JPS5910696B2 - binder composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a two-component epoxy asphalt bonding system suitable for various uses such as a binder, a sealant, a filler, an adhesive, and a paint for heated epoxy asphalt mixtures for paving. The present invention relates to material compositions.

Recently, pavements made from heated epoxy asphalt mixtures that use heated epoxy asphalt instead of paving asphalt have been found to be more susceptible to traffic such as cars than pavements made from conventional heated asphalt mixtures (e.g. asphalt concrete). Because it is stable and has excellent flow resistance, wear resistance, and durability, it is being considered for use in heavy traffic pavements, bridge surfaces, airport pavements, etc. However, the difficult construction method poses a major obstacle to its use. That is, epoxy asphalt is composed of two components: a component containing an epoxy resin and a component containing a curing agent for the epoxy resin.Asphalt is mixed with either of the components (or both), and the curing agent undergoes a heating reaction. A mold hardener is used. Heated epoxy asphalt mixtures are made by separately calculating and adding the above two components to heated aggregate in a heating mixing plant, but if the measurements are not accurate, unreacted substances may remain in the hardened epoxy asphalt. There was a risk that water resistance, weather resistance, etc. would deteriorate because of the remaining residue. Furthermore, although the curing reaction of epoxy asphalt progresses when heated, its pot life has been a problem. The two components of epoxy asphalt are added to heated aggregate in a heated mixing plant to create a heated epoxy asphalt mixture for paving, which is then transported to the paving site, laid on the paving site, and compacted. must be finished within the pot life of the product. The pot life of commercially available epoxy asphalt is about 1 hour at a temperature of about 150°C, and it is extremely difficult to carry out this much work within this time due to current traffic conditions. Although it is possible to extend the pot life by lowering the heating temperature, the development of strength of the pavement will be delayed and it will take a long time until it is finally completely cured. As a result, we were subject to severe restrictions on construction work. Furthermore, the curing agent for the epoxy resin in epoxy asphalt is a polymerized dimer or trimer of dicarboxylic acid, tricarboxylic acid, etc. of fatty acids such as soybean oil or saffron oil, and its properties vary widely. This method had the disadvantage of increasing fluctuations in the curing time, pot life, etc. of epoxy asphalt. As a way to improve this construction method,
Japanese Patent Publication No. 18506 proposes a method for constructing pavement using a reactive binder consisting of two compositions.

In this construction method, when paving is performed using a paving mixture consisting of two compositions, a reactive binder and aggregates,
In a mixture manufacturing plant, a predetermined amount of one composition of the binder is mixed with the aggregates in advance to form an intermediate mixture, and then this intermediate mixture is transported to the paving site and further mixed with another composition of the binder immediately before paving.
This is a pavement construction method in which a predetermined amount of two compositions are added and mixed thoroughly to create a curable pavement mixture, which is then leveled and finished.

This method eliminates pot life drawbacks, but because the two compositions of reactive binder contain an epoxy resin in one and a hardener for the epoxy resin in the other, one composition cannot be used at the paving site. The drawback is that it is difficult to accurately measure and mix when adding. The present invention provides an epoxy-bituminous pavement binder composition that improves the above-mentioned drawbacks.

The present invention also provides a binder composition suitable for a wide range of uses other than paving. The binder composition of the present invention includes:
Bisphenol type epoxy resin (a) with a melting point of 60°C or higher
and an aliphatic chain dicarboxylic acid (b) having a melting point of 60°C or more and having 12 to 28 carbon atoms, and a petroleum residue oil, etc., with an atomic ratio H/C of hydrogen atoms and carbon atoms of 1.20 or less. An asphalt-mixed process oil consisting of a powder component (1) consisting of a hydrocarbon resin (c) with a softening point of 60° C. or higher, and a process oil or a process oil and asphalt, the amount of asphalt being 50% by weight or less. In a binder composition consisting of two components, a liquid component (),
Total amount of epoxy resin and aliphatic chain dicarboxylic acid (a
+b) is 70 to 10 of the total amount (1+) of the binder composition
% by weight of the binder composition.

The bisphenol type epoxy resin used in the present invention with a melting point of 60°C or higher is a condensate of bisphenol and epichlorohydrin or a derivative thereof, and has one or more epoxy groups in one molecule, and has an epoxide equivalent of is between 400 and 4000.

For example, Epicote 1001, which is a condensate of bisphenol A and epichlorohydrin, Epicote JlOO4, Epicote 1007, Epicote 1009 (all trade names, manufactured by Shell Chemical), and Deitzke Epiclon 10, which is a condensate of bisphenol A and methylepichlorohydrin.
00, Deitsk Epiclon 4000 (all products manufactured by Dainippon Ink, trade names), Deitsk Epiclon 1030, which has an ether bond in the molecule by substituting a portion of the bisphenol of the above epoxy resin with dicarboxylic acid. Examples include Tsukuepikron 4030 (all products of Dainippon Ink, trade names).

A part of the above-mentioned bisphenol type epoxy resin may be replaced with polyglycidyl ether of a condensate of alkylphenol and aldehyde (including novolac type and resol type) or other epoxy resin. The aliphatic chain dicarboxylic acid having a melting point of 60°C or more and having 12 to 28 carbon atoms used in the present invention has the following general formulas (1) to (3): HOOC
-(CH2)l-COOH(1)HOOC-(CH2)
n]-CH:CH-(CH2)n-011(2)HOO
C-(CH2).

-CH:C(CH2)2CH:CH-(CH2), {
00H (3) where l is an integer of 10 to 20, m and n are integers of 4 to 10, o and p are integers of 4 to 10, and one or more aliphatic chain carboxylic acids It is a dicarboxylic acid with a melting point of 60°C or higher and whose main component is

These are obtained by synthesis. For example, 0SK-DA
SL-12, 0SK-DASL-16, 0SK-DAS
L-20 (formula (1) above), 0SK-DAUL-16 (
(Formula (2) above) and 0SK-DAUL-20 (Formula (3) above (all Okamura Oil products, trade names).These are solids with a melting point of 100℃ or higher and can be easily converted into powder. Hydrocarbon resin (hereinafter simply referred to as petroleum Solid resins) are heavy distillation residues, thermal decomposition residues, high-boiling fractions, oils produced by high-temperature heat treatment of crude oil or heavy oils, etc., produced in the petroleum refining process, and are treated with solvents such as propane, furfural, and phenol. A solid resin that is rich in aromatic components separated by solvent extraction or obtained by further processing such as heat treatment.
It consists mainly of hydrocarbons and is rich in aromatic components.

These include, for example, propane-deasphalted asphalt or its blown ink, solid resins mainly composed of asphaltenes separated by treating asphalt with solvents, and heavy fractions rich in aromatics obtained by treating them at high temperatures. Examples include modified petroleum resins. These petroleum-based solid resins are
3. It has a shiny black appearance and can be easily powdered by crushing. The petroleum-based solid resin has good compatibility with process oil or asphalt mixed process oil, which will be described later, and together with these, synthetic asphalt having properties equivalent to asphalt is produced. This synthetic asphalt is superior to general asphalt in terms of compatibility and affinity with epoxy resins and aliphatic dicarboxylic acids, which are curing agents for epoxy resins. Therefore, the reaction between the epoxy resin and its curing agent can proceed smoothly in this synthetic asphalt during heating. The process oil used in the present invention is a process oil produced in a petroleum refining process, and is generally used as a rubber softener, a compounding agent, and a compounding agent for polyvinyl chloride.

Its chemical components can be divided into aromatic components, naphthenic components, and paraffinic components, but it is desirable that the sum of aromatic components and naphthenic components be 50% by weight or more and that it has low volatility. In terms of viscosity, the kinematic viscosity at 98.9℃ is 10
It is recommended to use a material with a density of at least 15 centistokes, preferably at least 15 centistokes. Further, the asphalt includes petroleum asphalt such as straight asphalt, semi-prone asphalt, prone asphalt, and propane deasphalt, and lake asphalt.
Generally, straight asphalt, semiprone asphalt, propane-deasphalted asphalt, etc. with a penetration degree (25° C.) of about 10 to 200 are used. The proportions of each material in the present invention are as follows. The aliphatic chain dicarboxylic acid, which is a curing agent for the epoxy resin, is used in an amount equivalent to or close to the amount required to cause the epoxy group of the epoxy resin to react with the carboxyl group of the dicarboxylic acid. Petroleum-based solid resin is
The amount used is 50 to 400 parts by weight per 100 parts by weight of epoxy resin. The ratio of petroleum-based solid resin and process oil or asphalt mixed process oil can be selected within a wide range, but the physical properties of the synthetic asphalt produced by heating and mixing and dissolving these oils are
It is preferable that the temperature is 0° C. or lower and the penetration is 10 or more and 600 or less.

The total amount of epoxy resin and aliphatic chain dicarboxylic acid is
It accounts for 70-10% by weight of the total weight of the binder composition.

The total amount of epoxy resin and aliphatic chain dicarboxylic acid is 7
When it exceeds 0% by weight, the physical properties of the cured product of epoxy asphalt are stronger than necessary, and the elasticity, flexibility, elongation, etc. imparted by the characteristics of the bituminous material are not fully utilized. Moreover, when it is less than 10% by weight, the excellent properties, strength, adhesiveness, abrasion resistance, weather resistance, etc. of the epoxy resin cannot be fully utilized. The powder component (1) of the binder composition of the present invention is produced as follows. The epoxy resin, aliphatic chain dicarboxylic acid, and petroleum-based solid resin are each weighed and mixed and pulverized in a pulverizer to produce a fine powder in which each component is uniformly mixed. The petroleum-based solid resin improves uniform dispersion of the epoxy resin and aliphatic chain dicarboxylic acid, increase in their volume, and dispersion and dissolution in the liquid component ().
In addition, the aliphatic chain dicarboxylic acid prevents condensation of fine powders at room temperature and helps maintain a smooth powder form. It is also possible to add powdered filler of stone powder to these. Powdered components of the binder composition of the present invention (
The epoxy resin and aliphatic chain dicarboxylic acid in 1) are
It does not react at room temperature and only starts to react when heated. Therefore, when the binder composition of the present invention is used as a binder, etc., the powder component (1) and the liquid component (2) are mixed in a predetermined ratio, and the mixture is heated. Usually, the powdered component (1) is added to and mixed with the liquid component (H) after being heated, or the powdered component (1) is added and mixed with the liquid component (I) and then heated. The heating temperature is preferably 120° C. or higher. This heating causes the liquid component () and the powder component (1) to melt, and the liquid component () and the petroleum-based solid resin in the powder component (1) to become compatible, creating synthetic asphalt, in which the component ( Ioki's epoxy resin and aliphatic chain dicarboxylic acid melt and react and polymerize to form a binder with good physical properties.Next, as an application example of the binder composition of the present invention, it is used as a binder for a heated mixture for paving. A case will be explained.For example, an example will be given in which the asphalt as a binder in dense-grained asphalt concrete is replaced with the binder composition of the present invention.In other words, aggregate heated to about 170°C in a heated mixing asphalt plant is used. A predetermined amount of liquid component () is mixed with the heated mixed aggregate.The heated mixed aggregate is transported to the paving site.There, a predetermined amount of powdered component () is mixed into the heated mixed aggregate.
When 1) is added and mixed, the powdered component (1) dissolves into the liquid component 1) in the mixture and becomes integrated, which covers the aggregate. This mixture can be laid down with a paving machine such as a conventional asphalt finisher. After leveling it, it is compacted and finished using roller compaction. The reaction of the binder progresses, and the cured mixture becomes a pavement with high stability and excellent physical properties. In the above,
When the temperature of the heated mixed aggregate coated with the liquid component (1) drops at the paving site, it is preferable to heat it to raise the temperature before adding the powder component (1). The hot mixed aggregate coated with the liquid component () can maintain a uniform particle size without separation of the aggregate during transportation and other handling due to the liquid component (). Powdered component (1)
The pot life of a mixture obtained by adding and mixing the epoxy resin and its curing agent varies depending on the amount of the epoxy resin and its curing agent, but it is about 30 minutes to 1 hour when the mixture is maintained at a temperature of about 150°C. This mixture is paved immediately after mixing, so there is no need for a long pot life. Therefore, the binder of the mixture after paving hardens quickly and reaches sufficient strength within a short period of time, allowing the road to be opened to traffic sooner. Next, the characteristics and effects of the binder composition of the present invention will be summarized. (1) Something corresponding to asphalt is mainly composed of a petroleum-based solid resin rich in aromatic components and process oil.

Therefore, compared to ordinary asphalt, it has excellent compatibility and affinity between the epoxy resin and its hardening agent. (
2) Since an aliphatic chain dicarboxylic acid (having 12 to 28 carbon atoms) is used as a curing agent for the epoxy resin, the epoxy resin and the curing agent react by heating, and the temperature is 80°C or higher, preferably 120°C or higher. It is necessary to combine the two in step 3.

A cured product with excellent strength, flexibility, elasticity, etc. can be obtained. Furthermore, when a resin having two epoxy groups is used as the epoxy resin, the cured product becomes a thermoplastic polymer.
(3) The epoxy resin and its curing agent are increased in volume with some petroleum-based solid resins in synthetic asphalt and are in powder form, making them easy to handle and requiring separate weighing of the epoxy resin and its curing agent. Moreover, the ratio of the two is always constant, and since the amounts of both are increased, there is less variation, and the powder component (1) and the liquid component (2) can be blended without measurement error.

Therefore, the physical properties of the binder are stable with little variation. (4) If the binder composition is applied as a binder for a heated mixture for paving, a mixture of heated aggregate and liquid component (2) is produced in a heated mixing plant, transported to the paving site, and then A method can be used in which the powdered component (1) is added and mixed, spread out and rolled.

This method can solve the problems of conventional epoxy asphalt mixtures, such as pot life, metering, and curing time after paving. Moreover, it is easy to install, has high stability, little variation in quality, and has excellent flow resistance, wear resistance,
Paving bodies with excellent durability etc. can be made. Next, examples of the present invention will be described. The materials used in the Examples and Comparative Examples are as follows.

1) Epoxy resin Epicoat 1004 Shell Chemical Products, trade name, melting point 9
6-104°C, epoxy equivalent 875-975 2) Aliphatic chain dicarboxylic acid 0SK-DASL-20 Okamura Oil Products, trade name HOOC
・(CH2)8・COOH melting point 115-125CC3)
Petroleum-based solid resin FR-100 Fuji Kosan product, trade name Modified petroleum resin ANA-011 Kashima Oil product, made from aromatic-rich heavy distillates in petroleum fractions and specially treated at high temperatures. The residue obtained by solvent extraction of straight asphalt, mainly consisting of asphaltene.

Properties are shown in Table 1.

(5) Synthetic Asphalt Table 3 shows the properties of the synthetic asphalt made of the petroleum-based solid resin and process oil used in the formulation of the examples.

(6) Straight Asphalt Straight Asphalt 60-80 Nippon Oil Products Straight Asphalt 150-200 Nippon Oil Products properties are shown in Table 3.

Example 1 Epicoat resin Epicoat 1004 and its curing agent 0S
K+ASL-20 and petroleum-based solid resin FR-100 were weighed according to the composition shown in Table 4, and then placed in a ball mill and pulverized and mixed for 1 to 2 hours to make a fine powder. Let it be the powdered component (1) of the product.

On the other hand, the process oil Fuccoal Aromax 5 is used in the proportions shown in Table 4, and these are used as the liquid component () of the binder composition. Furthermore, FR-10
The ratio of 0:process oil was selected to be 50:50 for formulations 7f61-1 to 1-3 and 64:36 for formulations 1-4 to 1-6. For formulations A1-1 to 1-6, component (1) and component () were mixed and heated to 120° C. or higher to obtain a good cured product with a uniform composition. Example 2 A binder composition is prepared by replacing the process oil Fuscol Aromax 5 in Example 1 with Acrodex A-200.

Mix prescribed amounts of these components (1) and () and heat at 120°C.
A good cured product was obtained by heating to the above temperature. Example 3 A binder composition is prepared by replacing the process oil Fuscol Aromax 5 in Example 1 with 38 heavy process oil.

A good cured product was obtained by mixing predetermined amounts of component (1) and component () and heating the mixture to 120° C. or higher. [Application test for pavement mixtures] In order to find out the properties of the binder compositions of Examples 1, 2, and 3 as binders, a marshal stability test was conducted using them as binders for heated pavement mixtures. I went.

These results are shown below. (1) Test method “Asphalt Pavement Guidelines” published by Japan Road Association
According to the Marshall stability test method.

However, this excludes the method for preparing the specimen. (2) Mixture formulation (b) Type of mixture (b) Aggregate mixture The synthetic particle size is shown in Table 5.

(3) Amount of binding material 8.0% by weight of aggregate (external %), 1 for 1150g of aggregate
009 (4) Method for preparing specimens for marshal stability test The aggregate is heated to 160 to 170°C, and a predetermined amount of process oil as component () of the binder composition is added and mixed.

After confirming again that the temperature of the mixed aggregate is 160 to 170°C, a predetermined amount of the powder of component (1) of the binder composition is added and quickly mixed and stirred to bring the temperature of the mixture to 140°C.
Adjust the temperature to ~145°C, put it in a mold, and ram it with an automatic rammer 50 times on one side and 100 times on both sides.

After the compaction was completed, it was placed in an oven adjusted to a temperature of 120° C. and cured for 6 hours, and after curing, it was removed from the mold and used as a specimen. (
5) Marshall stability test results The test results are shown in Tables 6, 7 and 8.

In addition, in order to compare with the binder composition of each example, similar tests were conducted on the remaining synthetic asphalt and straight asphalt 60 to 80, which were obtained by removing the epoxy resin and its curing agent from the binder composition used in each example. The results are also shown in Tables 6, 7 and 8. The test result is 3
The average value of the same polarity test results conducted on each specimen is shown below.

Based on these results, the binder compositions of Example 2 and Example 3 were used as binders to bind to heated aggregate of fine-grained asphalt concrete (13F) aggregate size in a heated mixing plant using the same composition. The liquid component (4) of the material composition is added and mixed, the mixture is kept at a temperature of about 160°C at the paving site, and the powder component (1) is added to the mixture using a pug mill for about 30 seconds. Immediately after mixing for ~1 minute, these mixtures were leveled (finished thickness approximately 4 CfL) and thoroughly rolled with rollers to form compacted pavements.

As a result, workability was good, the binder cured quickly, and sufficient strength was obtained within the time it took for the temperature of the mixture to drop to atmospheric temperature (within about 2 hours), and it was cured to the point where it could be opened to heavy traffic. Example 4 Epicote 100430 parts by weight, 0SK-DASL-2
05.7 parts by weight of ANA-0113 and 1.3 parts by weight of ANA-0113 were weighed, and these were placed in a ball mill and pulverized for about 2 hours to obtain a powdered component ().

38 heavy process oil is used as the liquid component ().

A good cured product can be obtained by heating 33% by weight of the liquid component () to about 170°C, adding and mixing 67 parts by weight of the powdery component (1), and heating to about 120°C or higher. Ta. Example 5 Epicote 100430 parts by weight, 0SK-DASL-2
05.7 parts by weight and 4.3 parts by weight of FR-1002 are pulverized and mixed for about 2 hours using a ball mill to obtain a uniformly mixed powder component ().

24.3 parts by weight of 38 heavy process oil and 15.7 parts by weight of straight asphalt 60-80 at approximately 120℃
Mix by heating to obtain uniformly dissolved liquid component 1).

Claims (1)

[Claims] 1 Bisphenol-type epoxy resin with a melting point of 60°C or higher (
a), an aliphatic chain dicarboxylic acid having a melting point of 60° C. or higher and a carbon number of 12 to 28 (b), and a petroleum residue oil, etc. obtained by treating the hydrogen atom to carbon atom atomic ratio H/C of 1.20. An asphalt mixing process consisting of a powdered component (I) consisting of a hydrocarbon resin (c) with a softening point of 60°C or higher, and a process oil or process oil and asphalt, in which the amount of asphalt is 50% by weight or less: In a binder composition consisting of two components, including a liquid component (II) which is an oil, the amount of the sum a + b of the epoxy resin and the aliphatic chain dicarboxylic acid is the total amount of the binder composition (I + II).
70 to 10% by weight of a binder composition.