JPH07188357A - Repairing material and method for repairing asphalt structure - Google Patents

Abstract

PURPOSE:To obtain a repairing material for asphalt structures, containing a specific unsaturated ester, a (meth)acrylate and other monoacrylate, excellent in property sticking to asphalt, crack follow-up property and stress transmitting property. CONSTITUTION:This repairing material contains (A) an unsaturated ester obtained by reacting an epoxy resin with an unsaturated monobasic acid such as (meth)acrylic acid or an unsaturated polybasic acid such as (anhydrous) maleic acid, (B) a compound of formula I [R is H or methyl; R' is a 1-12C alkylene or a 4-12C oxaalkylene; R'' is a group of formula II, formula III or formula IV; (n) is 0 or 1] and (C) a monoacrylate monomer having 1150 molecular weight, except the component B.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to repair materials and methods for repairing asphalt structures.

[0002]

2. Description of the Related Art Conventionally, for repairing cracks in asphalt pavements, asphalt structures such as hydraulic asphalt, 1) a method of cutting the cracks to replace the pavement, 2) a method of injecting heated asphalt into the cracks , 3) A method of injecting asphalt emulsion for temporary sealing has been adopted. With the construction method 1), cracks occur again during the winter. In the method of 2), since the viscosity is high, it is not possible to inject to the depth of the cracks, and it is not possible to transfer the injected asphalt and pavement, and it is not possible to transmit stress. In many cases, the cracks expand again at low temperatures. However, the effect cannot be sustained. In the method of 3), the shrinkage of the emulsion at the time of decomposition is large and the cracks cannot be actually filled. Japanese Patent Publication Sho 58-30962
The publication proposes a binder in which coal tar is mixed with petroleum resin, xylene resin, soft aggregate and the like, but this material tends to have poor adhesion at low temperatures. In this way there are practically no effective measures,
Only the effect of temporarily preventing the infiltration of water can be expected, and it is customary that cracks may occur again in the winter, or the cracks may expand and be repaired repeatedly in early spring.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to solve the above-mentioned problems and is superior in permeability to an asphalt structure containing asphalt and aggregate as compared with conventional materials and has a large adhesive force. The present invention provides a repair material having an excellent ability to transmit stress and a repair method for an asphalt structure using the repair material.

[0004]

That is, the present invention provides an unsaturated ester obtained by reacting (a) an epoxy resin with at least one compound selected from the group consisting of unsaturated monobasic acids and unsaturated polybasic acids. , (B) the following general formula (I)

[Chemical 3] (However, R represents hydrogen or a methyl group, and R ′ is an alkylene group having 2 to 12 carbon atoms or two or more segments of an alkylene chain having at least 2 carbon atoms are bonded via an oxygen atom. Represents an oxaalkylene group having 4 to 12 total carbon atoms, and R ″ is

[Chemical 4] And n is 0 or 1, and (c) a repair material containing a monoacrylate monomer having a molecular weight of 150 or more (excluding the component (b)) and an asphalt structure using the repair material. Regarding the repair method of things.

The repair material of the present invention comprises the above-mentioned component (a),
The component (b) and the component (c) are contained,
The epoxy resin used as a raw material for the unsaturated ester of the component (a) is not particularly limited, and may be, for example, a compound represented by the general formula (II)

[Chemical 5] (In the formula, x represents an integer of 0 to 15) is used. Examples of this kind of compound include Epicoat 828, Epicoat 1001, Epicoat 1004 manufactured by Shell Chemical Co., Ltd., and AER-664H, A manufactured by Asahi Kasei Corporation.
ER-331, AER-337, D.C. manufactured by Dow Chemical Company. E. R. 330, D.I. E. R. 660, D.I. E. R
There are 664 etc.

A compound in which a part of hydrogen atoms of the epoxy resin is replaced with halogen (eg bromine) can also be used. Examples of this type of compound include Epotote YDB-400 and YDB-340 manufactured by Tohto Kasei Co., Ltd. and Sumiepoxy ESB-340, ESB-400 and ES manufactured by Sumitomo Chemical Co., Ltd.
B-500, ESB-700, DER made by Dow Chemical Company
-542, DER-511, DER-580, 1045, 1046, 1050, DX-248 manufactured by Yuka Shell Co., Ltd.
Etc.

Further, the following general formula (III)

[Chemical 6] (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group, and x represents an integer of 0 to 15). Examples of compounds of this type include D.I. E. N. Four
31, D.I. E. N. 438, Epicoat 152 and Epicoat 154 manufactured by Shell Chemical Co., and EPN113 manufactured by Ciba
There are 8 mag.

ERL42 manufactured by Union Carbide
11, CY208, CY221, C manufactured by Ciba Geigy
Y350, XB2615, CY192, CY184 and the like are also used. These epoxy resins can be used alone or in combination of two or more kinds. Further, in order to improve workability, a low viscosity epoxy resin may be used in combination with an EPbis type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin or the like.

The unsaturated monobasic acid to be reacted with the epoxy resin includes acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, tricyclo [5.2.1.0 ^2,6 ] -4-decene-8 or 9 A partially esterified carboxylic acid containing a residue and an unsaturated dibasic acid residue as constituent elements can be used. Examples of partially esterified carboxylic acids are 8- or 9-hydroxytricyclodecene-4- [5.2.1.
[0 ^2,6 ] of 1.00 to 1.20 moles is obtained by heating 1 mole of unsaturated dibasic acid such as maleic anhydride, itaconic acid, citraconic acid and the like at 70 to 150 ° C. under an inert gas stream. There are unsaturated dibasic acid monoesters.

Further, tricyclodecadiene-4,8-
Unsaturated dibasic acid obtained by adding an unsaturated dibasic acid such as maleic acid, fumaric acid or itaconic acid to [5.2.1.0 ^2,6 ] in the presence of a catalyst such as sulfuric acid or Lewis acid. Monoesters can also be used. This is shown below using maleic acid as an example.

[Chemical 7]

In addition to the unsaturated monobasic acid, an unsaturated polybasic acid can be used, but in this case, it is preferable to use it in combination with the unsaturated monobasic acid. Examples of unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, adipic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and trimellitic anhydride. Acid etc. are mentioned. Further, it is preferable to use a dibasic acid having 12 or more carbon atoms, for example, dodecanedioic acid, SLB-1 manufactured by Okamura Oil Co., Ltd.
2, ULB-20 manufactured by Okamura Oil Co., Ltd., which is a mixture of isomers of unsaturated dibasic acid having 16 carbon atoms, SL-20 manufactured by Okamura Oil Co., Ltd., which is a mixture mainly composed of saturated dibasic acid having 20 carbon atoms, There is a dimerized fatty acid obtained from tall oil fatty acid, which is commonly called dimer acid having 36 carbon atoms, as a raw material. Commercially available products of dimer acid include Empol 1022, Empol 1024 (manufactured by Emery), Versadim 216, Versadim 288 (manufactured by Daiichi General Co., Ltd.), and Haridimer # 200 (manufactured by Harima Chemical Co., Ltd.).

The epoxy resin and the unsaturated monobasic acid are
60 ° C to 150 ° C, preferably 70 ° C to 130
The reaction is carried out at a temperature of ° C to give the unsaturated ester. When the unsaturated monobasic acid and the unsaturated polybasic acid are used in combination, the ratio of both is preferably such that the carboxyl groups of these acid components and the epoxy groups of the epoxy resin are approximately equivalent.

The formation of unsaturated ester can be examined by quantifying the carboxyl group of unsaturated monobasic acid or polybasic acid and examining the acid value. This acid value is preferably 50 or less, more preferably 15 or less. During the reaction, hydroquinone, parabenzoquinone, to prevent gelation due to polymerization,
It is preferable to use a polymerization inhibitor such as p-tert-butyl catechol and hydroquinone monomethyl ether.

In the esterification reaction, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, triethylamine,
The reaction time can be shortened by using a tertiary amine such as dimethylaniline or the like, and an esterification catalyst such as ferric chloride, lithium hydroxide, lithium chloride or stannic chloride.

The repair material of the present invention further contains the component (b) represented by the above general formula (I). Examples of this compound include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl acrylate, dicyclopentenyloxypropyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, diethylene glycol monodicyclohexyl. acrylic acid esters or methacrylic acid esters of pentenyl ether, tricyclo [5.2.1.0 ^{2 '6]}
Deca-8-yl acrylate, tricyclo [5.2.
1.0 ^2'6] dec-9-yl acrylate, tricyclo [5.2.1.0 ^{2 '6]} dec-8-yl methacrylate, tricyclo [5.2.1.0 ^{2' 6]} dec -9 - yl methacrylate, tricyclo [5.2.1.0 ^{2 '6]} dec-8-yl oxy methacrylate, tricyclo [5.
2.1.0 ² ' ⁶ ] deca-3-ylmethyl acrylate,
Tricyclo [5.2.1.0 ^{2 '6]} dec-4-yl methyl acrylate, tricyclo [5.2.1.0 ^{2' 6]} dec-3-yl methyl methacrylate, tricyclo [5.
2.1.0 ² ' ⁶ ] Deca-4-ylmethyl methacrylate and the like can be mentioned. These compounds are known, and dicyclopentadiene is subjected to addition reaction with alkylene glycol or oxaalkylene glycol, and the produced alkylene glycol monodicyclopentenyl ether or oxaalkylene glycol monodicyclopentenyl ether is subjected to condensation reaction with methacrylic acid, or It can be produced by transesterification with methyl methacrylate. It is also possible to replace the methacrylic acid or methyl methacrylate with acrylic acid or methyl acrylate. It can also be produced by addition reaction of alkylene glycol monoacrylate or alkylene glycol monomethacrylate with dicyclopentadiene.

The repair material of the present invention further includes (c) above.
Contains ingredients. The component (c) is a monoacrylate monomer having a molecular weight of 150 or more. If the molecular weight is less than 150, the excellent effect of the present invention cannot be obtained. Preferred examples of this compound include, for example, methoxy (poly) ethylene glycol (meth) acrylates. This product having a molecular weight of 188 to 1068 is commercially available. For example, NK ester M-20G, M-40G, M-
90G, M-230G, etc. (all manufactured by Shin-Nakamura Chemical Co., Ltd.). Furthermore, β-methacryloyloxyethylhydrodiene phthalate (NK ester CB-1, manufactured by Shin-Nakamura Chemical Co., Ltd.), β-methacryloyloxyethyl hydrozine-succinate (NK ester SA, manufactured by Shin-Nakamura Chemical Co., Ltd.), phenoxyethyl acrylate (NK Ester AMP-10G (Shin Nakamura Chemical Co., Ltd.), PHE
(Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), phenoxydiethylene glycol acrylate (NK ester AMP-20G (manufactured by Shin-Nakamura Chemical Co., Ltd.), PHE-2 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), phenoxy polyethylene glycol acrylate (NK ester AMP-60G, Shin Nakamura Kagaku). Industrial), methoxy polyethylene glycol acrylate (NK ester AM-9
0G, manufactured by Shin Nakamura Chemical Co., Ltd.). Among them, those having a methoxy group or a phenoxy group are preferable.

The blending amount of the above-mentioned component (a) is (a),
The total amount of (b) and (c) is preferably 5 to 30 parts by weight, more preferably 10 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight, based on 100 parts by weight. If it is less than 5 parts by weight, the adhesive strength tends to be poor, and if it exceeds 30 parts by weight, the viscosity tends to be high and the permeability tends to be poor. The component (b) is preferably 40 to 90 parts by weight, particularly preferably 60 to 80 parts by weight, based on 100 parts by weight of the total amount of (a), (b) and (c). If the amount of the component (b) is less than 40 parts by weight, the viscosity tends to be high and the permeability to the asphalt structure tends to be poor, and if it exceeds 90 parts by weight, the adhesion tends to be weak. The component (c) is mainly used for imparting elongation to the cured product, and is preferably mixed in an amount of 5 to 30 parts by weight with respect to the total amount of (a), (b) and (c). If the amount is less than 5 parts by weight, the elongation effect is small and the following performance tends to be poor, and if it exceeds 30 parts by weight, the cured product tends to be soft and the adhesive force tends to be lowered.

Further, other known acrylic acid ester, methacrylic acid ester and the like may be used in combination with the repair material of the present invention to the extent that the curability of the present invention is not impaired. In addition to the above, the repair material according to the present invention contains a curing agent, and if necessary, an accelerator, a desiccant, and an aggregate.

A polymerization initiator such as an organic peroxide is used as the curing agent. The organic peroxide is preferably a peroxide that is easily dissolved in the compound, for example, a peroxide derived from a hydrocarbon having 3 to 18 carbon atoms, hydroperoxide, or the like, and specifically, t-butyl hydroperoxide, Cumene hydroperoxide, methyl ethyl ketone hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, t-butyl perbenzoate, 2,2- (t-butylperoxy) -butane,
Examples thereof include bis- (1-hydroxy-cyclohexyl) -peroxide and t-butylperoxyisopropyl carbonate. The curing agent is preferably used in the range of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the repair material. If it is less than 0.1% by weight, the repair material may not be sufficiently cured, and if it exceeds 10% by weight, the cured product tends to be soft.

Further, aniline, N, N as a promoter
-Dimethylaniline, N, N-diethylaniline, toluidine, N, N-dimethyl-p-toluidine, N, N-
Di (hydroxyethyl) toluidine or the like can be used. The usage amount is 0.01 to 1 with respect to the repair material.
The range of 0% by weight is preferable, and the range of 0.1 to 1% by weight is more preferable. If the amount used is less than 0.01% by weight, the accelerating effect is not sufficient, and if it exceeds 10% by weight, the plasticizing effect acts and the strength of the resin cured product decreases, which is not preferable.

As the desiccant, a polyvalent metal salt and / or a polyvalent metal complex is used. In general, metal salts of higher fatty acids are well known, for example, naphthenic acid, polyvalent metal salts such as octenoic acid, as the polyvalent metal, calcium, copper, zirconium, manganese, cobalt, lead, iron,
Vanadium or the like is used, and examples of preferable polyvalent metal salts include cobalt octenoate and cobalt naphthenate. As an example of the polyvalent metal complex, a complex of acetylacetone is well known, and examples thereof include cobalt acetyl acetate and manganese acetyl acetate. These are preferably used in the range of 0.01 to 5% by weight with respect to the repair material, and have a function of promoting the action of the organic peroxide.

The aggregate is composed of coarse sand, fine sand and stone powder. Coarse sand has a particle size of 0.3 to 2.5 mm, fine sand has a particle size of 0.6 mm or less, and stone powder has a particle size of 1.2 mm or less. It is preferable that the aggregate is coated and / or blended with asphalt in advance so that the adhesive strength is improved. When the aggregate is contained in the repair material, it is preferably contained in an amount of 30 to 90% by weight, particularly 60 to 70% by weight. Further, the repair material of the present invention can be added with a pigment, a dye, an antioxidant, an ultraviolet absorber, a flow control agent, a thixotropic agent, a plasticizer, etc., if necessary.

The present invention also relates to a method for repairing an asphalt structure using the above repair material. The asphalt structure is repaired by injecting the repair material of the present invention into the cracked portion of the asphalt structure and curing it. Asphalt structures include asphalt pavement and hydraulic asphalt, which are impermeable walls when dams are constructed. It is preferable to inject the asphalt-coated or blended aggregate into the cracks and then inject the repair material of the present invention.

[0024]

EXAMPLES The present invention will be described with reference to examples. In addition, "part" in an Example is a weight part and "%" is a weight%. [Synthesis of unsaturated ester (a)] Methacrylic acid 411 parts by weight, epibis type epoxy resin Epicoat 828 (manufactured by Shell) 453 parts by weight, Epicoat 1001 (manufactured by Shell) 1136 parts by weight, hydroquinone 0.4 parts by weight and trimethyl 1 part by weight of 4 parts by weight of benzyl ammonium chloride
It heated at 00 degreeC for 10 hours, and obtained the unsaturated ester (a) with an acid value of 15. Examples 1 to 5 With the formulation shown in Table 1, the unsaturated ester (a) obtained by the above synthesis method was dissolved in dicyclopentenyloxyethyl methacrylate as the component (b), and methoxy was added as the component (c). Polyethylene glycol # 400 methacrylate (molecular weight 468, NK ester M-90G,
Shin Nakamura Chemical Co., Ltd.) was mixed to obtain a mixed solution. To 100 parts of this mixed solution, 2 parts of 6% cobalt naphthenate (xylene solution) and cumene hydroperoxide (80
%) 4 parts were mixed to obtain repair materials IV.

Comparative Example 1 In Comparative Example 1, instead of the repair materials I to V, straight asphalt (penetration: 80/100) (Showa Shell Sekiyu KK)
Was manufactured by heating it to 150 ° C., injecting it into the repaired part, and allowing it to stand for 1 day before testing.

Evaluation of Properties Table 1 shows the tensile strength and the recovery rate when the asphalt specimens were repaired by using the repair materials of Examples and Comparative Examples. It is shown that the repair materials of the present invention used in Examples 1 to 5 have a higher tensile strength after repair and a higher recovery rate than Comparative Example 1.

[0027]

[Table 1]

The asphalt specimen was prepared and the tensile strength test was conducted as follows. 1. Preparation of Asphalt Specimen 1) Asphalt used was manufactured by Showa Shell Sekiyu KK (penetration grade: 80/100) having the properties shown in Table 2.

[0029]

[Table 2] 2) Table 3 shows the composition of the asphalt specimen.

[0030]

[Table 3]

3) Preparation of Asphalt Specimen (1) Aggregate and asphalt are weighed on the day before mixing, and the aggregate is put in a dryer and heated for about 16 hours so that the aggregate temperature becomes 150 ° C. did. (2) The aggregate and asphalt were put into a mixer and mixed (mixing temperature: 150 ° C., mixing time: 3 minutes). (3) A mixture of 1150 g of one specified Marshall specimen in the asphalt pavement guide was transferred to a container and heated to an appropriate temperature, then placed in a mold and tamped with an automatic rammer, 50 times on both sides, 100 times in total. . (4) Curing was performed at room temperature for 12 hours or more. (5) After curing, remove the mold using a hydraulic jack and set the diameter to 1
A cylindrical asphalt specimen having a thickness of 0.16 cm and a thickness of 6.5 cm was obtained.

2. Tensile Strength Test (Cleavage Test) The load performed using an Instron 1185 type tester was recorded on a chart recorder equipped with the Instron 1185 type tester. The tensile strength was determined by the procedure shown below. (1) The asphalt specimen obtained in 1 was subjected to a crush test, and the asphalt specimen was broken and broken to obtain the base metal strength. (2) The destroyed asphalt test piece obtained in (1) was arranged with a space of 2 mm, the repair material was injected into this space, and the periphery thereof was wrapped with gum tape. (3) Waiting for the repair material to completely cure, the gum tape wrapped around the periphery was removed on the day after the injection to obtain a repaired asphalt specimen. (4) Using the repaired asphalt specimen (I)
The crush test was conducted again under the same conditions as above. Recovery rate [(tensile strength of repaired asphalt specimen / tensile strength of asphalt specimen base material) x 100
(%)] Was calculated.

Examples 6 to 10 Instead of the NK ester M-90G used in Example 1, phenoxydiethylene glycol acrylate (N
Table 4 shows K ester AMP-60G, manufactured by Shin-Nakamura Chemical Co., Ltd.
A repair material was prepared in the same manner except that it was used in the composition shown in (1) and evaluated in the same manner. The results are shown in Table 4.

[0034]

[Table 4]

[0035]

INDUSTRIAL APPLICABILITY The repair material of the present invention has a large adhesive force to asphalt, a good crack-following property, an excellent ability to transmit stress, and is useful as a repair material for an asphalt structure.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Teruo Sugawara, 3-10-6 Makomanaizumimachi, Minami-ku, Sapporo-shi, Hokkaido (72) Inventor Kazuyuki Kawamura 1-3-34, Hiragishi, Toyohira-ku, Sapporo, Hokkaido Hokkaido Development Bureau Civil Engineering Research Institute (72) Inventor Katsunori Sasaki 1-3-4, Ichijo Hiragishi, Toyohira-ku, Sapporo, Hokkaido Development Bureau, Civil Engineering Research Institute (72) Fumio Tashiro Futao Sunayama, Hasaki-machi, Kashima-gun, Ibaraki Prefecture Hitachi Kasei Plant, Kasei Plant (72) Inventor Takeo Kojima, Gosan Ichiyama, Hasaki-cho, Kashima-gun, Ibaraki Prefecture Hitachi Chemical Co., Ltd., Kashima Plant

Claims (8)

[Claims] 1. An unsaturated ester obtained by reacting (a) an epoxy resin with at least one compound selected from the group consisting of unsaturated monobasic acids and unsaturated polybasic acids,
(B) The following general formula (I): (However, R represents hydrogen or a methyl group, and R ′ is an alkylene group having 2 to 12 carbon atoms or two or more segments of an alkylene chain having at least 2 carbon atoms are bonded via an oxygen atom. Represents an oxaalkylene group having a total of 4 to 12 carbon atoms, and R ″ is Where n is 0 or 1), and (c) a monoacrylate monomer having a molecular weight of 150 or more (however, excluding the component (b)), a repair material. 2. An unsaturated ester of component (a) 5 to 30 parts by weight, a compound of component (b) 40 to 90 parts by weight and (c).
The repair material according to claim 1, which comprises 5 to 30 parts by weight of the component monoacrylate monomer in a total amount of 100 parts by weight. 3. The repair material according to claim 1, further comprising an organic peroxide. 4. The repair material according to claim 1, 2 or 3, further comprising a polyvalent metal salt and / or a polyvalent metal complex. 5. The repair material according to claim 1, further comprising crushed stone, coarse sand, fine sand or stone powder as an aggregate. 6. The cracked portion of the asphalt structure according to claim 1.
5. A method for repairing an asphalt structure, which comprises injecting the repair material according to any one of 5 to 5 and curing it. 7. A method for repairing an asphalt structure, which comprises injecting an aggregate into a crack portion of the asphalt structure and then injecting and curing the repair material according to claim 1. 8. The method for repairing an asphalt structure according to claim 7, wherein the aggregate is an aggregate coated or blended with asphalt.