heated asphalt. Asphalt formulation 3 containing 0.05 to 5 parts by weight of the above additives
~ 10 parts by weight, aggregate of crushed stone, sand and filler 97 ~ 90
The present invention relates to a highly durable asphalt pavement composition, characterized by comprising:

The present invention further relates to a method for producing the above-mentioned highly durable asphalt pavement composition, which comprises kneading an asphalt mixture prepared by adding the above-mentioned additives to heated asphalt in advance and an aggregate.

The additive of the present invention may be a single compound or a mixture of a plurality of compounds.

Conventionally devised higher aliphatic polyamines and their derivatives are adsorbed and oriented in polar positive and negative polar groups,
Improves wetting between bituminous material and aggregate. However, it is effective for initial adhesion, but has a problem for long-term adhesion. For example, when external stress such as temperature rise and dynamic load is applied in the presence of water for a long period of time, since the additive itself is a surfactant, it acts as a bituminous emulsifier and removes bitumen from the aggregate. There is a drawback that

The present invention has a composition in which molecules are arranged most densely at the interface between the bituminous material and the aggregate, and further, as shown in the following reaction formula, a chemical bond is formed at the interface by a dehydration reaction to strengthen the structure. Adhesion does not replace the bituminous material even if water enters the surface of the aggregate, and it does not destroy the adhesive interface between the aggregate and the bituminous material even if it receives an impact, and exhibits an excellent anti-stripping effect. it is conceivable that. It should be noted that the anhydride is more excellent in peeling prevention effect than the divalent carboxylic acid.

[0016]

[Chemical 4]

In order to form an optimal adhesive interface which is dense in terms of molecular structure and sequence, R ¹ to R ¹ in a divalent carboxylic acid represented by the general formula (I) and / or (II) or an anhydride thereof can be used. R ³ is
A straight or branched chain, saturated or unsaturated one having 8 to 30 carbon atoms is preferable. If it is less than 8, since the hydrophobicity of the aggregate surface is low, it is necessary to increase the amount used, which is economically less advantageous. On the other hand, if it exceeds 30, the reactivity with the surface of the aggregate is lowered, so that the peeling prevention effect is lowered. The preferred carbon number is
12-18, with 18 being the most preferred carbon number.

Specifically, n- or iso-octenyl succinic acid, n- or iso-octyl succinic acid, n- or iso-dodecenyl succinic acid, n- or iso-dodecyl succinic acid, n- or iso-hexadecese succinic acid. Nylsuccinic acid, n- or iso-hexadecylsuccinic acid, n- or iso-octadecenylsuccinic acid, n- or iso-octadecylsuccinic acid, tetrapropenylsuccinic acid, hexapropenylsuccinic acid, and their anhydrides. Alternatively, di-octenylsuccinic acid, di-dodecenylsuccinic acid, di-octadecenylsuccinic acid, and their anhydrides can be used.

The additive of the present invention is contained in an amount of 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the bituminous or modified bituminous substance.
Is. If less than 0.05% by weight, the effect decreases, and 5.0% by weight
If it exceeds, it is effective but not economical.

Further, the additive of the present invention can enhance the adhesive strength of the modified bituminous substance by using in combination with one or more selected from rubbers, thermoplastic resins and thermosetting resins. .

As rubbers used in combination with the additive of the present invention, natural rubber, styrene / butadiene rubber, styrene / butadiene / styrene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, styrene / isoprene rubber,
Examples thereof include synthetic rubbers such as styrene / isoprene / styrene rubber, methyl methacrylate / butadiene rubber, and butadiene rubber, but are not limited thereto.

As the thermoplastic resin used in combination with the additive of the present invention, ethylene, propylene, vinyl acetate, acrylic acid ester, methacrylic acid ester, styrene,
Examples thereof include, but are not limited to, vinylidene chloride and vinyl propionate homopolymers and copolymers obtained by combining these. Among these, especially ethylene / vinyl acetate copolymers and ethylene / vinyl acetate
Copolymers of ethyl acrylate are preferred.

Examples of the thermosetting resin used in combination with the additive of the present invention include, but are not limited to, epoxy resin and urethane resin.

It is said that when a large amount of rubber, thermoplastic resin or thermosetting resin is used, the adhesive force of the modified bituminous material tends to be rather lowered, and it is suitable for the additive of the present invention. The combined use remarkably enhances the adhesive strength and solves the problem.

The amount of the modifiers such as rubbers, thermoplastic resins, and thermosetting resins added to the bituminous material is 80 to 99 parts by weight of the bituminous material and 20 to 1 parts by weight of the modifying material. The proportion of the modifying agent is preferably 15 to 2 parts by weight, and the bituminous and modifying agents are used in an amount of 100 parts by weight.

Further, in addition to rubbers, thermoplastic resins and thermosetting resins, the modified asphalt used in the present invention includes inorganic fillers and organic fillers such as calcium carbonate, slaked lime, Portland cement and activated carbon, petroleum resins and low molecular weight compounds. It is also possible to use the compound of the present invention in combination with a petroleum softening agent such as polyethylene, a vegetable oil softening agent such as oleic acid, various plasticizers and sulfur.

The crushed stone, sand, and filler used in the highly durable asphalt pavement composition of the present invention are provided for the present invention regardless of their materials as long as they are in accordance with the asphalt pavement procedure (edited by Japan Road Association). be able to. Crushed stone,
The mixing ratio of the aggregate consisting of sand and filler is 3 to 10 parts by weight of the asphalt mixture containing the additive of the present invention, and the aggregate 97.
~ 90 parts by weight is preferred.

The highly durable asphalt pavement composition of the present invention is prepared by adding the additive of the present invention to asphalt which has been heated in the range of 120 to 200 ° C. and kneading the thoroughly mixed asphalt mixture with crushed stone, sand and filler. It is characterized by being manufactured by In producing the highly durable asphalt pavement composition of the present invention, by adding the additive of the present invention to pre-heated asphalt, the additive of the present invention is uniformly dispersed in the asphalt, and a uniform high durability asphalt. A pavement composition is obtained.

As a method for mixing the additive of the present invention with the modified bituminous material, the modifier and the additive are simultaneously added to the bituminous material which is heated and melted at 100 to 250 ° C. under stirring, or it is previously modified. Either method of producing a bituminous substance and then adding an additive may be used.

The modified bituminous substances obtained by adding the above-mentioned modifiers to the bituminous substances appropriately selected in practical use have excellent temperature sensitivity and durability, and by adding the additive of the present invention, adhesion and peeling prevention can be achieved. A bituminous composition having improved properties and having various performances required by the market is obtained.

Therefore, it can be used for construction purposes other than road paving agents such as factory floors, roofing materials, underground protective materials for vehicles, etc. for the purpose of waterproof coating.

[0032]

EXAMPLES The present invention will be specifically described below, but the present invention is not limited to these examples. In addition,% in the following examples is% by weight. To confirm the effect of the present invention, a Riedel and Weber test and a water immersion Marshall test were performed.

Riedel and Weber Test (RIEDEL
AND WEBER TEST) is a method proposed by the British Road Research Institute and is as follows. Crushed stone 43 with a particle size of 0.15-0.075 mm 43
1 part by weight and 43 parts by weight of crushed stone with a particle size of 0.3 to 0.15 mm
Heat to 70 ° C. 14 parts by weight of asphalt or modified asphalt heated and melted at 150 ° C is added to this and mixed well, and the crushed stone is completely covered with asphalt or modified asphalt. 0.5 g of the coated asphalt mixture is placed in a beaker containing 25 ml of a sodium carbonate solution having a predetermined concentration shown in Table 1 and boiled for 1 minute. Record the first solution where crushed stones and asphalt have begun to completely peel off, and determine the number of adhesion points. Table 1 shows the relationship between sodium carbonate and the number of adhesion points.

[0034]

[Table 1]

The water immersion Marshall test was in accordance with the test method KODAN 202 “Marshall Test Method for Asphalt Mixtures” of the Japan Highway Public Corporation. However, the water immersion time of the test piece was increased from 48 hours to 96 hours, and the test was performed under more severe conditions.
The test was in accordance with the Marshall Stability Test Method (ASTM D 1559-65, Asphalt Paver, Appendix 4.10). The type of the asphalt mixture used in this test is a dense particle size asphalt mixture (13 mm), and the composition design of the mixture is about the optimum amount of asphalt (5.5%) obtained from the Marshall stability test using asphalt with a penetration of 60 to 80. A modified asphalt mixture was prepared with the same amount of asphalt for each modified asphalt. The test asphalt pavement composition test specimen was heated and melted asphalt at 165 to 180 ° C, and the additive of the present invention was added according to the conditions to prepare an asphalt mixture,
It was prepared by kneading with crushed stone, sand and filler heated to 165 to 180 ° C. Mixing conditions are mixing temperature 1
The temperature was 65 to 180 ° C and the compaction temperature was 165 to 180 ° C. Ten test pieces (10 cm in diameter, approximately 6.3 cm thick cylindrical) were made,
Of these, 5 have undergone the standard Marshall test and the remaining 5 have
The sample was immersed in a constant temperature water bath at 60 ° C. for 96 hours, and after completion of the immersion, the Marshall stability of the specimen was determined. Residual stability by the water immersion Marshall test was calculated from the following formula.

[0036]

[Equation 1]

Example 1 A sample asphalt was prepared by mixing various additives shown in Table 2 into slate asphalt (penetration: 60 to 80). The results of the Riedel and Weber test and the water immersion Marshall test are shown in Table 2.

[0038]

[Table 2]

Example 2 95% of slate asphalt (penetration 60 to 80) and 5% of the modifier shown in Table 3 were mixed, and 0.5% of various additives shown in Table 3 were mixed with the slate asphalt. The modified asphalt was prepared by the following. The results of the Riedel and Weber test and the water immersion Marshall test are shown in Table 3.

[0040]

[Table 3]

* 1 Styrene / butadiene / styrene block copolymer * 2 Styrene / isoprene / styrene block copolymer * 3 Ethylene / vinyl acetate copolymer * 4 Styrene / butadiene copolymer * 5 Styrene / butadiene copolymer Gel type

[0042]

[Effects of the Invention] From the examples, the bituminous materials prepared by using the highly durable additive for heating bituminous material of the present invention have improved adhesiveness between aggregate and asphalt, remarkably improved anti-peeling effect, and durability. It is clear that it is improving. This additive enables recent advances in new pavement technology such as drainage pavement, and improving the durability of asphalt pavement is expected to have great benefits not only in terms of total cost but also in terms of the environment, and its ripple effect. Is big.

Claims (5)

[Claims] 1. A highly durable additive for heated bituminous substances, which comprises a divalent carboxylic acid represented by the following general formula (I) and / or (II) or an anhydride thereof. [Chemical 1] (In the formula, R ^{1 to} R ³ are linear or branched, saturated or unsaturated hydrocarbon groups having 8 to 30 carbon atoms.) 2. A highly durable additive for heated bituminous substances, characterized by comprising an anhydride of a divalent carboxylic acid represented by the following general formula (I) and / or (II). [Chemical 2] (In the formula, R ^{1 to} R ³ are linear or branched, saturated or unsaturated hydrocarbon groups having 8 to 30 carbon atoms.) 3. The highly durable additive for hot bituminous substances according to claim 1 or 2, wherein one or more kinds selected from rubbers, thermoplastic resins and thermosetting resins are used in combination. 4. The heating asphalt in 100 parts by weight of claim 1.
To 3 to 10 parts by weight of the asphalt mixture containing 0.05 to 5 parts by weight of the additive according to any one of 3 to 3 and 97 to 90 parts by weight of an aggregate composed of crushed stone, sand and filler. Highly durable asphalt pavement composition. 5. The high durability according to claim 4, wherein the aggregate is kneaded with the asphalt mixture prepared by adding the additive according to any one of claims 1 to 3 to the heated asphalt in advance. Method for producing asphalt pavement composition.