JP2003064260A - Asphalt epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an asphalt epoxy resin composition for obtaining a good pavement having good workability due to a long pot life at a high temperature and capable of developing sufficient strengths immediately after application. SOLUTION: The asphalt epoxy resin composition comprises asphalt, an epoxy resin and an epoxy resin curing agent, wherein the epoxy resin curing agent comprises a 8-22C aliphatic primary amine and a bifunctional phenol resin having a softening point of 80 deg.C or more and/or a petroleum resin having a softening point of 80 deg.C or more.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pavement asphalt epoxy resin composition having excellent fluidity resistance, abrasion resistance, workability, and the like.

[0002]

BACKGROUND OF THE INVENTION Asphalt is used in a wide range of fields such as pavement for roads and waterproof / corrosion preventive paints. Asphalt, which is generally used as a road paving material, tends to soften and flow under high temperature conditions in the summer, and harden under low temperature conditions in the winter to reduce flexibility. have. If the flow resistance of asphalt is insufficient, shearing stress due to vehicle weighting and brake control will cause phenomena such as rubbing and waviness on the pavement surface. In addition, when the flexibility is lowered, there is a problem that embrittlement is likely to occur, wear resistance is lowered, and cracking occurs.

As a useful means for improving asphalt for road paving, a method of forming a complex of asphalt and epoxy resin is typical. The characteristics of the asphalt epoxy mixture are excellent in flow resistance, wear resistance, and fatigue resistance, but the working time is shorter under high temperature conditions where asphalt and aggregate are mixed. there were. In particular, in the case of drainage pavement and water-permeable pavement, which have been increasingly used recently, since high-viscosity asphalt is used, the compounding temperature with the aggregate may be as high as about 180 ° C in some cases. In this temperature range, the pot life of the conventional epoxy resin system becomes extremely short, which causes a problem that fluidity is lost during construction and sufficient compaction cannot be achieved. In addition, there is a problem that when an epoxy resin having a long pot life in a high temperature range is used, the strength after construction is not sufficiently obtained, and a product having satisfactory performance for all has not been obtained.

[0004]

The object of the present invention is to provide an asphalt epoxy mixture, particularly an asphalt epoxy mixture for drainage (water permeability) pavement, which has excellent fluidity and abrasion resistance, and has a long pot life at high temperature. The purpose of the present invention is to provide an asphalt epoxy resin composition having improved workability.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy resin containing 60 parts by weight or more of an aromatic polyepoxy compound and 8 carbon atoms. To 22 aliphatic primary amines and a bifunctional phenol resin having a softening point of 80 ° C. or higher and / or a softening point of 80
The inventors have found that an asphalt epoxy resin composition characterized by comprising a petroleum resin having a temperature of not lower than 0 ° C. is the optimum means for solving these problems, and completed the present invention.

That is, in the present invention, 50 to 90 parts by weight of straight asphalt or asphalt containing rubber / thermoplastic elastomer, or a mixture thereof, and 10 to 50 parts by weight of both the epoxy resin and the curing agent are blended,
An epoxy resin containing 60 parts by weight or more of the aromatic polyepoxy compound, an aliphatic primary amine having 8 to 22 carbon atoms, a bifunctional phenol resin having a softening point of 80 ° C or higher, and / or a petroleum having a softening point of 80 ° C or higher. The present invention provides an asphalt epoxy resin composition for paving, which is characterized by comprising a resin.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The details of the present invention will be described below. Asphalt used in the present invention is JIS
The straight asphalt having a penetration of 20 to 120, preferably 40 to 100 defined in K2207 can be mentioned. This is because if it is less than 20, the reactivity with the epoxy resin becomes fast and the workability becomes poor, and if it exceeds 120, the strength after construction is lowered.

Further, asphalt containing thermoplastic elastomer such as rubber or SBS, specifically modified asphalt type 1 and modified asphalt type 2, high viscosity modified asphalt for drainage (water permeability) pavement is used. In particular, high viscosity modified asphalt used at high temperature is preferable.

The epoxy resin used in the present invention is characterized by containing 60 parts by weight, preferably 80 parts by weight or more of an aromatic polyepoxy compound. When compounding an aliphatic polyepoxy compound and a reactive diluent as an epoxy resin other than an aromatic polyepoxy compound, it is used in an amount of less than 40 parts by weight, preferably 2
It can be used in an amount of 0 parts by weight or less. This is because these resins are effective in reducing the viscosity and prolonging the pot life, but if the blending amount exceeds 40 parts by weight, the strength of the asphalt pavement may decrease.

The epoxy resin used in the present invention is an aromatic polyepoxy compound such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol C type epoxy resin, bisphenol AD type epoxy resin, Aniline type epoxy resin, bisphenol type epoxy resin such as molecular distillation product of liquid bisphenol type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac type epoxy resin and a mixture thereof are particularly preferable. Are a bisphenol A type liquid epoxy resin and a bisphenol F type liquid epoxy resin.

Examples of aliphatic polyglycidyl ethers include aliphatic polyglycidyl ethers such as neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and 1.6 hexanediol diglycidyl ether. It is a mixture of these.

As the reactive diluent, butyl glycidyl ether, phenyl glycidyl ether, m, p cresyl glycidyl ether, paratertiary butylphenol glycidyl ether, tertiary carboxylic acid glycidyl ester, higher alcohol glycidyl ether, propylene carbonate, etc. Is mentioned.

The curing agent used in the present invention has 8 to 22 carbon atoms.
60 to 95 parts by weight of the aliphatic primary amine and a softening point of 80 ° C. or higher, preferably 100 ° C. or higher of a bifunctional phenol resin and / or petroleum resin 5 to 40 parts by weight, preferably 10 to 30
It is characterized by comprising parts by weight. Softening point 8
5% of bifunctional phenol resin and / or petroleum resin above 0 ℃
If it is less than 40 parts by weight, the pavement may have insufficient strength, and if it exceeds 40 parts by weight, the flexibility is deteriorated. This is because when the softening point of the bifunctional phenol resin and / or petroleum resin is 80 ° C. or lower, sufficient strength is not obtained immediately after the asphalt epoxy resin composition is applied, and more preferably 100 ° C. or higher. Although there is no upper limit of the softening point, it is preferably 150 ° C. or lower in consideration of manufacturing problems and compatibility with asphalt. When the number of carbon atoms of the aliphatic primary amine is less than 8, the pot life is short and flexibility of the pavement is lowered, and when it exceeds 22, compatibility with asphalt is poor and viscosity is high and handling property is poor. Specific examples of the aliphatic primary amine having 8 to 22 carbon atoms include dodecylamine, tetradecylamine,
Examples include octadecylamine, hexadecylamine, oleylamine, stearylamine and the like.

The production of a bifunctional phenol resin having a softening point of 80 ° C. or higher is a so-called direct synthesis method in which bisphenols and epichlorohydrin are reacted in the presence of an alkali metal hydroxide catalyst, or a low molecular weight bisphenol type epoxy resin and bisphenols are used. It can be synthesized by either of the so-called indirect synthesis methods in which the reaction is performed in the presence of a basic catalyst.

In the case of the direct synthesis method, it can be obtained by reacting epichlorohydrin with excess bisphenol and then removing the remaining unreacted bisphenol. In the case of the indirect synthesis method, it can be obtained by reacting a low molecular weight bisphenol type epoxy resin with an excess of bisphenols, and then removing the remaining unreacted bisphenols. By adjusting the molar ratio of the epoxy group and the phenolic hydroxyl group, a bifunctional phenol resin having an average degree of polymerization of n ≧ 0 and a softening point of 80 ° C. or higher can be obtained.

Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol S, bisphenol C, bisphenol AD, and tetrabromobisphenol A. These can be used alone or in combination of two or more. A is preferred.

The bifunctional phenolic resin having a softening point of 80 ° C. or higher used in the present invention is preferably one represented by the following general formula (1).

[Chemical 2] (In the formula (1), X is a bisphenol residue, and a plurality of X may be the same or different. Further, the average degree of polymerization n
Is the number of repeating units, and n ≧ 0. ) And, the terminal phenolic hydroxyl group equivalent of the bifunctional phenol resin of the general formula (1) is 300 g / eq or more. This is because when the terminal phenolic hydroxyl group equivalent is less than 300 g / eq, a sufficient pot life cannot be obtained when the asphalt epoxy resin composition is used. Further, it is preferable that the residual unreacted bisphenols is less than 5% by weight. When the amount of unreacted bisphenols remaining exceeds 5% by weight, the pot life is shortened and the handleability is deteriorated. It is preferable that the amount of unreacted bisphenols is small also from the influence on the environment. More preferably, it is 1% by weight or less.

C5 as a petroleum resin having a softening point of 80 ° C. or higher
A petroleum resin, a C9 petroleum resin, a C5C9 copolymer petroleum resin, a C5C9 / phenol copolymer petroleum resin, a cyclopentadiene petroleum resin, a hydrogenated cyclopentadiene petroleum resin, and a mixture thereof. Although the upper limit of the softening point is not particularly limited, it is preferably 150 ° C. or lower in consideration of the compatibility with the aliphatic primary amine and asphalt.

The curing agent used in the present invention has 8 to 8 carbon atoms.
22 aliphatic primary amines and bifunctional phenolic resins and / or petroleum resins having a softening point of 80 ° C. or higher, aliphatic phenols, indene-coumarone resins, cyclic terpene compounds,
Styrenated phenolic resin, cardanol and the like can be added as necessary.

The compounding amount of the curing agent with respect to the epoxy resin is
It is determined by the active hydrogen of the epoxy group in the epoxy resin and the amino group of the curing agent, and the number of moles of active hydrogen relative to the epoxy group is in the range of 0.6 to 1.1 moles, more preferably 0.7. It is selected to be within the range of 1.0 mol.

In the asphalt epoxy resin composition of the present invention, the total amount of the epoxy resin and the curing agent is usually 10 to 100 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of asphalt. This is because if the blending ratio is less than 10 parts by weight, the effect of modifying the asphalt is small and the strength is insufficient so that rubbing of the pavement is likely to occur, and if it is 100 parts by weight or more, it becomes hard and brittle. In addition, the asphalt epoxy resin composition of the present invention includes a filler, a reinforcing agent, a modifier such as a thermoplastic resin or a rubber, a filler, a coloring material such as a dye, an antioxidant, and an ultraviolet ray depending on its use and purpose. Stabilizers such as absorbents can be added.

The asphalt epoxy resin composition of the present invention can be produced by mixing the epoxy resin and the curing agent, and then mixing with a predetermined amount of the asphalt base material. The mixing temperature is not particularly limited, but may be 120 ° C. to 180 ° C. in consideration of mixing with the aggregate.

The method for applying the asphalt epoxy resin composition of the present invention can be performed by mixing the asphalt epoxy resin composition and the aggregate and rolling the pavement at a pavement location. The aggregate may be blended when the mixture of the epoxy resin and the curing agent is mixed with the asphalt base material. Mixing temperature with aggregate is 120-180 ℃, compaction temperature is 1
It can be performed at 20 to 160 ° C.

[0024]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, unless otherwise specified. 50 toughness tests were performed in the examples.
The test was conducted at ℃ because the temperature at which traffic is released in actual road construction is generally about 50 to 60 ℃, and the condition is reproduced. In addition, the normal toughness test is based on the load-displacement curve when the metal hemisphere with a radius of 11.1 mm is embedded in the asphalt in the test container with the spherical surface facing down, and the metal hemisphere is pulled out at a speed of 500 mm / min at 25 ° C. It is what you want.

Production Example of Phenol Resin Phenolic Resin TH-5000 (manufactured by Tohto Kasei Co .: bifunctional phenol resin: softening point 102 ° C., phenolic hydroxyl group equivalent 525 g / eq, residual BPA 0.05% or less) 83
And 17 parts of epoxy resin Epotote YD-128 (bisphenol A type liquid epoxy resin manufactured by Tohto Kasei Co., Ltd .; epoxy equivalent 187 g / eq) are mixed and heated at 150 ° C., and melted, and then triphenylphosphine is used as a catalyst at 500 ppm
The reaction mixture was added and reacted at 170 ° C. for 5 hours to obtain a phenol resin (B1). The obtained bifunctional phenol resin has a phenolic hydroxyl group equivalent of 1560 g / eq and a softening point of 11
It was 8 ° C.

Preparation Example 1 of Curing Agent 80 parts of oleylamine and 20 parts of TH-5000 were added and mixed at 100 ° C. for 2 hours to obtain a curing agent (A1).

Preparation Example 2 of Curing Agent 80 parts of oleylamine and 20 parts of the phenol resin (B1) obtained in the preparation example of phenol resin were added and mixed at 120 ° C. for 2 hours to obtain a curing agent (A2).

Production Example 3 of curing agent Add 80 parts of oleylamine and 20 parts of PM130 (Toho Chemical Co., Ltd .: petroleum resin: softening point 130 ° C.) and add 2 at 140 ° C.
The mixture was mixed for a time to obtain a curing agent (A3).

Production Example 4 of Curing Agent 80 parts of oleylamine, 10 parts of PM130 and TH-5
000 10 parts was added and mixed at 140 ° C. for 2 hours to obtain a curing agent (A4).

Production Example 5 of Curing Agent 80 parts of oleylamine and 20 parts of orthocresol novolac resin GCN85 (manufactured by Gunei Chemical Co., Ltd .: softening point 85 ° C.) were added and mixed at 100 ° C. for 2 hours to obtain a curing agent (A5). It was

Production Example 6 of Curing Agent A curing agent (A6) was obtained by adding 80 parts of oleylamine and 20 parts of bisphenol A and mixing at 100 ° C. for 2 hours.

Example 1 30 parts of a mixture obtained by heating 55 parts of YD-128 and 45 parts of a curing agent (A1) to 50 ° C. and 70 parts of modified asphalt heated to 170 ° C. were mixed to obtain an asphalt epoxy. A resin composition was obtained. After curing this asphalt epoxy resin composition for 2 hours at 160 ° C., the temperature is lowered to 50 ° C. and the toughness and maximum strength are obtained by performing a toughness and tenacity test according to the Japan Asphalt Emulsion Association Standard JEAAS at the same temperature and calculating the numerical values. Indicated. Further, in order to confirm the strength change after the construction, the same test was conducted by leaving it at 20 ° C. for 2 weeks and raising the temperature to 50 ° C. The pot life was defined as the time until the viscosity of the asphalt epoxy resin composition at 160 ° C. was recorded hourly by a stirrer equipped with a torque meter until the viscosity reached twice the initial viscosity. The results are shown in Table 1.

Example 2 An asphalt epoxy resin composition was prepared in the same manner as in Example 1 except that the curing agent (A1) was changed to (A2), and the toughness test and the pot life were measured. Is shown in Table 1.

Example 3 An asphalt epoxy resin composition was prepared in the same manner as in Example 1 except that the curing agent (A1) was changed to (A3), and the toughness test and the pot life were measured. Is shown in Table 1.

Example 4 An asphalt epoxy resin composition was prepared in the same manner as in Example 1 except that the curing agent (A1) was changed to (A4), and the toughness test and the pot life were measured. Is shown in Table 1.

Example 5 55 parts of YD-128, 50 parts of YD-128 and PG-2
07 (polypropylene glycol diglycidyl ether manufactured by Tohto Kasei Co., Ltd .; epoxy equivalent 340 g / eq) except that the amount was changed to 5 parts to prepare an asphalt epoxy resin composition in the same manner as in Example 1 for a toughness test and a pot life. Was measured and the results are shown in Table 1.

Comparative Example 1 An asphalt epoxy resin composition was prepared in the same manner as in Example 1 except that the curing agent (A1) was changed to (A5), and a toughness test and a pot life were measured. Is shown in Table 1.

Comparative Example 2 An asphalt epoxy resin composition was prepared in the same manner as in Example 1 except that the curing agent (A1) was changed to (A6), and the toughness test and the pot life were measured. Is shown in Table 1.

Comparative Example 3 An asphalt epoxy resin composition was prepared in the same manner as in Example 1 except that the mixture of the epoxy resin and the curing agent was changed to 5 parts with respect to 70 parts by weight of asphalt, and a toughness test was conducted. The pot life was measured and the results are shown in Table 1.
It was shown to.

Reference Example As a reference example, a modified asphalt alone was subjected to a toughness test and a pot life was measured. The results are shown in Table 1.

[0041]

[Table 1]

[0042]

INDUSTRIAL APPLICABILITY The asphalt epoxy resin composition of the present invention has a long pot life at a high temperature, is excellent in workability, and is useful for providing an excellent pavement capable of exhibiting sufficient strength immediately after construction.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuko Tabuchi             3-17-14 Higashikasai, Edogawa-ku, Tokyo Tohka             Sei product Co., Ltd. F-term (reference) 2D051 AA02 AF01 AG01 AG03 AG14                       AG15 AH02 AH03 EA06 EB06                 4J002 AG00W BA013 CD00X CD01X                       CD05X CD06X CD11X CD13X                       CH083 EN026 FD143 FD146                       GL00                 4J036 AA01 DC03 DC06 DC12 FB12                       FB18 FB21 JA14

Claims (5)

[Claims] 1. An asphalt epoxy resin composition comprising asphalt, an epoxy resin, and an epoxy resin curing agent, wherein the epoxy resin curing agent is an aliphatic primary amine having 8 to 22 carbon atoms and a bifunctional phenol having a softening point of 80 ° C. or higher. An asphalt epoxy resin composition comprising a resin and / or a petroleum resin having a softening point of 80 ° C. or higher. 2. The bifunctional phenol resin having a softening point of 80 ° C. or higher contains a terminal phenolic hydroxyl group having a phenolic hydroxyl group equivalent of 300 g / eq or more represented by the following general formula (1). The asphalt epoxy resin composition according to 1. [Chemical 1] (In the formula (1), X is a bisphenol residue, and a plurality of X may be the same or different. Further, the average degree of polymerization n
Is the number of repeating units, and n ≧ 0. ) 3. The asphalt epoxy resin composition according to claim 1, wherein the epoxy resin according to claim 1 contains 60 parts by weight or more of an aromatic polyepoxy compound. 4. The epoxy resin curing agent according to claim 1 is a bifunctional phenol resin having 60 to 95 parts by weight of an aliphatic primary amine having 8 to 22 carbon atoms and a softening point of 80 ° C. or higher, and / or a softening point of 80 ° C. An asphalt epoxy resin composition comprising 5 to 40 parts by weight of the above petroleum resin. 5. The asphalt epoxy resin composition according to claim 1, wherein the total amount of the epoxy resin and the curing agent is 10 to 100 parts by weight with respect to 100 parts by weight of asphalt.