JP3197998B2 - Highly durable heated bituminous additive, highly durable asphalt pavement composition using the same, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heated bituminous additive comprising a specific acidic organophosphate compound, an asphalt pavement composition using the same, and a method for producing the same. The additive for heated bituminous material, which makes it possible to strengthen the adhesion between the material and the aggregate, and as a result, makes it possible to develop an extremely excellent anti-stripping agent effect on bituminous material, asphalt pavement composition using the same, and the like It relates to a manufacturing method.

[0002]

BACKGROUND ART Bitumens such as asphalt, tar, and pitch obtained from petroleum or coal are used for paving materials, roofing materials, and waterproofing materials. Is big. However, since bituminous material is nonpolar, it does not sufficiently adhere to the aggregate and has a potential defect that the bituminous material is separated from the aggregate due to the intervening action of water such as precipitation or groundwater.

In addition, as vehicles become larger and heavier, asphalt pavement is subjected to rutting and fluidization phenomena, which impairs traffic smoothness and travelability. As a countermeasure, a method of mixing a thermoplastic resin or rubber into bituminous material has been devised.
However, bitumen mixed with a thermoplastic resin or rubber has a problem that the adhesion between aggregate and bituminous material is lower than that of the original bituminous material.

[0004] As described above, the technical problem of improving the adhesion between bituminous material and aggregate is a very important problem for improving the performance of asphalt pavement, and various methods have been devised for solving the problem. . For example, according to Japanese Patent Publication No. 55-38995, higher aliphatic polyamines and derivatives thereof are used as a countermeasure, but higher aliphatic polyamines and derivatives thereof conventionally devised have improved initial adhesion improving performance. However, the durability of the effect of preventing peeling is said to be about one year.

Japanese Patent Application Laid-Open No. 57-51745 also proposes a method for improving the adhesion performance by adding a silane compound. However, when adding to a heated bituminous material or during the production of a heated mixture, it is harmful. It has a serious odor and steam generation, leaving safety and health problems, and is economically and practically ineffective.

Further, a composition obtained by adding and mixing a phosphoric acid compound such as phosphorus pentoxide, polyphosphoric acid, phosphorus pentasulfide and the like to asphalt is used as an asphalt modifying additive in Japanese Patent Publication No. Sho 54-2.
Although disclosed and proposed in Japanese Patent No. 3691, these phosphate compounds are inorganic substances, and their dispersion state in organic substances is not always good, and the adhesion performance of asphalt to aggregates is insufficient. Further, in recent years, while there is a concern that the quality of asphalt and aggregates may be deteriorated, in the recycling method using pavement waste material, strong adhesion cannot be expected because asphalt with reduced quality is used, and asphalt reforming is not possible. Although increasingly desired, no means has yet been developed to eliminate all of the above-mentioned problems and the performance demands of the market.

[0007] Japanese Patent Application Laid-Open No. 60-188462 discloses that acidic organic phosphoric acid compounds have an effect of preventing peeling. However, under the current situation where the level of asphalt pavement is increasing due to heavy traffic and the like, The performance is insufficient to satisfy these requirements, and there is a demand for the development of an additive having further anti-peeling performance.

[0008]

Means for Solving the Problems The present inventors have made intensive efforts to obtain a bitumen composition having further excellent anti-peeling properties, and as a result, have obtained a saturated or unsaturated linear or branched chain having 16 to 18 carbon atoms.
It is composed of a monoaliphatic phosphate (A) and a linear or branched saturated or unsaturated dialiphatic phosphate having 16 to 18 carbon atoms (B), and A / (A + B) × 100 (mol%) ) Is 40 ~
The present inventors have found that an acidic organic phosphoric acid compound having a ratio of 95 has the ability to exhibit a particularly excellent exfoliation preventing effect in bituminous matter, and have completed the present invention.

That is, the present invention relates to a straight-chain or
Branched saturated or unsaturatedMonoaliphatic phosphate ester
(A) and saturated or unsaturated of a linear or branched chain having 16 to 18 carbon atoms
Sum ofDialiphatic phosphate ester(B)
(A + B) × 100 (mol%) is 40 to 95.
And a highly durable heated bituminous additive.

[0010] The present invention also relates to an asphalt composition obtained by adding 0.05 to 5 parts by weight of the above-described additive to 100 parts by weight of heated asphalt, and 97 to 90 parts by weight of aggregate comprising crushed stone, sand and filler. And a high-durability asphalt pavement composition comprising:

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

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

The conventionally devised higher aliphatic polyamines and derivatives thereof are adsorbed and oriented to the positive and negative electric groups of the polar group,
Improves wetting between bituminous material and aggregate. Although effective for initial adhesion, it has problems with 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, the additive itself is a surfactant and acts as a bituminous emulsifier to peel bitumen from aggregate. There is a disadvantage.

The present invention has a composition for arranging molecules most densely at the interface between bituminous material and aggregate, and furthermore, forms a chemical bond at the interface by a dehydration reaction as shown in the following reaction formula, thereby making it stronger. Adhesion and polymerization of the acidic organic phosphoric acid compound itself form a strong hydrophobic coating on the surface of the aggregate, so even if water enters the surface of the aggregate, it will not be replaced with bituminous material and will not impact. It is considered that the adhesive agent exhibits an excellent exfoliation preventing effect in which the adhesive interface between the aggregate and the bituminous material is not destroyed even when it is subjected.

[0015]

Embedded image

In order to form an optimum adhesive interface dense in molecular structure and arrangement, a linear or branched saturated or unsaturated mono- or mono-phosphate mono-aliphatic ester having 16 to 18 carbon atoms (A) is required 16-18 linear or branched saturated or unsaturated diphosphates
A / (A + B) × 100 consisting of aliphatic ester (B)
(Mol%) is important to be a composition ratio of 40 to 95, and it is difficult to obtain such a dense molecular arrangement and chemical bond even if the monophosphate ratio is less than 40 or more than 95, The anti-peeling performance is insufficient. More preferably, A
/ (A + B) × 100 (mol%) is 60 to 90.

The values of A and B used herein can be obtained by the following method for analyzing an acidic organic phosphoric acid compound (for example, the method described in JP-B-58-8746). That is, 1 g of the product was subjected to potentiometric titration with an alkali by an ordinary method, and the required amount of alkali (amg) by the first equivalent point and the required amount of alkali (bmg) by the second equivalent point were determined. After the addition of silver nitrate having a chemical equivalent or more than the phosphate acidic OH group present in the above, a potentiometric titration with an alkali is performed in the same manner to obtain an alkali amount (cmg) required up to the third equivalent point. Calculate the content.

[0018]

(Equation 1)

The acidic organic phosphoric acid compound in the present invention comprises:
Examples of the phosphorylating agent include, but are not limited to, phosphorus pentoxide (P ₂ O ₅ ), phosphorus oxytrichloride (P
OCl _3), phosphorus trichloride (PCl _3), such as using a polyphosphoric acid and as alcohol starting material, an alcohol, saturated or unsaturated straight-chain or branched-chain having 16 to 18 carbon atoms is used, for example, cetyl alcohol , Stearyl alcohol, oleyl alcohol, Guerbet alcohol and the like. An acidic organic phosphoric acid compound having a predetermined ester composition ratio can be obtained depending on the kind of the phosphorylating agent used, the molar ratio of the alcohol to the phosphorylating agent, and the addition of water.

The acidic organic phosphoric acid compound of the present invention may be an alcohol having a different number of carbon atoms from the viewpoint of the raw material for synthesis (for example, Kao Corporation)
(Calcol series) may be mixed, but it is desirable to use it as an alcohol raw material containing alcohol of 16 to 18 carbon atoms in an amount of 70% by weight or more. However, there is no problem in performance, and it is included in the scope of the present invention.

The additive of the present invention is used in an amount of 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the bituminous material or the modified bituminous material.
It is.

Further, the additive of the present invention can enhance the adhesive strength of the modified bituminous material by using at least one selected from rubbers, thermoplastic resins and thermosetting resins. .

The rubber used in combination with the highly durable heated bituminous additive of the present invention includes natural rubber, styrene / butadiene rubber, styrene / butadiene / styrene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, styrene / isoprene rubber, Examples include, but are not limited to, synthetic rubbers such as styrene / isoprene / styrene rubber, methyl methacrylate / butadiene rubber, and butadiene rubber.

The thermoplastic resin used in combination with the high-durable heated bituminous additive of the present invention includes ethylene, propylene, vinyl acetate, acrylate, methacrylate, styrene, vinylidene chloride and vinyl propionate. Examples thereof include homopolymers and copolymers obtained by combining these, but are not limited thereto. Of these, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer are particularly preferred.

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

It is said that when a large amount of rubbers, thermoplastic resins and thermosetting resins are used, the adhesive strength of the modified bituminous material tends to be rather reduced, and the modified bituminous acid has a moderate adhesive strength with the acidic organic phosphoric acid compound. The combined use remarkably enhances the adhesive strength and solves the problem.

The amount of modifying material such as rubbers, thermoplastic resins, and thermosetting resins added to bituminous material is such that the ratio of 20 to 1 part by weight of modifying material to 80 to 99 parts by weight of bituminous material is used. Preferably, the ratio is 15 to 2 parts by weight of the modifying agent, and the amount of the bituminous material plus the modifying agent is 100 parts by weight.

Further, in addition to rubbers, thermoplastic resins and thermosetting resins, inorganic and organic fillers such as calcium carbonate, slaked lime, Portland cement and activated carbon, petroleum resins, low molecular A petroleum softener such as polyethylene, a vegetable oil softener such as oleic acid, various plasticizers, sulfur and the like can be used in combination with the acidic organic phosphoric acid compound of the present invention.

The crushed stone, sand, and filler used in the highly durable asphalt pavement composition of the present invention can be used in the present invention irrespective of the material and the like as long as they conform to the asphalt pavement guidelines (edited by The Japan Road Association). be able to. Crushed stone,
The mixing ratio of the aggregate composed of the sand and the filler was 3 to 10 parts by weight of the asphalt mixture to which the additive of the present invention was added,
~ 90 parts by weight are preferred.

The highly durable asphalt pavement composition of the present invention is prepared by adding the additive of the present invention to asphalt previously heated to a temperature of 120 to 200 ° C. and kneading a well-mixed asphalt mixture with crushed stone, sand and filler. It is characterized by being manufactured by doing. During the production of the highly durable asphalt pavement composition of the present invention, the additive of the present invention is uniformly dispersed in the asphalt by adding the additive of the present invention to preheated asphalt, and the uniform high durable asphalt A pavement composition is obtained. If the additive of the present invention is previously mixed with crushed stone, sand, filler, or the like, the additive is localized and a homogeneous asphalt pavement composition cannot be obtained.

In order to better achieve the object of the present invention, various aliphatic amines may be used in combination with the acidic organic phosphoric acid compound of the present invention. This means that the initial wetting is further enhanced by having a nitrogen atom in the molecule. The amines are not particularly limited, but generally include higher aliphatic polyamines and derivatives thereof such as tallow propylene diamine, and alkylolamines such as alkylhydroxyamine, monoethanolamine, diethanolamine, and triethanolamine. Is preferably used on the neutral or acidic side. Various aliphatic amines used in combination with the acidic organic phosphoric acid compound of the present invention are not limited to these.

In the present invention, the bitumen to which the acidic organic phosphoric acid compound is added is a bitumen produced from petroleum slate asphalt, semi-pron asphalt, cut pack asphalt, natural asphalt, petroleum tar, pitch or solvent deasphalting. Asphalt produced by adding a softening agent so as to meet the asphalt standard is exemplified.

The modified bitumin obtained by adding the above-mentioned modifier to a bitumin appropriately selected for practical use is excellent in temperature sensitivity and durability, and by adding an acidic organic phosphoric acid compound,
It is possible to obtain a bitumen composition having various properties required by the market by improving the adhesion and the anti-peeling property.

Accordingly, the present invention can be used for construction for the purpose of waterproof coating of factory floors, roofing materials, underground protection materials for vehicles, etc. other than road paving agents.

As a method of mixing the acidic organic phosphoric acid compound into the modified bituminous material in the present invention, the modifying agent and the acidic organic phosphoric acid compound are simultaneously added to the bitumen heated and melted at 100 to 250 ° C. with stirring. Either a method or a method in which a modified bituminous material is produced in advance and then an acidic organic phosphoric acid compound is added.

[0036]

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

The 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 to 0.075 mm
Parts by weight and 43 parts by weight of crushed stone with a particle size of 0.3 to 0.15 mm
Heat to ° C. Add 14 parts by weight of asphalt or modified asphalt heated and melted to 150 ° C and mix well,
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 predetermined concentration of sodium carbonate solution shown in Table 1 and boiled for 1 minute. Record the first solution in which the crushed stone and asphalt begin to separate completely, even in small quantities, to determine the number of deposits. Table 1 shows the relationship between sodium carbonate and the number of adhered points.

[0038]

[Table 1]

The water immersion marshalling test conformed to the test method KODAN202 “Marshalling test method for asphalt mixture” of Japan Highway Public Corporation. However, the water immersion time of the specimen was increased from 48 hours to 96 hours, and the test was performed under more severe conditions.
The test followed the Marshall Stability Test Method (ASTM D 1559-65, Asphalt Pavement Guidelines, Appendix 4.10). The type of asphalt mixture used in this test was a dense-grained asphalt mixture (13 mm), and the blend design of the mixture was based on the optimum asphalt amount (5.5%) obtained from a marshall stability test using asphalt with a penetration of 60 to 80. A modified asphalt mixture was prepared using the same amount of asphalt for each of the modified asphalts. The asphalt pavement composition test specimen for the test was prepared by melting asphalt by heating at 165 to 180 ° C., adding the additive of the present invention according to the conditions to prepare an asphalt mixture,
It was prepared by kneading with crushed stone, sand and filler heated to 165-180 ° C. Mixing conditions are as follows: Mixing temperature 1
The test was performed at 65 to 180 ° C and at a compaction temperature of 165 to 180 ° C. Ten specimens (cylindrical shape with a diameter of 10 cm and a thickness of about 6.3 cm) were prepared.
Five of them were subjected to the standard marshall test, and the remaining five were
The sample was immersed in a constant temperature water bath at 60 ° C. for 96 hours. After the immersion, the marshall stability of the test specimen was determined. The residual stability by the water immersion marshall test was calculated from the following equation.

[0040]

(Equation 2)

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

[0042]

[Table 2]

Example 2 95% of slate asphalt (penetration of 60 to 80) was mixed with 5% of a modifier shown in Table 3, and various additives shown in Table 3 were added to slate asphalt by 0.5% (solid Min) to prepare a modified asphalt. Table 3 shows the results of the Riedel and Weber test and the water immersion marshall test.

[0044]

[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

[0046]

As can be seen from the examples, bitumen using the additive for highly durable heated bituminous material of the present invention has improved adhesion between aggregate and asphalt, remarkably improved delamination prevention effect, and improved durability. It is clear that it has improved. This additive enables the development of new pavement technology such as recent 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. Is big.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Akitoshi Tsuji 64-5, Nishiisaka, Uchida-cho, Naga-gun, Wakayama Prefecture (56) References Japanese Patent Publication No. 40-5640 (JP, B1) (58) Fields surveyed Cl ^7, DB name) C08L 1/00 -. 101/16 C08K 3/00 - 13/08 E01C 7/22

Claims (5)

(57) [Claims] A linear or branched saturated or unsaturated mono-aliphatic phosphoric acid monoester (A) having 16 to 18 carbon atoms and a carbon atom having 16 carbon atoms.
~ 18 linear or branched saturated or unsaturated diphosphate phosphates
A highly durable heated bituminous additive comprising an aromatic ester (B), wherein A / (A + B) × 100 (mol%) is 40 to 95. 2. The highly durable heated bituminous additive according to claim 1, wherein at least one selected from rubbers, thermoplastic resins and thermosetting resins is used in combination. 3. A phosphate ester of cetyl alcohol or stearyl alcohol.
Or a highly durable heated bituminous additive according to 2. 4. The method according to claim 1, wherein 100 parts by weight of the heated asphalt is added.
3 to 10 parts by weight of an asphalt blend containing 0.05 to 5 parts by weight of the additive according to any one of Items 1 to 3, and 97 to 90 parts by weight of aggregate composed of crushed stone, sand and filler. Durable asphalt pavement composition. 5. A highly durable asphalt according to claim 4, wherein an asphalt mixture in which the additive according to any one of claims 1 to 3 is added to the heated asphalt in advance and an aggregate. A method for producing a pavement composition.