JP2005023278A - Hardenable composition for repairing concrete crack - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardenable composition for repairing concrete cracks that can repair the cracks on the concrete base material in an air atmosphere or in water, has excellent adhesion to the base material, water resistance and shows excellent filling properties into the crack spaces occurring on the base material, particularly good filling into fine spaces and can effectively inhibit the corrosion from the cracks. <P>SOLUTION: The hardenable composition for repairing concrete cracks comprises (A) a liquid epoxy resin having a viscosity of 800 to 30,000 mPa s/25°C, (B) an amine hardener, (C) a silane coupling agent, (D) pigments having a specific gravity of 2-3 and (E) (e-1) a reactive diluent bearing epoxy groups having a viscosity of 10 to 5,000 Pa s/25°C and (e-2) a liquid hydrocarbon resin. In this case, the amount of the pigment (D) is 10 to 40 vol.% in 100 vol.% of the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is capable of repairing cracks generated in a concrete base material in the air and water, has excellent adhesion to the base material, water resistance, and effectively prevents corrosion of the base material. The present invention relates to a curable composition for repairing concrete cracks that can form a cured product.

  Conventionally, a concrete base material is used in many structures and facilities. However, in recent years, shrinkage due to drying of the concrete base material, expansion and contraction of the base material due to changes in environmental temperature, expansion due to rusting of reinforcing bars inside the base material, cracks in the concrete base material due to alkali aggregate reaction, etc. Is a problem.

  For example, if a crack occurs in a concrete structure installed in a place such as the sea, beach, river, lake, etc., or in a facility that uses seawater or freshwater, Seawater and fresh water infiltrate, corrode the concrete base material from the inside, and as a result, the base material peels and collapses. Therefore, there is a need for repairing cracks in the concrete substrate.

  Repair coating is an example of a crack repair method for concrete base materials. As this repair coating, it is known that the surroundings of the cracked concrete base material are dammed and drained, and the work is performed in the atmosphere. However, this coating method is very expensive. For this reason, underwater repair coatings have been put to practical use that can be used to prevent clogging and draining the surrounding area and reduce the work cost. As an underwater coating type composition used for such underwater repair coating, a composition containing a polyamide cured epoxy resin, a modified amine cured epoxy resin, an unsaturated polyester resin, or the like is used.

  However, when the underwater coating type composition containing each of the above resins is coated on a concrete base surface, the resulting coating film has insufficient water resistance in water, in seawater or on a wet surface, or has good water resistance. Even if it exists, it had the problem that the adhesiveness with respect to a base material was inadequate. Moreover, even if it painted using this composition in air | atmosphere, it had the same problem.

In order to solve such problems, curing agents and resin compositions as shown in the following (1) to (5) have been proposed so far.
(1) A polyester obtained by polycondensation of a dibasic acid and a dihydric alcohol at a certain molar ratio is reacted with a polyvalent amine in an amount such that the amine residue with respect to the number of acid residues in the polyester is a fixed ratio. An epoxy resin-based underwater paint curing agent (see Patent Document 1 (Japanese Patent Laid-Open No. 54-1224028)),
(2) An epoxy resin containing at least one epoxy group in the molecule, and a resin composition having a room temperature curable curing agent as a color developing agent, and an amide compound having a specific structure added to the underwater coating type epoxy Resin composition (refer to Patent Document 2 (JP-A-2-29479)),
(3) (a) a thermosetting resin curable in water and a color developing material comprising the curing agent thereof, and (b) an underwater paintable underwater curable resin composition containing a polycarboxylic acid having a specific structure or a salt thereof. Thing (refer patent document 3 (Unexamined-Japanese-Patent No. 2-251577)),
(4) A resin composition containing a surfactant having a specific structure as a main component of an underwater curable thermoplastic resin (see Patent Document 4 (Japanese Patent Laid-Open No. Hei 2-298563)), (5 ) An epoxy resin and an epoxy resin composition containing a phosphorus atom-containing epoxy compound having a specific structure in a resin composition mainly composed of an epoxy resin and its curing agent (Patent Document 5 (Japanese Patent Laid-Open No. 3-199229)) Publication))) etc.

  However, using the curing agent or resin composition described in the publications of (1) to (5), even when repair coating is applied to a concrete substrate in water (or in the air), the coating film obtained is the substrate. There was room for improvement in adhesion, water resistance or corrosion resistance.

Furthermore, as an underwater paint type epoxy resin composition,
(6) An epoxy resin having an average of 1.7 or more epoxy groups per molecule and having an epoxy equivalent (weight) of about 70 to 1000, an underwater curable epoxy resin curing agent, and a silane coupling An underwater curable epoxy resin composition (Patent Document 6 (Japanese Patent Application Laid-Open No. Sho 62-270668)) containing an agent is proposed.

  However, the coating film obtained from the resin composition described in the above publication (6) is excellent in adhesion to a concrete substrate, but has a problem in water resistance or corrosion resistance.

  On the other hand, when cracks have occurred deep inside the concrete base material, repairing cracks by repair coating effectively prevents the composition from entering the interior of the cracks, especially the details, and effectively corrodes the cracks. It is hard to say that it can be prevented. Therefore, as a repair method in such a case, a repair method in which a resin composition is injected into a crack of a concrete base material has been conventionally used.

Examples of the resin composition used in the repair method by such injection include those shown in the following (7) to (9).
(7) The repaired part of the concrete structure is enclosed in a water-tight formwork, the inside of the formwork is drained and depressurized, and immediately after pouring resin with good fluidity into the formwork, mortar is injected into the formwork. The resin with good fluidity used in the repair method for replacing the resin in the same mold (Patent Document 7 (Japanese Patent Laid-Open No. 55-140680)),
(8) In the crack repairing method from the upper surface of the concrete foundation pile column body, a low-viscosity water-curable epoxy resin that is press-fitted by a plunger pump (Patent Document 8 (Japanese Patent Laid-Open No. 9-3951)),
(9) A low-viscosity water-curing epoxy resin (Patent Document 9 (Japanese Patent Laid-Open No. 9-4238)) or the like that is press-fitted by a plunger pump in a crack repair method for a crack surface generated in a concrete column.

  When the resin composition described in the publication (7) is used, in order to fill the composition into the cracks of the concrete base material, the composition must be injected under pressure, When the resin composition described in the publications (8) and (9) is used, in order to fill the composition into the cracks of the concrete base material, a hole is formed in the base material, and the resin is then discharged by a pump or the like. The composition must be injected under pressure.

  However, in the method of injecting these resin compositions by applying pressure, there is a possibility that cracks may further occur in the concrete base material due to the pressure or the operation of making a hole in the base material. Furthermore, if too much pressure is applied to the resin composition, the concrete substrate itself may be destroyed.

As a crack repair method for a concrete base material that solves such problems, there is a repair method by natural fall (filling) using the self-weight and fluidity of the resin composition. However, in the method of repairing a crack in a concrete base material by this natural fall (filling), when a conventional resin composition is used, there is a problem in the fillability to the inside of the crack, particularly to the details. Furthermore, the cured product obtained from the resin composition has problems in adhesion to the substrate and water resistance.
JP 54-1224028 A JP-A-2-29479 Japanese Patent Laid-Open No. 2-251577 JP-A-2-298563 Japanese Patent Laid-Open No. 3-199229 JP-A-62-270668 JP-A-55-140680 Japanese Patent Laid-Open No. 9-3951 Japanese Patent Laid-Open No. 9-4238

  The present invention is intended to solve the problems associated with the prior art as described above, and crack repair of a concrete base material is possible in the air and water, and adhesion to the base material, water resistance, It is another object of the present invention to provide a curable composition for repairing concrete cracks, which is excellent in filling of cracks generated in the substrate, particularly in details, and can effectively prevent corrosion from cracks.

The curable composition for concrete crack repair according to the present invention is:
(A) a liquid epoxy resin having a viscosity of 800-30000 mPa · s / 25 ° C.
(B) an amine curing agent,
(C) a silane coupling agent,
(D) a pigment having a specific gravity of 2 to 3, and (E) (e-1) an epoxy group-containing reactive diluent having a viscosity of 10 to 5000 mPa · s / 25 ° C. and / or (e-2) a liquid hydrocarbon resin. A curable composition for repairing concrete cracks comprising:
The pigment (D) is contained in an amount of 10 to 40% by volume in 100% by volume of the composition.

The specific surface area of the pigment (D) is preferably 4 m ² / g or less.

Equivalent ratio (b / g) of epoxy equivalent (a) (g / equiv) of liquid epoxy resin (A) to active hydrogen equivalent (b) (g / equiv) of amino group of amine-based curing agent (B) The component (A) and the component (B) are preferably contained so that a) is 1.0 or less, preferably 0.8 or less.

The viscosity of the concrete crack repairing curable composition is preferably 10,000 mPa · s or less.
The method for repairing a concrete base material according to the present invention is characterized by injecting the curable composition for repairing a concrete crack into a crack portion of the concrete base material.

  According to the curable composition for repairing a concrete crack according to the present invention, a concrete base material can be repaired, and adhesion to the base material, water resistance, and the inside of the crack generated in the base material, particularly to the details. Therefore, corrosion from cracks can be effectively prevented.

This curable composition for repairing concrete cracks can be repaired even in water and has such excellent characteristics as described above, so it is installed in places such as the sea, beaches, rivers, and lakes. It can be suitably used for crack repairing of a concrete base material in a concrete structure or a facility using seawater / freshwater.

  Hereinafter, the present invention will be specifically described.

<Curable composition for repairing concrete cracks>
The concrete crack repairing curable composition according to the present invention includes (A) a liquid epoxy resin having a viscosity of 800 to 30000 mPa · s / 25 ° C., (B) an amine-based curing agent, (C) a silane coupling agent, (D A pigment having a specific gravity of 2 to 3, and (E) (e-1) an epoxy group-containing reactive diluent having a viscosity of 10 to 5000 mPa · s / 25 ° C. and / or (e-2) a liquid hydrocarbon resin. And
The pigment (D) is contained in an amount of 10 to 40% by volume in 100% by volume of the composition.

Further, the curable composition for repairing concrete cracks according to the present invention comprises an epoxy equivalent (a) (g / equiv) of the liquid epoxy resin (A) and an active hydrogen equivalent of the amino group of the amine-based curing agent (B). (B) The equivalent ratio (b / a) to (g / equiv) is 1.0 or less, preferably 0.8 or less, more preferably 0.5 to 0.8, particularly preferably 0.6 to 0. It is desirable to contain this component (A) and this component (B) so that it may become 0.8.

  Due to the equivalence ratio, the composition of the present invention is adjusted in its curing rate and is filled to the details of cracks generated in the concrete substrate. Therefore, the composition can form a cured product that cures in the details of cracks, has excellent water resistance, and can effectively prevent corrosion from cracks generated in the concrete substrate.

  Furthermore, it is desirable that the curable composition for repairing concrete cracks of the present invention has a viscosity (25 ° C.) of 10,000 mPa · s or less, preferably 100 to 8000 mPa · s, more preferably 500 to 6000 mPa · s. Further, the specific gravity is preferably 1 or more, 1.2 to 2.5, and more preferably 1.4 to 2.0.

  Such a curable composition for repairing a concrete crack according to the present invention is excellent in fluidity, has good workability, and can repair cracks in a concrete base material by natural fall (filling) using its own weight. . Therefore, since it can be filled to the detail of the crack which arose in the base material, without damaging a concrete base material, the corrosion from a crack can be prevented effectively.

  The components (A) to (D) will be described below.

Liquid epoxy resin (A)
The liquid epoxy resin (A) is an epoxy resin that is liquid at normal temperature (temperature of 15 to 25 ° C.), has a viscosity in the range of 800 to 30000 mPa · s / 25 ° C., and has a weight average molecular weight of 300 to 750. And polymers or oligomers containing two or more epoxy groups in the molecule, and polymers or oligomers produced by a ring-opening reaction of the epoxy groups. Furthermore, this liquid epoxy resin (A) has an epoxy equivalent of 100 to 2000 (g
/ equiv), preferably 150 to 1000 (g / equiv).

  From the liquid epoxy resin (A) used in the present invention, the epoxy group-containing reactive diluent (e-1) described later is excluded.

  When a curable composition for repairing concrete cracks comprising such a liquid epoxy resin (A) is used, a coating film excellent in coating workability, and having excellent adhesion to the substrate, water resistance, and corrosion resistance is formed. This is preferable because it can be performed.

  Such liquid epoxy resins (a1) include bisphenol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, cresol type epoxy resins, dimer acid-modified epoxy resins, aliphatic epoxy resins. And epoxy resins such as alicyclic epoxy resins and epoxidized oil-based epoxy resins. Among them, bisphenol type epoxy resins are preferable, bisphenol A type and F type epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferably used.

In this invention, such a liquid epoxy resin (A) can be used 1 type or in combination of 2 or more types. When two or more kinds of liquid epoxy resins are used in combination as described above, the molecular weight and epoxy equivalent (g / equiv) of the liquid epoxy resin (A) are both shown as average values.

  Among such liquid epoxy resins (A), so-called bisphenol A type epoxy resins (epoxy equivalents of 150 to 1000 (g / equiv)) are preferable.

  Examples of bisphenol A type epoxy resins that are particularly preferably used include, for example, the bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, water, and the like. Examples thereof include polycondensation products such as bisphenol A type diglycidyl ether such as bisphenol A propylene oxide diglycidyl ether.

In this invention, such a liquid epoxy resin (A) can be used 1 type or in combination of 2 or more types. Thus, when using in combination of 2 or more types of liquid epoxy resins (A), the molecular weight of a liquid epoxy resin (A) and an epoxy equivalent (g / equiv) are all shown by the average value.

Typical examples of the epoxy resin include “Epicoat 828 (trade name), general name: bisphenol A diglycidyl ether” (manufactured by Shell Co., Ltd., weight average molecular weight of about 360, epoxy equivalent of 180 to 190, viscosity of 12,000 to 15,000 mPa · s / 25 ° C.), “Epototo YDF-170 (trade name), general name: bisphenol F diglycidyl ether” (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 160-180, viscosity 2,000-5) 000 mPa · s),
“Flep 50 (trade name)” (manufactured by Toraythiol Co., Ltd., epoxy equivalent of about 330, viscosity of about 27,000 mPa · s / 25 ° C.) Equivalent weight of about 280, viscosity of about 17,000 mPa · s / 25 ° C.)
“Epicoat 828X-90 (trade name), generic name: bisphenol A diglycidyl ether / xylene solution” (828 type epoxy resin, manufactured by Shell Co., Ltd., weight average molecular weight of about 360, epoxy equivalent of about 210, viscosity of about 800 mPa · s / 25 ° C),
“Epicoat 834X-85 (trade name), generic name: bisphenol A type epoxy / xylene solution” (834 type epoxy resin, manufactured by Shell Co., Ltd., weight average molecular weight of about 470, epoxy equivalent of about 282, viscosity of about 3000 mPa · s / 25 ° C),
“Epicoat 1001X-75 (trade name), generic name: bisphenol A type epoxy / xylene solution” (1001 type epoxy resin, manufactured by Shell Co., Ltd., weight average molecular weight of about 900, epoxy equivalent of about 633, viscosity of about 10,000 mPa · s / 25 ° C),
And so on. In the present invention, one or more of these epoxy resins may be contained.

Amine-based curing agent (B)
The amine-based curing agent (B) used in the present invention has an amino group active hydrogen equivalent of 50 to 150 (g / equiv), preferably 70 to 120 (g / equiv), more preferably 80 to 115 (g). / equ
iv) is desirable. Such an amine curing agent (B) and the liquid epoxy resin (
When a curable composition for repairing concrete cracks comprising A) is injected into a crack, a cured product that is excellent in water resistance and that can effectively prevent corrosion from cracks generated in the base material is formed. Can do.

  Examples of such amine curing agents (B) include polyamine compounds that are usually used as epoxy resin curing agents, such as aliphatic polyamines, modified aliphatic polyamines, alicyclic polyamines, modified alicyclic polyamines, and aromatic polyamines. Modified aromatic polyamines, polyamidoamines, and the like can be used. These polyamines can be used alone or in combination of two or more.

  Specific examples of the aliphatic polyamine, alicyclic polyamine and aromatic polyamine include the following polyamines, modified with epoxide addition, Michael addition, Mannich addition, thiourea addition, acrylonitrile addition, ketone blockage, etc. Preferred are aliphatic, alicyclic or aromatic polyamines.

  Specific examples of the aliphatic polyamine include ethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyoxypropylenediamine, and polyoxypropylenetriamine.

  Specific examples of alicyclic polyamines include mensendiamine, 1,2-diaminocyclohexane, isophoronediamine, piperazine, N-aminoethylpiperazine, 1,3-bis (aminomethyl) cyclohexane, metaxylenediamine, bis (4-Amino-3-methylcyclohexyl) methane, polycyclohexylpolyamine, norbornenediamine, furfurylamine, tetrahydrofurfurylamine, methylenebis (furanmethanamine), phenalkamine, 3,9-bis (3-aminopropyl)- 2,4,8,10-tetraoxaspiro (5.5) undecane adduct and the like.

  Specific examples of aromatic polyamines include metaphenylenediamine, diaminodiphenylmethane, diaminodimethyldiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldimethyldiphenylmethane (eg, 4,4′-diamino-3,3′-diethyl-5,5 '-Dimethyldiphenylmethane), diethyltoluenediamine, 3,5-dimethylthiotoluenediamine and the like.

  In the present invention, these amine curing agents may be used alone or in combination of two or more.

  Specific examples of the amine curing agent (B) include “Ancamine 1784” and “Ancamine 1884” (both manufactured by Air Products Japan Co., Ltd.). In the present invention, these amine curing agents may be used alone or in combination of two or more.

Such a mixture of the amine curing agent (B) and the liquid epoxy resin (A) is 60 to 90% by volume, preferably 70 to 85% in 100% by weight of the curable composition for repairing concrete cracks of the present invention. It is desirable that it is contained in an amount of volume%.

  By containing the amine-based curing agent (B) and the liquid epoxy resin (A) in the above amounts, it is excellent in adhesion to a concrete base material and water resistance, and effectively corrodes the base material. A cured product that can be prevented can be formed.

Silane coupling agent (C)
The silane coupling agent (C) used in the present invention has a reactive functional group such as an epoxy group, amino group, mercapto group, vinyl group, methacryloxy group, acryloxy group, styryl group, or isocyanate group, A silane coupling agent having an epoxy group, an amino group, a mercapto group, and more preferably an epoxy group is desirable.

  Examples of the epoxy group-containing silane coupling agent include (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyl. And methyldiethoxysilane.

  Specific examples of such an epoxy group-containing silane coupling agent include compounds (1) to (4) shown in Table 1 below, and (2) is preferably used. .

  In the present invention, one or more of these silane coupling agents (C) may be contained.

  In the present invention, the silane coupling agent (C) is added to the composition (100% by weight) of the present invention in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight. It is desirable that When the composition contains the silane coupling agent (C) in the above amount, the adhesion between the cured product of the composition of the present invention and the surface of the concrete substrate is improved, and the composition is kept in water for a long time. Even when immersed, there is almost no peeling of the cured product, and corrosion from cracks generated in the concrete substrate can be effectively prevented. These effects are prominent when a silane coupling agent containing an epoxy group is added.

Pigment (D)
The pigment (D) used in the present invention has a specific gravity of 2 to 3, preferably 2.4 to 2.8. Further, the pigment (D) preferably has a specific surface area of 4 m ² / g or less.

  When the specific gravity and the specific surface area of the pigment (D) are in the above ranges, a curable composition for repairing concrete cracks having a low viscosity and a specific gravity adjusted as described above can be obtained.

  Such a pigment (D) is preferably 10 to 40% by volume, preferably 10 to 40% by volume, in order to obtain the desired good injectability of the resulting curable composition for repairing concrete cracks. Is preferably contained in an amount of 15 to 35% by volume. Thereby, it is possible to obtain a curable composition for repairing concrete cracks that is excellent in natural descent even in water. Furthermore, the composition is excellent in fluidity and has sufficient details for cracks generated in a concrete base material. Since it is filled, the cured product formed from the composition can effectively prevent corrosion from cracks.

  Examples of such a pigment (D) include extender pigments. A colored pigment may be used instead of the extender, or an extender and a colored pigment may be used in combination.

  Examples of the extender pigment include calcium carbonate, potassium feldspar, kaolin, clay, talc, bentonite, magnesium carbonate, and silica fine powder. Of these, calcium carbonate, potassium feldspar, and silica fine powder are preferable. The extender pigments can be used alone or in combination of two or more.

  Examples of the color pigment include inorganic pigments such as carbon black, titanium dioxide, petiole, iron oxide, iron hydroxide and ultramarine, and organic pigments such as cyanine blue and cyanine green. A color pigment can be used individually by 1 type or in combination of 2 or more types.

When the pigment (D) used in the present invention is used in combination of two or more of the pigments, the specific gravity and specific surface area of the pigment (D) are expressed as average values. Therefore, when two or more pigments are used in combination, pigments having a specific gravity of more than 3 such as alumina white, barium sulfate, barium carbonate, and titanium oxide can be used as long as the specific gravity and specific surface area are included in the above ranges. . Specifically, pigments having a specific gravity exceeding 3 are used in combination so that the total amount of pigment is 30% by volume or less.
(E) Epoxy group-containing reactive diluent (e-1) and / or liquid hydrocarbon resin (e-2)
The curable composition for repairing concrete cracks of the present invention comprises an epoxy group-containing reactive diluent (e-1
And / or liquid hydrocarbon resin (e-2).

Although it will not specifically limit if the viscosity of the curable composition for concrete crack repair of this invention is adjusted to the above-mentioned range, When the said (e-1) component is used independently, the composition 10 of this invention is used.
In 0% by weight, it is desirable that the component (e-1) is contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight. When the component (e-2) is used alone, the component (e-2) is contained in 1 to 40% by weight, preferably 5 to 100% by weight in the composition of the present invention.
It is desirable to be included in an amount of 20% by weight. Furthermore, when the components (e-1) and (e-2) are used, the components (e-1) and (e-2) are contained in 100% by weight of the composition of the present invention. It is desirable that the total is contained in an amount of 1 to 40% by weight, preferably 5 to 20% by weight.

Since the composition of the present invention containing the components (e-1) and / or (e-2) in such an amount has sufficient fluidity, the workability is good, and the concrete substrate Therefore, it is possible to satisfactorily prevent the cracks from being corroded.

Epoxy group-containing reactive diluent (e-1)
The epoxy group-containing reactive diluent (e-1) used in the present invention has a viscosity of 10 to 5000 mPa.
-It is preferable that it is below s / 25 degreeC.

The liquid epoxy resin (A) described above is excluded from the epoxy group-containing reactive diluent (e-1) used in the present invention.

As such an epoxy group-containing reactive diluent (e-1), for example, phenyl glycidyl ether, alkyl glycidyl ether (alkyl group having 1 to 10, preferably 1 to 5, eg, butyl glycidyl ether), versatic acid (versatic acid) glycidyl ester ^{[R 1 R 2 R 3 C} -COO-Gly, alkyl group of ^{R 1 + R 2 + R 3} = C8~C10, Gly: glycidyl group], alpha-olefin epoxide (CH ₃ - (CH ₂ ) _n -Gly, n
= 11 to 13, Gly: glycidyl group), 1,6-hexanediol diglycidyl ether _{(Gly-O- (CH 2)} 6 -O-Gly, Gly: the same as above), neopentyl glycol diglycidyl ether (Gly-O —CH ₂ —C (CH ₃ ) ₂ —CH ₂ —O—Gly, Gly: same as above), trimethylolpropane triglycidyl ether (CH ₃ —CH ₂ —C (CH ₂ —O-Gly) ₃ , Gly: same as above) ), Alkylphenol glycidyl ether [alkyl group having 1 to 10 carbon atoms, preferably 1 to 5, examples: methylphenol glycidyl ether, ethylphenol glycidyl ether, propylphenol glycidyl ether] and the like.

Among these epoxy group-containing reactive diluents (e-1), the alkylphenol glycidyl ether is preferable because it has a low viscosity and can exert a dilution effect.

  These epoxy group-containing reactive diluents can be used alone or in combination of two or more.

  As such an epoxy group-containing reactive diluent, specifically, “NC-513” (alkylated phenol glycidyl ether, manufactured by Cardlite Co., Ltd.) is particularly preferable because of its low viscosity and dilution effect. .

Such an epoxy group-containing reactive diluent (e-1) can contribute to the improvement of curing acceleration at low temperatures, and further reacts with the amine-based curing agent (B), so that it is stronger. A cured product can be formed.

Liquid hydrocarbon resin (e-2)
The liquid hydrocarbon resin (liquid petroleum resin) (e-2) used in the present invention has a normal temperature (15-25).
Liquid hydrocarbon resin having a viscosity of 10 to 5000 mPa · s / 25 ° C., and specific examples of such liquid hydrocarbon resins include aliphatic hydrocarbons ( C9 petroleum resin), aromatic hydrocarbon (C5 petroleum resin), chroman resin, xylene resin, toluene resin, and modified products thereof.

  In the present invention, such liquid hydrocarbon resins can be used alone or in combination of two or more. Thus, when using in combination of 2 or more types of liquid hydrocarbon resin, the said molecular weight of liquid hydrocarbon resin is shown by the average value.

  Among the liquid hydrocarbon resins, it is necessary to have good compatibility with the epoxy resin, and preferably, aromatic hydrocarbon (C5 petroleum resin), xylene resin, or toluene resin is used. desirable.

  The average molecular weight and the like of such a liquid hydrocarbon resin are not generally determined depending on the coating curing conditions (eg, normally dry coating or baking coating) of the obtained paint, but the number average molecular weight is usually 150 to The one of 720 is used.

The typical liquid hydrocarbon resin is specifically,
Examples of aliphatic hydrocarbons (C9 petroleum resin) include Nesiles EPX-L, Nebuchem NL-10, Nebuchem NL-20, Nebuchem NL-30, Nesiles EPX-T6 (trade names, all manufactured by Nevcin Polymers co.), Etc. Can be mentioned.

  Examples of the aromatic hydrocarbon (C5-based petroleum resin) include Maruka Clear H and Maruka Clear V (trade names, both manufactured by Maruzen Petroleum Co., Ltd.).

  Examples of the xylene resin include Nicanol DS, LLL, LL, L, and H (trade names, all manufactured by Mitsubishi Gas Chemical Co., Ltd.) and Hysol SASLH (trade names, manufactured by Shin Nippon Petrochemical Co., Ltd.). it can.

  Examples of the chroman resin include Escron L-5 and L-20 (trade names, both manufactured by Nippon Steel Chemical Co., Ltd.).

  Examples of the toluene resin include Epoxy L (trade name, manufactured by Anchor Chemical Co., Ltd.).

  In the present invention, these liquid hydrocarbon resins may be used alone or in combination.

  In addition to the above components, the following components can also be added to the curable composition for repairing concrete cracks of the present invention.

Other components In the curable composition for repairing concrete cracks of the present invention, if necessary, as other components, a fiber material, a sag-preventing agent, an anti-settling agent, a pigment dispersant, described in JP-A-2-298563 A surfactant, a polycarboxylic acid or a salt thereof described in JP-A-2-251579, a rust preventive pigment, a scaly pigment, a metal powder and the like can be appropriately added. These addition amounts are not particularly limited.

  Examples of the fiber material include asbestos / plant fiber, glass fiber, carbon fiber, and synthetic fiber.

  Examples of the anti-sagging / anti-settling agent include organic viscosity Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax, polyamide wax And a mixture thereof, synthetic fine powder silica, oxidized polyethylene wax, and the like. Polyamide wax, synthetic fine powder silica, oxidized polyethylene wax, and organic clay are preferably used.

Examples of the pigment dispersant include a polymer block copolymer, an acrylic copolymer, a solution of a salt of an unsaturated polyaminoamide and a low molecular weight acid polymer, a solution of a salt of a long-chain polyaminoamide and a polar acid ester, a hydroxyl group Containing carboxylic acid ester, low molecular weight unsaturated polycarboxylic acid polymer solution, low molecular weight unsaturated polycarboxylic acid polymer and polysiloxane copolymer solution, low molecular weight unsaturated acidic polycarboxylic acid polyester and polysiloxane copolymer solution, α-
A partial ester solution of an olefin / maleic anhydride copolymer and a titanate coupling agent are used.

  As the surfactant, surfactants described in JP-A-2-298563 can be used. Specifically, the following general formulas (1), (2), (3), (4), (5)

(In the formula, M represents hydrogen, metal, or basic nitrogen-containing group.)
A surfactant having at least one acid group represented by the formula (or a salt thereof) is used.

  As the polycarboxylic acid or a salt thereof, a polycarboxylic acid or a salt thereof described in JP-A-2-251777 is used, and specifically, two or more carboxyl groups close to each other in the molecule and the number of carbon atoms. A polycarboxylic acid having 4 or more saturated or unsaturated branched or cyclic structures and a hydrophobic hydrocarbon group or a salt thereof is used.

  Examples of the rust preventive pigment include chromic acid, molybdic acid, phosphoric acid, boric acid, ferrite, and lead acid.

  Examples of the flake pigment include glass flakes, stainless steel flakes, aluminum flakes, and plastic flakes.

  Examples of the metal powder include stainless steel powder, zinc powder, and aluminum powder.

  Moreover, if the curable composition for concrete crack repair of this invention is used, crack repair is possible also in air | atmosphere and water (including in seawater). Therefore, the curable composition for repair does not substantially contain a solvent used for dissolving the resin component. When the curable composition for repairing concrete cracks according to the present invention is used only for repairing in the air, there are practical problems, that is, the removal of the solvent from the coating film becomes worse, resulting in problems in coating film formation, etc. It is also possible to add a solvent to such an extent that no adverse effects are observed.

Preparation method of curable composition for repairing concrete cracks The curable composition for repairing concrete cracks of the present invention includes a main component containing the liquid epoxy resin (A) and a curing containing the amine-based curing agent (B). It may be prepared as a two-component type with an agent component. In this case, before use, it is stored in separate containers, and is used by mixing at the time of use.

The silane coupling agent (C), a pigment (D) having a specific gravity of 2 to 3, a liquid hydrocarbon resin (e-2
), “Other components” may be contained in either the main component or the curing agent component, or in both components, or added when mixing the main component and the curing agent component. May be. The epoxy group-containing reactive diluent (e-1) may be contained in the main agent component or added when the main agent component and the curing agent component are mixed.

  In the case of using a curing agent modified so as not to react with the liquid epoxy resin (A) during storage as the amine-based curing agent (B), the concrete crack repairing curable composition is a one-component type. Can be used. Examples of the modified curing agent include ketimine type amine block curing agents. Specific examples of ketimine type amine block curing agents include EpiCure H30 (manufactured by Japan Epoxy Resin Co., Ltd.), Adeka Hardener EH-235R (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like. In addition, this ketimine type amine block curing agent can be used in combination with other amine curing agents in a two-component concrete crack repairing curable composition.

<Repair method of concrete base material>
The concrete base material repair method according to the present invention is a repair method in water or in the air using the concrete crack repairing curable composition of the present invention prepared as described above.

  As such a repair method, a conventional surface coating method, filling method, injection method, or the like can be used. In this invention, it is preferable to repair the crack part of a concrete base material by the injection method.

  As described above, the curable composition for repairing concrete cracks of the present invention has its composition and viscosity, and in a preferred embodiment, the specific gravity of the composition is adjusted. It is not necessary to inject an object, and it is filled up to the details of the cracked part by natural fall (filling) using its own weight. In the case of using a pump, the composition can be injected even if the pump and the repair site are separated.

  Thus, the curable composition for repairing a concrete crack according to the present invention filled in the details of the crack portion of the concrete base material is cured at the crack portion of the concrete base material, and corrosion from the crack portion of the base material is prevented. It can be effectively prevented.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

In addition, Table 2 shows the raw materials used in this example.
[Examples 1-4, Comparative Examples 1-3]
<Method for preparing curable composition for repairing concrete cracks>
According to the composition shown in Table-3, I agent and III agent are previously stirred in separate containers to prepare homogeneous I agent and III agent.

Immediately before the test, a prescribed amount of II agent is placed in I agent, mixed with electric disperser and homogenized, then added with III agent, and further mixed with electric disper to make it uniform, and this is a curable composition. Test as a thing.
<Method for creating specimen>
1. As shown in FIG. 1, an upper surface 12a of a transparent acrylic plate 12 having a thickness of 5 mm (thickness) × 30 cm × 30 cm.
A rubber plate 14 of 1 cm (thickness) × 2 cm × 30 cm is bonded with a cyanoacrylate adhesive along the edge 12c of the rubber plate, and further a rubber plate 16 of 1 cm (thickness) × 6.5 cm × 30 cm is attached to the rubber plate 14. Is pasted to create a laminated plate 10. In this way, two bonded plates 10 are produced.

  2. As shown in FIG. 2, a 1 mm square and 3 cm long acrylic rod 18 is attached to a lower surface 12b of one bonded plate 10 to which the rubber plate 14 is not attached so as to be substantially perpendicular to the end 12c. Affixed with an acrylate adhesive to produce a bonded plate 10 ′.

3. The bonded plates 10 and 10 'obtained as described above are bonded to the end 12e of the lower surface 12b.
The transparent acrylic plates 12 and 12 are fixed with a double clip so that the acrylic rods 18 are held between the two lower surfaces 12b. The end side 12d, the end side 12f, and the end side 12e are bonded to each other with a cyanoacrylate adhesive. In this way, the transparent acrylic plates 12 and 12 are bonded to each other only on the three sides, and the substantially bag-shaped gap portion 20 is formed in which the end sides 12c and the lower surface 12b are not bonded to each other. By forming in this way, the space | gap part 20 becomes a shape where a space | gap becomes narrow gradually as it goes to the end side 12e from the end side 12c.

4). Further, as shown in FIG. 4, between the rubber plates 16 and 16, 1 cm (thickness) × 2.5 cm × 4.5
A rubber plate 22 of 1 cm and a rubber plate 24 of 1 cm (thickness) × 4.5 cm × 30 cm are fixed with a cyanoacrylate adhesive to prepare a bonded plate 30 having an opening 26 as shown in FIG.

5. A hot-melt adhesive (vinyl acetate resin-based adhesive (Hakumi Co., Ltd.)) that melt-bonds the laminated plate 30 thus prepared to an iron plate 32 of 10 cm × 30 cm × 3.2 mmt as shown in FIG. The test body 40 is prepared by fixing using a).
<Injection test method>
1. As shown in FIGS. 6 and 7, the specimen 40 prepared above is placed in a plastic container 50 having a depth of 40 cm, and a lead weight (not shown) is placed and fixed on the iron plate 32 so as not to float when the water is stretched.

  2. One in which a polyethylene funnel 44 is inserted into one of injection tubes 42 made of a transparent vinyl chloride resin is prepared. The injection tube 42 is inserted to the bottom of the opening 26 of the test body 40, and 1 m from the upper surface of the test body 40. The funnel 44 is fixed by fixing means (not shown) so as to have a height.

  3. Further, a drainage tube 46 made of a transparent vinyl chloride resin is installed in the opening 26 in order to discharge water when the resin is injected. The opening 26 is closed with an acrylic plate 48 using a hot melt adhesive. The acrylic plate 48 is provided with two through holes, and the injection tube 42 and the discharge tube 46 are disposed on the water surface through the through holes.

  4). As shown in FIG. 7, water is filled in a plastic container 50 having a depth of 40 cm in which the test body is installed to make the water full (water depth of about 40 cm), and water is filled in the gap 20 and the opening 26 of the test body 40. . The drainage tube 46 provided in the opening 26 is installed so as to come out above the water surface.

  5. The curable composition to be tested is poured into a funnel 44 connected to the injection tube 42 and dropped by gravity, and the curable composition is injected into the test body 40. When the curable composition of the funnel 44 is reduced, it is added as appropriate so that the funnel 44 is always filled with the curable composition. The injection is terminated when the funnel composition no longer decreases.

6). After the curable composition is cured, the specimen 40 is pulled up and the injection fluidity / fillability of the curable composition is evaluated according to the following evaluation method. The results are shown in Table-4.
<Evaluation method>
1. Injection fluidity of curable composition The surface area observed from the side surface of the test body 40 (upper surface of the transparent acrylic plate 12) was evaluated. Specifically, as shown in FIG. 8, a calibration curve for evaluation is drawn in accordance with the inclination of the cured product substantially at the center of the specimen, the height in contact with the edge 12 c is defined as “edge height”, and the edge With the height in contact with 12e as the “injection port height”, the injection area of the curable composition filled in the gap 20 is calculated by the following formula. The injection fluidity of the curable composition was evaluated from the area value.

Formula: Injection area of curable composition = [(edge height + injection port height) × 30 cm] / 2
2. Fillability of curable composition The test body 40 is disassembled, and the thickness of the cured product filled on the end side 12e side of the gap 20 is measured with a micrometer. Since the space | gap part 20 became narrow as the space | gap part 20 went to the edge 12e, it was judged that the filling property of a curable composition was excellent, so that the thickness of hardened | cured material was small.

  When the cured state of Comparative Example 3 was observed, the barium sulfate of pigment settled in the direction closer to the bottom, and the pigment was excessive, while the upper end portion was almost free of pigment. Thus, since the composition of Comparative Example 3 has no homogeneity, there is a practical problem in using it as a curable composition for repair.

FIG. 1 is a diagram showing a state of creating a test body used in the examples. FIG. 2 is a diagram illustrating a creation state of a test body used in the example. FIG. 3 is a diagram showing a state of creating a test body used in the examples. FIG. 4 is a diagram showing a state of creating a test body used in the examples. FIG. 5 is a diagram showing a test body used in the examples. FIG. 6 is a view showing a state in which an injection tube and a discharge tube are installed on the test body. FIG. 7 is a schematic cross-sectional view when a curable composition is injected into a test body. FIG. 8 is a diagram showing the injection area when evaluating the injection fluidity of the curable composition.

Explanation of symbols

10, 10 'Laminated plate 12a Upper surface 12b Lower surface 12c, 12d, 12e, 12f End side 14, 16 Rubber plate 18 Acrylic bar 20 Gap portion 22, 24 Rubber plate 26 Opening portion 30 Laminated plate 32 Iron plate 40 Test body 42 Injection Tube 44 Funnel 46 Discharge tube 48 Acrylic plate 50 Plastic container

Claims (7)

(A) a liquid epoxy resin having a viscosity of 800 to 30,000 mPa · s / 25 ° C.,
(B) an amine curing agent,
(C) a silane coupling agent,
(D) a pigment having a specific gravity of 2 to 3, and (E) (e-1) an epoxy group-containing reactive diluent having a viscosity of 10 to 5000 mPa · s / 25 ° C. and / or (e-2) a liquid hydrocarbon resin. A curable composition for repairing concrete cracks, comprising:
The curable composition for repairing concrete cracks, wherein the pigment (D) is contained in an amount of 10 to 40% by volume in 100% by volume of the composition. ^{2. The} curable composition for repairing concrete cracks according to claim 1, wherein the specific surface area of the pigment (D) is 4 m ² / g or less. Equivalent ratio (b / g) of epoxy equivalent (a) (g / equiv) of liquid epoxy resin (A) to active hydrogen equivalent (b) (g / equiv) of amino group of amine-based curing agent (B) The curable composition for concrete crack repair according to claim 1 or 2, wherein a) is 1.0 or less. Equivalent ratio (b / g) of epoxy equivalent (a) (g / equiv) of liquid epoxy resin (A) to active hydrogen equivalent (b) (g / equiv) of amino group of amine-based curing agent (B) The curable composition for repairing concrete cracks according to claim 1 or 2, wherein a) is 0.8 or less.   The liquid epoxy resin (A) is a bisphenol type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a phenol novolac type epoxy resin, a cresol type epoxy resin, a dimer acid-modified epoxy resin, an aliphatic epoxy resin, an alicyclic ring. The curable composition for repairing concrete cracks according to claim 1, wherein at least one selected from the group consisting of a group epoxy resin and an epoxidized oil-based epoxy resin is selected.   The curable composition for repairing concrete cracks according to claim 1, wherein the viscosity of the curable composition for repairing concrete cracks is 10,000 mPa · s / 25 ° C. or less.   A method for repairing a concrete base material, comprising injecting the curable composition for repairing a concrete crack according to any one of claims 1 to 6 into a crack of the concrete base material.

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