KR20150032783A - Epoxy resin composition - Google Patents

Abstract

An epoxy resin composition contains a two or more functional epoxy resin (a) derived from high fatty acid or derivatives of the same; an epoxy resin (b) except for (a); a terminal end reactive butadiene acrylonitrile copolymer (c); and polyamide amine (d). According to the present invention, provided is an epoxy resin composition which has crack to be additionally repaired, and can protection concrete structure by a simple method of such as roller painting or brush painting. Moreover, the epoxy resin composition of the present invention has long term anti corrosion properties for such as seawater and adhesion to a wet surface of concrete, rebar, stainless plate, and corrosive surface.

Description

Epoxy resin composition < RTI ID = 0.0 >

The present invention relates to an epoxy resin composition having excellent flexibility.

Conventionally, concrete is widely used in many structures and facilities.

Recently, however, cracks in concrete structures have been a problem due to shrinkage due to drying of concrete, expansion or shrinkage accompanying changes in environmental temperature, swelling of reinforcing bars in concrete, and alkaline aggregate reaction. For example, in a concrete structure constructed at a place such as a beach, a river, a lake, or a facility using a large amount of seawater or fresh water, once a crack occurs in the concrete structure, seawater or fresh water intrudes from the crack So that the steel material buried in the steel is corroded, and as a result, a part of the concrete structure is peeled or collapsed.

Therefore, it is considered that a material capable of harvesting and protecting cracks occurring in concrete structures is required.

Also, concrete structures constructed in places such as beaches, rivers, lakes, etc. are often in a wet environment, so that such materials are also desired to be able to be applied to wet surfaces as well.

As a material for solving these problems, JP-A-11-21430 proposes an epoxy resin composition excellent in flexibility. However, the epoxy resin composition described in the above publication is not intended to be applied to a wet surface, and thus it could not be used under a humid environment.

Japanese Unexamined Patent Publication No. 59-84915 discloses a water-curable epoxy resin that can be applied to water or a droplet. However, since the epoxy resin composition described in the above publication is a putty-like composition, it can not be applied by a simple method such as roller coating and brush coating in construction.

Japanese Patent Application Laid-Open No. 11-21430 Japanese Patent Application Laid-Open No. 59-84915

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a concrete structure which is excellent in adhesion to a wet surface of a concrete structure as well as a dry surface of a concrete structure, It is another object of the present invention to provide a composition excellent in flexibility which is capable of preventing the deterioration of concrete structures.

The present invention adopts the following means to solve such a problem.

That is, the epoxy resin composition of the present invention

(B) a bifunctional or higher functional epoxy resin derived from a higher fatty acid or a derivative thereof,

The epoxy resin (b) other than the above (a)

The terminal reactive butadiene acrylonitrile copolymer (c) and

The polyamide amine (d)

Lt; / RTI >

The epoxy resin composition preferably contains at least a modified alicyclic polyamide amine (d1) as the polyamide amine (d).

The epoxy resin composition preferably contains a polyamide amine (d2) obtained by modifying polyoxyalkylene polyamine with polycarboxylic acid as the polyamide amine (d).

In the epoxy resin composition, it is preferable that the bifunctional or more epoxy resin (a) is a castor-modified epoxy resin. The epoxy resin composition preferably contains 0.2 to 5% by mass of the terminal reactive butadiene acrylonitrile copolymer (c) in terms of solid content.

The epoxy resin composition preferably further contains a tertiary amine (e).

The epoxy resin composition preferably further contains a silane coupling agent (f).

It is preferable that the epoxy resin composition further contains a pigment (g).

In the epoxy resin composition, it is preferable that the pigment (g) is an acicular pigment (g-1) and / or a hollow spherical pigment (g-2).

The epoxy resin composition preferably further contains a fiber (h).

In the epoxy resin composition, it is preferable that the fiber (h) is a vinylon fiber.

The anticorrosive coating composition of the present invention is composed of the above epoxy resin composition.

A preferred use of the anticorrosive coating composition is for wet surface application.

The method of repairing or reinforcing a concrete structure of the present invention is a method of repairing or reinforcing a concrete composition by applying the anticorrosive coating composition on the surface of the concrete structure and curing the anticorrosive coating composition.

The method of preventing the falling of the concrete structure of the present invention is a method of anti-foaming in which the epoxy resin composition is coated on the surface of the concrete structure and then the epoxy resin composition is cured.

According to the present invention, it is possible to provide an epoxy resin composition capable of being harvested in cracks and capable of protecting a concrete structure by a simple method such as roller coating and brush coating on a wet surface.

In addition, the epoxy resin composition of the present invention also has long-term anticorrosion properties against seawater and adhesion to concrete wet surfaces, reinforcing bars, steel plates and rusty surfaces.

Furthermore, since the epoxy resin composition of the present invention can be made into a solvent-free type, it is excellent in terms of safety and hygiene of a worker and natural environment.

[Epoxy resin composition]

The epoxy resin composition of the present invention comprises

(B) a bifunctional or higher functional epoxy resin derived from a higher fatty acid or a derivative thereof,

The epoxy resin (b) other than the above (a)

The terminal reactive butadiene acrylonitrile copolymer (c) and

The polyamide amine (d)

Lt; / RTI >

(F), pigment (g) and fiber (h) as optional components and further contains other components as long as the effects of the present invention are not impaired .

≪ bifunctional or higher functional epoxy resin derived from higher fatty acid or derivative thereof (a)

The bifunctional or higher functional epoxy resin (a) derived from a higher fatty acid or a derivative thereof is blended so as to give an elongation to the cured product by increasing the distance between the crosslinking points of the epoxy resin cured product. Such an epoxy resin is obtained by subjecting a functional group having a plurality of higher fatty acids or derivatives thereof as a precursor to a chemical reaction and introducing an epoxy group into the higher fatty acid. The term "higher fatty acid" as used herein refers to an aliphatic carboxylic acid having 8 or more carbon atoms, preferably 12 or more carbon atoms. As the derivative, triglyceride, which is an ester of a higher fatty acid and glycerin, is preferably used.

As the bifunctional or higher functional epoxy resin (a) derived from a higher fatty acid or a derivative thereof, for example, an epoxy resin obtained by oxidizing a double bond of a higher fatty acid or a derivative thereof can be used. Specific examples of the epoxy resin obtained by such a method include a linseed oil modified epoxy resin obtained by oxidizing a double bond of linseed oil mainly composed of triglyceride of linoleic acid which is an unsaturated fatty acid.

And those obtained by a method in which a higher fatty acid or its derivative has a hydroxyl group as a glycidyl ether can also be used. Specific examples of the epoxy resin obtained by such a method include a castor-modified epoxy resin obtained by glycidylating castor oil containing triglyceride of ricinoleic acid, which is a hydroxycarboxylic acid, as a main component.

And those obtained by a method in which a higher fatty acid having a plurality of carboxyl groups is used as the glycidyl ether may also be used. Specific examples of the epoxy resin obtained by this method include dimer acid-modified epoxy resins which are glycidyl esters of dimer acid (a mixture mainly comprising dimer of linoleic acid), which is a polycarboxylic acid.

Further, products obtained by reacting these glycidyl ether compounds and glycidyl ester compounds with polyepoxy compounds such as bisphenol A glycidyl ether can also be preferably used.

Of these, a castor-modified epoxy resin is particularly preferable from the viewpoint of improving the flexibility of the composition.

Examples of the bifunctional or higher functional epoxy resin derived from such a higher fatty acid or a derivative thereof include Erisys (R) GE-35 (available from CVC Thermoset Specialties), Heroxi (R) 505 (Manufactured by Ai Japan Limited) or ACR epoxy R-1353 (manufactured by A-Seo Aluminum Co., Ltd.) can be used. (R) GE-120 (manufactured by CVC Thermoset Specialties), Epikote (R) 871, Epikote (R) 872 (manufactured by Yucca Shell Epoxy Co., Ltd.) YD-171, Ephoto (R) YD-172 (manufactured by Toto Hoso Co., Ltd.) and HEROXY (R) 71 (manufactured by A · C · i · Japan Limited) can be used. Epodil (R) 759 (manufactured by CVC Thermoset Specialties), which is a glycidyl ether having 12 to 14 carbon atoms, can also be used. Further, (R) of the trade name indicates a registered trademark or the like (the same applies to (R) described later).

In the epoxy resin composition of the present invention, these bifunctional or higher functional epoxy resins may be used singly or in combination of two or more.

The blending amount of the bifunctional or higher functional epoxy resin (a) derived from the higher fatty acid or its derivative in the epoxy resin composition of the present invention is not particularly limited, but is preferably from 2 to 12 mass% in terms of solid matter, more preferably from 3 to 10 mass% % Is more preferable. If it is more than 12% by mass, anticorrosiveness and adhesion may be lowered. If it is less than 2% by mass, the flexibility tends to be lowered. In the present invention, the blending amount in terms of solid content means the mass ratio of the solid content of each component to the mass of the solid component contained in the epoxy resin composition. The solid content means non-volatile matter excluding volatile substances such as solvents.

≪ Epoxy resin (b) other than the above (a)

As the epoxy resin (b) other than the above (a), for example, a non-tar epoxy resin described in JP-A-11-343454 and JP-A-10-259351 can be used.

Examples of the epoxy resin (b) include a polymer or an oligomer containing two or more epoxy groups in the molecule, and a polymer or oligomer produced by a ring-opening reaction of the epoxy group. Examples of the epoxy resin include epoxy resins such as bisphenol epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, phenol novolac epoxy resin, cresol epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, And an epoxy resin such as an epoxy resin. Among them, a bisphenol-type epoxy resin is preferred, and moreover, a bisphenol A-type or F-type epoxy resin is preferable, and a bisphenol A-type epoxy resin is particularly preferably used. When a bisphenol-type epoxy resin is used, a coating film having excellent adhesion can be formed.

Examples of such epoxy resins include bisphenol A type epoxy resins (bisphenol A diglycidyl ether type), bisphenol AD epoxy resins, epichlorohydrin and bisphenol F (4,4'-methylene bisphenol) Epoxy phenol-3 ', 4'-epoxyphenylacetoxy methane, etc., epichlorohydrin-bisphenol A epoxy resin, epoxy-novolac resin An aliphatic epoxy resin having a structure in which epichlorohydrin is reacted with an aliphatic divalent alcohol, epichlorohydrin and tri (hydroxyphenyl) methane di-condensation polymerization A polyfunctional epoxy resin having a reacted structure, and the like.

Examples of the bisphenol A type epoxy resin which is particularly preferably used include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A, propylene oxide diglycidyl ether, and other bisphenol A diglycidyl ether.

In the epoxy resin composition of the present invention, these epoxy resins may be used singly or in combination of two or more kinds. When two or more kinds of epoxy resins are used in combination as described above, the average molecular weight and the epoxy equivalent of the epoxy resin are all expressed by their average values.

The epoxy resin preferably has a liquid to solid phase at room temperature (15 to 25 DEG C, the same applies hereinafter), and its epoxy equivalent is usually 150 to 1,000 g / equiv, preferably 150 to 600 g / equiv, Is from 180 to 500 g / equiv.

The average molecular weight and the like of such an epoxy resin are not uniformly determined depending on paint curing conditions (for example, room temperature drying painting or baking painting) of the resulting paint, but the average molecular weight thereof is usually from 350 to 20,000, To 15 Pa 占 퐏 / 25 占 폚, and the epoxy equivalent is usually in the above range. Here, the average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatograph).

As typical examples of the epoxy resin, NPEL-128 (bisphenol A diglycidyl ether, manufactured by NAN YA PLASTICS CORPORATION, epoxy equivalence of 180 to 190, viscosity of 12,000 to 15,000 cPs / 25 ° C) (R) YDF-170 (general name: bisphenol A diglycidyl ether, manufactured by Shell Co., Ltd., epoxy equivalent of 180 to 190, viscosity of 12,000 to 15,000 cPs / Epoxy equivalent weight: 160 to 180, viscosity: 2,000 to 5,000 cPs / 25 占 폚), Prep (R) 60 (manufactured by Toray Industries, 280, viscosity about 17,000 cPs / 25 占 폚), Epikote (R) 828X-90 (bisphenol A diglycidyl ether xylene solution, manufactured by Shell Co., ) Epikote (R) 1001X-75 (generic name: Bisphenol A type epoxy xylene solution, manufactured by Shell Co., Ltd., epoxy equivalent weight: about 282) , Manufactured by Shell Co., Ltd., epoxy equivalent: about 633). (R) YD-134 (general name: bisphenol A type epoxy, manufactured by Toto Chemical Industry Co., Ltd., epoxy equivalent: 230 to 270) may be used. Epikote (R) 1001 (trade name: bisphenol A type epoxy, manufactured by Shell Co., Ltd., epoxy equivalent: 450 to 500) which is solid at room temperature. The epoxy resin composition of the present invention may contain only one kind of these epoxy resins, or may contain two or more kinds of these epoxy resins.

The blending amount of the epoxy resin (b) in the epoxy resin composition of the present invention is not particularly limited, but is preferably 15 to 35% by mass, more preferably 20 to 30% by mass in terms of solid content. If it is more than 35% by mass, flexibility may be lowered. When the amount is less than 15% by mass, the anticorrosiveness and adhesiveness tend to be lowered.

≪ Terminal reactive butadiene acrylonitrile copolymer (c) >

Examples of the terminal reactive butadiene acrylonitrile copolymer (c) include those having an acrylonitrile polybutadiene skeleton in the main chain and functional groups reacting with the epoxy group at the terminals, such as an amino group, a carboxyl group and a hydroxyl group have.

The terminal reactive butadiene acrylonitrile copolymer (c) imparts flexibility to the epoxy resin composition, thereby improving the crack followability of the concrete. In addition, since the terminal reactive butadiene acrylonitrile copolymer (c) is inserted into the structural skeleton of the epoxy resin composition during the reaction curing process, the drawback of impairing the water resistance, which is a problem in the resin composition in which the non-reactive rubber component is blended Can be reduced.

The amount of the terminal reactive butadiene acrylonitrile copolymer (c) in the epoxy resin composition of the present invention is not particularly limited, but is preferably 0.2 to 5% by mass, more preferably 1 to 3% by mass in terms of solid content . If it is more than 5% by mass, viscosity may increase and workability may be lowered. If it is less than 0.2% by mass, flexibility tends to decrease.

Examples of such terminal reactive butadiene acrylonitrile copolymer (c) include "Hypro (R) ATBN 1300 × 16 (manufactured by CVC THERMOSET SPECIALTIES Co.)", "Hypro (R) ATBN 1300 × 42 (CVC THERMOSET SPECIALTIES Hypro (R) CTBN 1300 x 8 (manufactured by CVC THERMOSET SPECIALTIES Co., Ltd.) and Hypro (R) CTBN 1300 x 31 (manufactured by CVC THERMOSET SPECIALTIES Co., Ltd.) having a carboxyl group at the terminal .

A preferred type of such terminal reactive butadiene acrylonitrile copolymer (c) comprises a structural unit selected from the following formulas (Ia) to (Id) and an end group selected from the following formulas (IIa) to (IId).

(Ia-Id)

(Wherein R ^a represents a hydrogen atom or a methyl group, R ^b represents -COOH, -COOR ^c or -CONH ₂ , and R ^c represents an aliphatic group, preferably a methyl group)

≪ RTI ID = 0.0 > [IIa]

(Wherein R represents an alkylene group)

The proportion of the structural units represented by the formulas (Ia), (Ib) and (Ic) in the terminal reactive isocyanuric acid copolymer (c) is preferably 5 to 50 mass% The ratio of the structural units is preferably 1 to 30 mass%.

≪ Polyamide amine (d) >

The polyamide amine (d) is mainly produced by the condensation of a dimer acid and a polyamine, and has a first and a second amino group having reactivity in the molecule. The molar ratio of the dimer acid and the polyamine used in the condensation reaction, the ratio of the monomeric acid / dimeric acid / trimeric acid in the fatty acid composition, the kind of the polymer, the molecular weight, the viscosity, and the amine value of the polyamideamine produced by the number of functional groups.

Examples of commercially available products include Ancamide (R) 2353 (modified alicyclic polyamide amine manufactured by Air Products), Ancamide (R) 2396A (modified alicyclic polyamide amine, manufactured by Air Products) (Amine value: 300, 80-120 poise / 40 占 폚), Tomaide (R) 210 (amine value: 100, , Tomaide (R) 213A (polyamide adduct, amine value 85, xylene / butanol 50% solution), Tomaide (R) 2500 (amine value 330, 5-10 poise / (R) 100 (amine value 90, semi-solid), Vasadide (R) 115 (amine value: 30%), and the like, such as polyamide adduct, amine value 230, 75% solution of xylene / (A polyamide adduct, an amine value 125, a xylene / butanol 60% solution), and the like, such as Vasamide (R) 125 (amine value 345, 75-100 poise / 40 ° C) Above, (Amine 440, 5 to 10 poise / 25 占 폚) and Jenamide (R) 2000 (amine value 600, 10 to 25 poise / 25 占 폚) Lactamid (R) N-153 IM 65 (amine value 100, 65% solution of xylene / butanol), lacamide (R) TD966 (amine value 170, 60% solution of xylene / butanol) (Commercially available from Dainippon Ink and Chemicals, Inc.) and Sunmaride (R) TD973 (polyamine adduct, amine value 170, 60% solution of xylene / butanol) (Amine value 210, 500 to 700 poise / 40 占 폚), sunmide 占 316 (amine value 310, 90 to 110 poise / 40 占 폚), sunmide 占 2000 Polyamide (R) L-10-3 (amine value 100, semi-solid), polyamide L-55-3 (amine value 380, 9.5 ~ 25.5 poise / 20 占 폚) and the like (more, Sanyo And the like; Company). Examples of the polyamide amine obtained by modifying a polyoxyalkylene polyamine with a polycarboxylic acid include anchoramide (R) 910 (air) obtained by modifying diethylene glycol diaminopropyl ether with a dimer acid Ltd.) and the like.

Further, a copolymerized polyamide obtained by polycondensing two or more of the aforementioned polyamides-forming amines or acids and a polyamideimide (a reaction product of anhydrous trimellitic acid and an aromatic diamine) and the like can be given.

These polyamide amines may be used singly or in combination of two or more kinds.

These polyamide amine-based curing agents are available from N.V. And the viscosity at 25 ° C measured by the E-type viscometer at this time is in the range of 100 to 100,000 cPs, preferably 500 to 10,000 cPs, since it is excellent in handling property and coating property .

The polyamide amine (d) is preferably contained in the epoxy resin composition in an amount of 10 to 35 mass% in terms of solid content, more preferably 15 to 30 mass%. When the polyamide amine (d) is contained in such an amount, it is preferable from the viewpoints of flexibility, painting workability, and the like.

Among these polyamide amines (d), it is preferable to use the modified alicyclic polyamide amine (d1) from the viewpoint of the adhesion to the concrete wet surface. From the viewpoint of crack followability of concrete, it is preferable to use polyamide amine (d2) obtained by modifying polyoxyalkylene polyamine with polycarboxylic acid.

Examples of the modified alicyclic polyamide amine (d1) include ancamid (R) 2353 and ancamid (R) 2396A described above. Examples of the polyamide amine (d2) obtained by modifying a polyoxyalkylene polyamine with a polycarboxylic acid include ancamide (R) 910, which is a polyamide amine obtained by modifying the above diethylene glycol diaminopropyl ether with a dimer acid .

Use of a curing agent having a larger molecular weight than polyamine or the like as the polyamide amine (d) can provide an epoxy resin composition excellent in low temperature curability.

In addition to the polyamide amine (d), polyamine compounds conventionally known as amine curing agents such as epoxy resin curing agents, for example, aliphatic polyamines, modified aliphatic polyamines, alicyclic polyamines, Family polyamines, modified alicyclic polyamines, aromatic polyamines, modified aromatic polyamines and the like may be used in combination. Examples of the thermal latent curing agent include dicyandiamide and the like.

<Tertiary amine (e)>

When the epoxy resin composition of the present invention contains a tertiary amine (e), curing is preferably promoted.

Specific examples of the tertiary amine (e) include triethanolamine (N (C ₂ H ₅ OH) ₃ ), dialkylaminoethanol {[CH ₃ (CH ₂ ) _n ] ₂ NC ₂ H ₅ OH, (CH ₂ N (CH ₃ ) ₂ ] ₃ -), triethylenediamine [1,4-diazacyclo (2,2,2) octane], 2,4,6- C ₆ H ₅ OH}, Vasamin (R) EH30 (manufactured by Henkel Hakusui Co., Ltd.), and Ancamine (R) K-54 (manufactured by Air Products).

The tertiary amine (e) is preferably contained in an amount of 0.1 to 3.0% by mass, more preferably 0.2 to 1.0% by mass in terms of solid content in the epoxy resin composition.

It is preferable that the polyamide amine (d) is contained in an amount of 1 to 20 parts by mass based on 100 parts by mass (solid content) of the polyamide amine (d) from the viewpoints of curability and pot life.

&Lt; Silane coupling agent (f) &gt;

The silane coupling agent (f) usually has two kinds of functional groups in the same molecule. The silane coupling agent (f) contributes to the improvement of the adhesion to the inorganic base material and the decrease of the paint viscosity. The silane coupling agent (f) is represented, for example, by the formula X-Si (OR) ₃ . In the formulas, X represents a functional group or an alkyl group capable of reacting with an organic substance. Examples of the functional group capable of reacting with the organic substance include amino groups, vinyl groups, epoxy groups, mercapto groups, halogen groups, and groups formed in addition to groups in which a hydrocarbon group or an ether bond is interposed in the hydrocarbon group . OR represents a hydrolyzable group, and examples thereof include a methoxy group and an ethoxy group.

Specific examples of such a silane coupling agent include Silicone KBM-403 (? -Glycidoxypropyltrimethoxysilane, produced by Shin-Etsu Chemical Co., Ltd.) and Silane S-510 (manufactured by Chisso Corporation) .

 The silane coupling agent (f) is preferably contained in the epoxy resin composition in an amount of 0.2 to 3 mass% in terms of solid content, more preferably 0.5 to 2 mass%. By containing the silane coupling agent (f) in such an amount, the adhesion between the cured product of the epoxy resin composition and the surface of the concrete structure is improved, and even if the cured product is immersed in water for a long time, Corrosion can be effectively prevented. These effects are conspicuous when a silane coupling agent containing an epoxy group is added.

&Lt; Pigment (g) &gt;

The epoxy resin composition of the present invention may contain a pigment (g) if necessary. The pigment (g) is not particularly limited, and known coloring pigments, extender pigments, rust-preventive pigments and the like can be used. The pigment (g) may be spherical, acicular, or fibrous in shape depending on the shape thereof, and is generally classified in accordance with the difference in the aspect ratio, which is the ratio of the major axis to the minor axis of the particles.

Examples of the coloring pigments include inorganic pigments such as carbon black, titanium dioxide, red iron oxide, iron oxide, iron hydroxide and stearic acid, and organic pigments such as cyanine blue and cyanine green. The color pigments may be used singly or in combination of two or more kinds.

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

Examples of the anticorrosive pigment include, but are not limited to, zinc powder, a zinc alloy powder, a zinc phosphate compound, a calcium phosphate compound, an aluminum phosphate compound, a magnesium phosphate compound, a phosphorus acid anhydride compound, a calcium phosphite compound, It is preferably one or more selected from the group consisting of strontium phosphite-based compounds, aluminum tripolyphosphate-based compounds, molybdate-based compounds, cyanamide-based compounds, borate compounds, nitro compounds and composite oxides.

The coloring pigments, extender pigments, and anti-corrosive pigments may be used in any combination.

Such a pigment (g) is preferably contained in the epoxy resin composition in an amount of 25 to 50 mass% in terms of solid content, more preferably 30 to 45 mass%.

When the needle-shaped pigment (g-1) is used among the above-mentioned pigments (g), the mechanical strength such as crack resistance and impact resistance of the coating film can be improved.

Examples of the needle-shaped pigment (g-1) include wollastonite, sepiolite, chrysotile, amosite, tremolite and zeolite, Wollastonite is preferable from the viewpoints of improvement in strength, durability and water resistance. Specifically, NYAD325 (trade name, manufactured by NYCO Mineral, Walasunonite) can be mentioned. When such an acicular pigment (g-1) is blended, it is preferably contained in the epoxy resin composition in an amount of 2 to 25 mass% in terms of solid content, more preferably in an amount of 10 to 20 mass% .

Furthermore, among the above-mentioned pigments (g), the use of the hollow spherical pigment (g-2) is advantageous in terms of weight reduction and sagging.

Examples of the hollow spherical pigment (g-2) include pearlite, fly ash, resin hollow balloon and the like, among which hollow spherical particles such as pearlite are preferable.

The hollow spherical pigment (g-2) is not a hollow, but a complete or incomplete hollow, and contains a gas such as air having a low thermal conductivity, or a hollow portion in a vacuum state or a reduced pressure state. As the hollow spherical pigment (g-2), for example, ceramic balloons and plastic balloons can be used, and ceramic balloons are more preferable because they can be used even at high temperatures.

Examples of such ceramic balloons include glass balloons such as borosilicate type, silica balloons, shirasu balloons, fly ash balloons, zirconia balloons, alumina silicate balloons, sintered vermiculite balloons and pearl balloons. From the viewpoint of strength of the coating film surface, perlite balloons are preferable .

As the perlite balloons, those having an average particle size of 3 to 100 mu m and an average specific gravity of 0.2 to 0.8 can be preferably used. An example of a commercially available perlite balloon is Onyxell ON4150 (trade name, manufactured by KD Ceratech).

The hollow spherical pigment (g-2) is preferably contained in the epoxy resin composition in an amount of 0.2 to 5 mass% in terms of solid content, more preferably 0.3 to 3 mass%.

&Lt; Fiber (h) &gt;

The epoxy resin composition of the present invention may contain the fiber (h) if necessary.

Specific examples of the fiber (h) usable in the present invention include fibers such as glass fiber, carbon fiber, vinylon fiber, nylon, aramid, polypropylene, acrylic and polyester, cellulose fiber, steel and alumina fiber . These fibers (h) are used in the case of imparting anticorrosion property and film reinforcement property to concrete.

Among the fibers (h), vinylon fibers are preferable from the viewpoint of concrete anticaking property. An example of a commercially available vinylon fiber is Vinylon AA 1.8 dtex x 4 mm (manufactured by UNITICA CO., LTD.).

The fiber (h) is preferably contained in the epoxy resin composition in an amount of 0.3 to 3 mass% in terms of solid content, more preferably 0.5 to 2 mass%.

<Other ingredients>

In the epoxy resin composition of the present invention, a pigment dispersing agent, a leveling agent, an anti-sagging agent, a defoaming agent and the like may be used as needed to aid dispersion of the pigment (g). They are not particularly limited, and conventionally known ones can be used.

&Lt; Preparation of epoxy resin composition &gt;

The epoxy resin composition of the present invention can be prepared by mixing the above components.

The epoxy resin composition of the present invention can be suitably used as a two-component mixed epoxy resin composition. A preferred embodiment is a form in which a hardener containing the components (a) and (b) and the components (c) and (d) is mixed before use. When the epoxy resin composition of the present invention is used as a two-component mixed epoxy resin composition, the epoxy resin composition of the present invention can also be used in a method of curing by heat curing by appropriately selecting a curing agent.

Further, the liquid epoxy resin composition of the present invention can be used as a one-component epoxy resin composition by blending a thermosetting curing agent in addition to the components (a) and (b). In this case, it is mainly used for a method of hardening by heating.

When the epoxy resin composition of the present invention contains the above components (e) to (h) and this is used as a two-component mixed epoxy resin composition, the components (e) to (h) It may be contained in one. The fibers (h) may be prepared separately from other components and added after mixing components other than the fibers (h). Further, the two solutions may be prepared from components other than the fibers (h), and the fibers (h) may be added after mixing the two solutions before use.

&Lt; Use of the epoxy resin composition of the present invention &

The epoxy resin composition of the present invention is excellent in flexibility and can be harvested in cracks of concrete and the like and is excellent in adhesion to a wet surface of a concrete structure so that the wet surface of a concrete structure can be obtained by a simple method such as roller coating or brush coating Can be applied. In addition, the epoxy resin composition of the present invention has excellent long-term anticorrosive properties against seawater and adhesion to reinforcing bars, steel plates, and rusted surfaces.

Therefore, the epoxy resin composition of the present invention can be used as an anticorrosive coating composition such as a concrete structure, and can be effectively used as a anticorrosive coating composition for wet surface construction.

This type of coating composition is used, for example, by applying it to the surface of a structure such as a concrete structure and hardening it. In this manner, repair or reinforcement of concrete structures and the like can be performed.

When the epoxy resin composition of the present invention contains the fiber (h), the anticorrosive property of the concrete is enhanced. Therefore, the epoxy resin composition of the present invention containing the fibers (h) is applied to the surface of the concrete structure and then hardened, thereby preventing the concrete structure from peeling off.

Further, when the epoxy resin composition of the present invention contains the fiber (h) and further contains a large amount of the hollow spherical pigment (g-2), it can be suitably used as a section repairing material.

Further, when a large amount of silica sand is blended in the epoxy resin composition of the present invention, it can be suitably used as a resin mortar.

Furthermore, it is also possible to form a top coat by further coating an upper coat paint on the coat formed by using the epoxy resin composition of the present invention. In particular, when weatherability or aesthetics (color) of the organs are required, fluororesin-based or polyurethane-based top coatings are suitably used.

Example

[Examples 1 to 5, 7, Comparative Examples 1 to 4]

(Preparation of the subject)

Each of the raw materials shown in the &quot; Topic &quot; in Table 1 was mixed at a compounding ratio (mass ratio) shown in Table 1 and stirred with a high-speed disperser to prepare a subject used in Examples and Comparative Examples.

(Preparation of hardener)

Each of the raw materials shown in Table 1 as "curing agent" was mixed at a compounding ratio (mass ratio) shown in Table 1 and stirred with a high-speed disperser to prepare a curing agent for use in Examples and Comparative Examples.

(Preparation of epoxy resin composition)

Immediately before the test, the epoxy resin composition was prepared by mixing the above-prepared base and the curing agent in a mixing ratio (mass ratio) shown in Table 1 in a dispenser. This epoxy resin composition was provided in the following test.

The test results are shown in Table 2.

[Example 6]

The raw materials shown in Table 1 were mixed in the mixing ratios (mass ratio) shown in Table 1 and stirred with a high speed dispenser to prepare a base and a curing agent. The subject matter and the curing agent were mixed using a dispenser at a mixing ratio (mass ratio) indicated by a small amount in Table 1, and the fibers (h) shown in Table 1 were mixed at a mixing ratio (mass ratio) And mixed with an electric stirrer to prepare an epoxy resin composition. This epoxy resin composition was provided in the following test.

The test results are shown in Table 2.

The raw materials used in Examples and Comparative Examples are summarized in Table 3.

<Wet surface>

A concrete pavement board (substrate) of 300 mm x 300 mm x 60 mm specified in JIS A5371 was completely immersed in water at 23 DEG C for 24 hours and then pulled up from the water. The epoxy resin composition obtained by mixing the above-mentioned subject and curing agent adjusted to a temperature of 23 占 폚 immediately thereafter by the above-mentioned preparation method was applied to a concrete pavement plate with a short-side roller (manufactured by Otsuka Brush Co., Ltd.) based on 0.5 kg / Manufactured by Urethane group (trade name) Small roller short-haired length 6 mm size 4 inch part number 4S-C10) at a roller moving speed of 10 to 20 cm / s at an angle of about 45 degrees upward from the surface of the pavement plate , And from one end to the other end of the pavement plate was coated so as to evaluate the arrival property of the epoxy resin composition on the substrate and the slipperiness of the roller. Evaluation criteria are shown below.

A: It is possible to reach the substrate, and the roller did not slip during coating.

B: It is possible to arrive at the base material, but the roller slip occurred at the time of coating.

C: It was impossible to arrive for the equipment.

<Cracking Followability>

The crack follow-up test was carried out in accordance with JSCE-K532-2010 "Test method for crack follow-up of surface coating material" of Civil Engineering Society.

Mortar with a water / cement ratio of 50% and a sand / cement ratio of 3 was molded using a metal mold of 40 mm × 120 mm × 10 mm and cured for 24 hours at 20 ° C. and a relative humidity of 80% Deg.] To obtain a test substrate. The test substrate was then cured in water at a temperature of 20 ° C for 6 days. After the completion of the underwater curing, the test substrate was cured for 7 days at a temperature of 23 ° C and a relative humidity of 50%. A cut of 5 mm in depth was placed on the upper surface of the mold, that is, the side opposite to the surface to which the epoxy resin composition was applied, The substrate was cut in two.

The two divided substrates were placed on a 0.8 mm thick SUS304 plate, and the whole circumference of the side surface was covered with an adhesive tape and fixed. The unevenness adjustment material was applied along the cutting line in a manner that the unevenness adjustment material was put in a spatula. After the hardening, the unevenness adjustment material was polished using the abrasive paper No. 150 specified by JIS R 6252 to remove the excess unevenness adjustment material. The epoxy resin composition was coated with a brush with a film thickness of 600 쨉 m leaving 30 ㎜ at both ends with care so that the material did not flow into the cut surface, and the material was cured for 28 days at a temperature of 23 캜 and a relative humidity of 50%. In some test samples, a fluororesin paint (Fluorex topcoat, manufactured by Chukogyo Kogyo Co., Ltd.) was applied on the coating film of the epoxy resin composition to a thickness of 25 탆. In this way, a test body with a top and a test body without a top surface were prepared.

The following tests were conducted. After the accelerated weathering test, the test specimen provided with the SUS304 plate was subjected to the weather resistance test for 1,500 hours under the cycle A condition using a xenon arc lamp type weather resistance tester (Atlas Material Testing Solutions Ci-4000) according to JSCE-K511 , And the test was carried out in the same manner as in the standard test body.

The test specimens were fixed so as to allow clearance between the chucks and subjected to a test of RTC-1350A manufactured by A & D Co., Ltd. at a constant speed of 5 mm / min.

The elongation at which the surface coating material was in any one of the following states was measured from the tensile stress-elongation curve.

· When the surface covering material is broken

· When the breakage of a part of the surface covering material is confirmed with the naked eye

· When the maximum tensile strength is shown on the stress-strain curve

&Lt; Adherence (standard state) &gt;

The adhesion test was carried out in accordance with the JSCE-K531-2010 "Test Method for Bond Strength of Surface Coating Material" of Civil Engineering Society.

Mortar with a water / cement ratio of 50% and a sand / cement ratio of 3 was molded using a metal mold of 70 mm × 70 mm × 20 mm and cured for 24 hours at 20 ° C. and a relative humidity of 80% To obtain a test substrate. The test substrate was then cured in water at a temperature of 20 ° C for 6 days. After completion of the underwater curing, the substrate for test was cured for 7 days at a temperature of 23 캜 and a relative humidity of 50%, and the lower surface of the substrate during polishing was sufficiently polished using a polishing pad 150 specified by JIS R 6252.

An epoxy resin composition was coated on the test substrate in a film thickness of 600 mu m and cured for 28 days at a temperature of 23 DEG C and a relative humidity of 50%. The following tests were conducted using the test substrate with the coating film as a test body.

The test specimen was placed horizontally in an atmosphere of a temperature of 23 DEG C and a relative humidity of 50%, and the epoxy resin composition coating film was coated with an adhesive. The upper jig for tensile strength of 40 mm in width and 40 mm in length was slowly put up and gently rubbed. Kg of the weight was raised to wipe out the adhesive which had been released to the periphery, and was allowed to stand for 24 hours. The weights were removed and a 1 mm deep incision was made in the square on the specimen along the periphery of the upper jig for tensile gluing to the specimen.

The maximum tensile load T (N) was obtained by applying a tensile force in the vertical direction to the test piece surface with RTC-1350A manufactured by A & D Co., Ltd. using a forced jig for lower tensile force and a forced damper. The test was carried out at a load speed of 1,500 N / min until fracture. The bond strength was determined by the following equation. The test was carried out twice.

&Quot; Substrate breakdown &quot; in Table 2 indicates that when the adhesion strength of the coating film was measured, the adhesion strength exceeded the strength of the concrete substrate, indicating that the concrete substrate was broken.

&Lt; Adherence (wet state) &gt;

Immediately after the test substrate used in the above adhesion test was completely immersed for 6 days and then pulled up, an epoxy resin composition was applied to the test substrate to a film thickness of 600 mu m, and the adhesion strength was determined in the same manner as in the adhesion evaluation test.

<Punching Test>

The punching test was conducted on the epoxy resin composition of Example 5 in accordance with JSCE-K533-2010 &quot; Punching Test Method of Surface Coating Applied to Prevent Peeling of Concrete Fragments &quot;

The test specimens were subjected to a test using 300 specimens (400 mm x 600 mm x 60 mm) of one type of U-shaped upper lid (lid) specified in JIS A5372. The core of the U-shaped lid was core-cut with a core drill for concrete in the shape of a circle having a diameter of 100 mm. The core withdrawing direction was a direction from the back surface (the surface opposite to the surface to which the epoxy resin composition was applied (hereinafter referred to as a construction surface)) to the installation surface, and the depth from the back surface was 55 mm.

Surface treatment was carried out using a diamond cup wheel on the construction surface. The U-shaped lid was immersed in water maintained at 23 DEG C for 24 hours. The upper part of the U-shaped lid was lifted from the water, and the water level of the surface of the U-shaped lid was removed by a mop while the lower 30 mm of the U-shaped lid was soaked. Within 5 minutes after the upper part of the U-shaped lid was lifted from the water, the epoxy resin composition was applied to a square area of 400 mm on one side of the center of the construction surface with a film thickness of 1.0 mm. The construction was carried out with the lower 30 mm of the U-shaped lid immersed in water. Curing was carried out at 23 캜 for 28 days in a state where the bottom 30 mm of the U-shaped lid was immersed in water to obtain a specimen.

The test was carried out by the following test method using RTC-1350A (manufactured by A & D Co., Ltd.).

Three sets of specimens produced under the same conditions were used as one set. The specimen was set on the spot at a span of 450 mm with the coated film side of the epoxy resin composition facing downward, and it was confirmed that no spot came into contact with the coating film of the epoxy resin composition. And a load was applied to the central portion of the core by sandwiching the ball so that the load would be evenly applied to the vertical portion. Loads and displacements were recorded during the loading process. The concrete was first loaded at a speed of 1 mm / min until the concrete in the core part was destroyed. Then, when the initial peak was confirmed, it was loaded at 5 mm / min, and the maximum load appeared thereafter. The load was terminated when the load decreased to about 50% of the maximum load after the maximum load was measured.

At the angular displacements of 10 mm, 20 mm, and 30 mm, the load was temporarily stopped, the peeling range was marked on the specimen, and the photograph was recorded. The test was terminated at the stage when the final load-bearing capacity was confirmed. A load - displacement curve was constructed from the data of the load and the displacement stroke obtained in the test, and the maximum load at a displacement of 10 mm or more was obtained. The maximum load was calculated for three specimens and the average value P was calculated. The mean value P was rounded to the second decimal place.

<Salt spray test>

A sandblasted steel sheet (Sa2.5) having a length of 150 mm, a width of 70 mm and a thickness of 2.3 mm, a hot rolled galvanized steel sheet having a length of 150 mm, a width of 70 mm and a thickness of 2.3 mm, a length of 150 mm, a width of 70 mm and a thickness of 2.0 mm An epoxy resin composition was coated on an SUS304 steel sheet to a thickness of 600 mu m and dried at a temperature of 23 DEG C and a relative humidity of 50% for 28 days to prepare a test plate.

A scratch was applied to each test plate, followed by a neutral salt spray test (35 ° C) in accordance with JIS K5600 7-1, using STP-90V-3 manufactured by Suga Tester Co., Ltd.

The test time was 2,000 hours. After the test, the appearance of the test plate, such as swelling and contamination, and the creep of corrosion from scratch were observed.

The case where the test plate was observed for expansion, contamination or corrosion from scratch was evaluated as &quot; abnormal &quot;, and the case where the test plate was not observed for expansion, contamination and corrosion from scratch was evaluated as &quot; no abnormality &quot;.

Claims (15)

(B) a bifunctional or higher functional epoxy resin derived from a higher fatty acid or a derivative thereof,
The epoxy resin (b) other than the above (a)
The terminal reactive butadiene acrylonitrile copolymer (c) and
The polyamide amine (d)
And an epoxy resin. The method according to claim 1,
Wherein the polyamide amine (d) contains at least a modified alicyclic polyamide amine (d1). 3. The method of claim 2,
(D2) obtained by modifying a polyoxyalkylene polyamine with a polycarboxylic acid as the polyamide amine (d). The method according to claim 1,
Wherein the bifunctional or more epoxy resin (a) is a castor-modified epoxy resin. The method according to claim 1,
And 0.2 to 5% by mass of the terminal reactive butadiene acrylonitrile copolymer (c) in terms of solid content. The method according to claim 1,
Further comprising a tertiary amine (e). The method according to claim 1,
Further comprising a silane coupling agent (f). The method according to claim 1,
Further comprising a pigment (g). 9. The method of claim 8,
Wherein the pigment (g) is an acicular pigment (g-1) or a hollow spherical pigment (g-2). The method according to claim 1,
Further comprising a fiber (h). 11. The method of claim 10,
Wherein the fiber (h) is a vinylon fiber. An anticorrosive coating composition comprising the epoxy resin composition according to any one of claims 1 to 11. 13. The method of claim 12,
Wherein said anticorrosive coating composition is for wet surface construction. A method for repairing or reinforcing a concrete structure in which the anticorrosion coating composition according to claim 12 is applied to a surface of a concrete structure and then the anticorrosive coating composition is cured. A method for preventing the fall of a concrete structure in which the epoxy resin composition according to claim 10 or 11 is applied to a surface of a concrete structure and then the epoxy resin composition is cured.