KR101336976B1 - Water-soluble epoxy resin composition and method of forming a coating film using the same - Google Patents

Abstract

The present invention relates to a water soluble epoxy resin composition for preventing salt attack and neutralization of concrete, and a method of forming a coating film using the same. The water soluble epoxy resin composition improves chemical properties including adhesive resistance, solvent resistance, and water resistance, and mechanical properties including promotion weathering resistance and shock resistance of a concrete structure. Also, the salt attack and neutralization of the concrete structure is prevented using the water-soluble epoxy resin composition, and the durability of the concrete structure is improved. An environmentally friendly resin coating layer without volatile organic compounds and harmful components is obtained using the water-soluble epoxy resin composition without a volatile organic solvent.

Description

Water-Soluble Epoxy Resin Composition and Method of Forming a Coating Film using the Same}

The present invention relates to a water-soluble epoxy resin composition for preventing concrete salting and neutralization, and a method of forming a coating film using the same, using the water-soluble epoxy resin composition, having excellent adhesive resistance to concrete structures, and having excellent solvent resistance and water resistance. And excellent mechanical properties of accelerated weather resistance and impact resistance. In addition, by applying the water-soluble epoxy resin composition to prevent salt and neutralization of the concrete structure can improve the durability of the concrete structure, and the resin composition does not use a volatile organic solvent, it can be eco-friendly water without volatile organic compounds or harmful components Can provide a coating.

Specifically, the present invention is chemically eroded by structures, harbor structures, underground structures, exposed materials, structures that have been neutralized for a long life, bridge structures subjected to wet and dry repetitive action, calcium chloride and SOx, NOx, etc. under various marine environments. The present invention relates to a water-soluble epoxy resin composition for preventing concrete salting and neutralization to prevent salting, contamination and neutralization of air or underwater concrete structures, such as generated structures, and is environmentally friendly and free of salt, pollution, And it is excellent in the anti-neutralization ability, and also excellent adhesion to concrete structures.

Currently, a method of coating a resin with a finishing agent for protecting and strengthening various surfaces such as concrete and metal and improving the environmental structure is mainly applied. However, concrete structures are deteriorated due to salts or chlorides present in the brine, ultraviolet rays, external pressure, sulfates in the water, carbon dioxide, and water.

Concrete structures initially produce strong alkaline calcium hydroxide with a pH of 12-13 when the main material cement is mixed with water, so that the reinforcing steel in the concrete is surrounded by alkaline poisoning and does not rust. If there is no coating film on the surface of the concrete structure, harmful compounds such as chloride are easily attached to the porous concrete surface, and easily penetrates because they easily fall off by rain or wind.

In addition, the chloride rapidly penetrates in the weak parts such as construction joints and joints in which the concrete composition is unevenly distributed in the concrete structure, and the accumulation increases, thereby prematurely corroding the concrete and reinforcing bars. Moreover, chloride attracts large amounts of moisture, causing winter freezing. Even without these defects in concrete, the amount of chloride attached to the concrete surface is known to move inside.

In addition, the carbonation reaction of carbon dioxide and concrete, acid rain from outside, polluted air, carbon dioxide, sulfur dioxide, salts, etc., the neutralization proceeds slowly to deteriorate the concrete structure and eventually shorten the life of the concrete structure. Therefore, it is known that it is useful for concrete structures to initially form a coating for harmful compounds.

In order to form a coating film, the resin composition used in concrete must have impregnation resistance, water resistance, alkali resistance suitable for the properties of concrete, and excellent performance as a coating film such as abrasion resistance, accelerated weather resistance, and the like. In addition to chemical resistance, mechanical strengths such as water tightness, abrasion resistance, and high hardness are required. In the case of a resin composition having such physical properties, it is difficult to attach various harmful compounds such as chloride to the surface of the coating film, and it is easily washed off by rain water. . Furthermore, since the chloride ion permeability of the coating film having such conditions is also extremely small, there is almost no internal penetration of chloride ions.

In general, paint resins used in concrete structures used at home and abroad are mainly composed of metal powders and adhesives, and ceramic-based anticorrosive paints.

In addition, epoxy resins have excellent water resistance, adhesiveness, and chemical resistance, and are widely used as adhesives and coating agents for structures, and resins most commonly used as binders for epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, Polyfunctional epoxy resins, novolac epoxy resins and the like.

In the case of using the epoxy resin, while excellent in chemical resistance, mechanical properties, etc., there is a problem of causing environmental pollution, deterioration of working environment, explosion, etc. due to the organic solvent used for the injection of the epoxy resin, overcome To this end, water-soluble epoxy resins have been studied until now.

In addition, in the case of the water-soluble resin, a product in which a general chemical resin is applied in addition to the epoxy resin produced in Korea is mainly used, but also its shape is white and the harmony of concrete and appearance is greatly inferior. It is reported that the water dispersibility does not have the perfect hydrophilicity, and thus, it is not reported to bring about the effect of maintaining or increasing the original function of the resin at the same time as the neutralization of such toxicity. This does not apply to the situation.

Korean Patent No. 0153086 discloses an anticorrosive coating composition comprising an inorganic powder including cement, a synthetic polymer dispersion, a fatty acid-based aqueous dispersion and a nitrite-based metal salt, and Korean Patent Publication No. 2009-0108357 , Steel powder, epoxy resin, and steel rust preventive agent comprising a blended water. Patent No. 0661494 discloses a polymer coating composition for preventing concrete neutralization and salt, and has a main material and a hardening material. In Patent No. 526418, an organic compound is applied to concrete to protect concrete, and protection of concrete is disclosed. However, such a resin composition has a problem in that water resistance, rust prevention performance, durability, and in particular, sufficient adhesion resistance with steel and concrete are not secured.

The present invention relates to a water-soluble epoxy resin composition for preventing concrete salting and neutralization, and a method of forming a coating film using the same, using the water-soluble epoxy resin composition, having excellent adhesive resistance to concrete structures, and having good solvent resistance and water resistance. It is possible to improve excellent mechanical properties of physical properties, accelerated weather resistance and impact resistance.

In addition, by applying the water-soluble epoxy resin composition to prevent salt and neutralization of the concrete structure can improve the durability of the concrete structure, the resin composition does not use a volatile organic solvent, there is no volatile organic compound or harmful components It is to provide a resin coating film.

According to an aspect of the present invention,

Water-soluble epoxy resin which adds the polyether glycol represented by General formula (1) of the number average molecular weight in the range of 200-30000 to the epoxy oligomer which has an epoxy equivalent of 100-1000 g / eq;

[Formula 1]

H- (O- (CH2) m) x-0H

(In Formula 1, m is an integer of 2 to 4, x is an integer satisfying the number average molecular weight.)

Organo silicon-containing compounds represented by Formula 2;

(2)

(In Formula 2, R1 is selected from aminoethyl group, vinyl group, methyl group, glycidoxypropyl group, methacryloxybutyl, methacryloxypropyl, propyl substituted with fluorine, ethyl group substituted with fluorine, hydrogen group, R2 to R4 may be selected from an ethoxy group, a butoxy group, a hydrogen group and a methoxy group, respectively, and R1 to R4 are not all hydrogen.)

Glycidyl ether-based diluents; Water dispersible curing agents; And a solvent comprising at least one selected from the group consisting of water, celluloid, alcohol, glycol ether, ketone, and carbitol; It provides a water-soluble epoxy resin composition for preventing concrete salt and neutralization.

Here, the epoxy oligomer is characterized in that at least one selected from glycidyl ether type epoxy oligomer, glycidyl ester type epoxy oligomer, bisphenol A type epoxy oligomer, bisphenol F type epoxy oligomer.

And, the glycidyl ether diluent is butyl glycidyl ether, phenyl glycidyl ether, aliphatic glycidyl ether, carboxylic glycidyl ether, hexanediol diglycidyl ether, ethoxyglycidyl ether , Polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and 1-4-butanediol diglycidyl ether.

The water dispersible curing agent is selected from the group consisting of acyclic polyamines, aliphatic polyamines, aromatic polyamines, and amine adducts.

In addition, the compound of Formula 2 is 3-glycidoxypropyltriethoxysilane, 3-aminopropyltributoxysilane, 3-methacryloxybutylsilane, 3-mercaptopropyltriethoxysilane, 3-mercapto Propylmethoxysilane, 3-methacryloxyethoxysilane, 3-methacryloxybutylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, vinylmethyldimethoxysilane, methyltriisopro And at least one member selected from foxysilane, methyltriacetoxysilane, beta-aminoethyl-gamma-aminopropylethoxysilane, fluoropropyltriethoxysilane, and trifluoropropyltrimethoxysilane.

And it is characterized in that it further comprises at least one additive selected from colorants, curing accelerators, antifoams, dispersants, ultraviolet stabilizers, sunscreens, inorganic fillers, emulsifiers, surfactants, viscosity regulators, antioxidants.

(I) at least one compound selected from styrene, a-methylstyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, 2-hydroxyethyl (meth) acrylate, and (ii ) Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, n-pentyl (meth) acrylate , alkyl groups of n-hexyl (meth) acrylate, n-decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate Epoxy groups of alkyl (meth) acrylates and glycidyl (meth) acrylates containing hydroxyl groups of alkyl (meth) acrylates, hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate Alkyl (meth) acrylate containing, benzyl (meth) acryl Alkyl (meth) acrylates containing an aryl group of a nitrate N, N-dimethylaminoethyl (meth) acrylate further copolymerized copolymer resin of at least one compound selected from alkyl (meth) acrylates containing an amino group It is characterized by including.

And 80 to 200 parts by weight of the water-soluble epoxy resin, 10 to 100 parts by weight of the glycidyl ether-based diluent, 150 to 250 parts by weight of the water dispersible curing agent, and the organosilicon-containing compound represented by the general formula (2) with respect to the entire water-soluble epoxy resin composition. It is characterized by including 1 to 15 parts by weight, and the remaining amount of the solvent.

In addition, it is characterized in that it comprises 10 to 80 parts by weight of the copolymer resin.

On the other hand, the coating method of the water-soluble epoxy resin for preventing concrete salting and neutralization is apply | coated to the surface of a concrete structure and the surface of a pier using the water-soluble epoxy resin composition in any one of Claims 1-9. .

Moreover, the coating film using the water-soluble epoxy resin composition for concrete salt prevention and neutralization prevention is obtained by apply | coating the water-soluble epoxy resin composition for concrete salt prevention and neutralization prevention in any one of Claims 1-9. It is characterized by the above-mentioned.

According to the present invention, the present invention relates to a water-soluble epoxy resin composition for preventing concrete salting and neutralization, and a method of forming a coating film using the same, wherein the water-soluble epoxy resin composition is used, and has excellent adhesive resistance to concrete structures, and is solvent resistant and water resistant It can improve the excellent chemical properties, excellent weather resistance, excellent mechanical properties of impact resistance.

In addition, the durability of the concrete structure can be improved by preventing salting and neutralization of the concrete structure, and the resin composition does not use a volatile organic solvent, thereby providing an environmentally friendly coating material free of volatile organic compounds or harmful components.

Hereinafter, a water-soluble epoxy resin composition for preventing concrete salting and neutralization of the present invention and a method of forming a coating film using the same will be described in detail.

According to one embodiment of the present invention, the epoxy oligomer may use an epoxy oligomer selected from one or more of glycidyl ether epoxy oligomer, glycidyl ester epoxy oligomer, bisphenol A type epoxy oligomer, bisphenol F type epoxy oligomer. have. Glycidyl ether-based epoxy oligomer may be selected from the group consisting of ethylene glycol, propylene glycol, butanediol, 2-methyl propanediol, neopentyl glycol, 1,6-hexanediol, triol protane, The cydyl ester epoxy oligomer may be selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, adipic acid, tetrahydro phthalic acid and hexahydrophthalic acid.

Typically, the epoxy oligomer may be used without limitation as long as it has an epoxy equivalent of 100 to 1000 g / eq, a weight average molecular weight of 3000 to 1000000, and a viscosity of 25 to 500 to 20000 cps. Bisphenol A epoxy resins having an epoxy equivalent of 180 to 220 g / eq (Kukdo Chemical, YD-128) are used.

The bisphenol A epoxy oligomer is prepared by reacting epichlorohydrin with a hydroxyl group of bisphenol A. Bisphenol A type epoxy oligomers are bifunctional oligomers similar to the case of bisphenol F type epoxy oligomers. The bisphenol A epoxy oligomer is a mixture of oligomers of various molecular weights depending on the molar ratio of bisphenol A to epichlorohydrin.

In the present invention, the bisphenol A epoxy oligomer in the epoxy oligomer has an epoxy equivalent of 100 to 1000 g / eq, an oligomer having a weight average molecular weight of 3000 to 1000000 and a viscosity of 25 to 500 to 20000 cps.

Polyether glycol that can be used to prepare a water-soluble epoxy resin is represented by the formula (1), examples of the polyether glycol include polyethylene glycol, polypropylene glycone, polybutylene glycol and the like having a number average molecular weight in the range of 200 to 30000 These can be mentioned, These can be used individually or in combination of 1 or more types.

[Formula 1]

H- (O- (CH2) m) x-0H

(In Formula 1, m is an integer of 2 to 4, x is an integer satisfying the number average molecular weight.)

If the number average molecular weight of the polyether glycol is less than 200, the number of epoxy functional groups decreases, the reactivity becomes poor at the time of forming the coating film, and the water resistance becomes weak, and if the number average molecular weight of the polyether glycol exceeds 30000, The viscosity may be excessively increased, and the mechanical properties of the coating film may be lowered.

Therefore, in the present invention, in order to prepare a water-soluble epoxy resin, it is preferable that the polyether glycol has a number average molecular weight in the range of 200 to 30000.

Linear aliphatic polyamines, aromatic polyamines, acid anhydrides, and imidazoles are well known as water dispersible curing agents in the present invention, but in the present invention, amine curing agents selected from the group consisting of acyclic polyamines, aliphatic polyamines, aromatic polyamines, and amine adducts The reason is because the physical properties, adhesion and chemical resistance of the cured resin, as well as the room temperature curability, physical properties, curing rate and safety of the curing agent. Typically the alicyclic polyamine is isophoronediamine and the aliphatic / aromatic polyamine is m-xylenediamine.

The amine adducts are adducts of polyamines with epoxy or similar resins. More specifically, the amine adducts include m-xylenediamine and isophoronediamine to which various epoxy resins such as bisphenol A epoxy resin are added. Epoxy resins capable of forming adducts with these polyamines include non-alicyclic epoxy resins, and examples of the amine adducts include m-xylenediamine, isophononediamine, and adducts of bisphenol A-based liquid epoxy resins.

In the present invention, the glycidyl ether-based diluent is used to adjust the viscosity of the resin composition, the glycidyl ether-based diluent is butyl glycidyl ether, phenyl glycidyl ether, aliphatic glycidyl ether, carboxylic Group consisting of glycidyl ether, hexanediol diglycidyl ether, ethoxyglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether It may be selected from one or more. In addition, the epoxy equivalent of the glycidyl ether-based diluent may be used having a 100 to 500 g / eq.

In addition, the organosilicon-containing compound has an epoxy group, a mercapto or an amino group in its molecule. The organosilicon-containing compound having an epoxy group or an amino group is effective in enhancing adhesion to concrete because the silane group in the molecule reacts with the concrete to be hydrolyzed to the silanol group and is also bonded together with the water dispersible curing agent. The containing compound can improve the interfacial properties of the coating film and concrete, and is effective in improving the interfacial wetting properties.

It may be represented by the formula (2) of the organo silicon-containing compound.

(2)

R1 is selected from aminoethyl group, vinyl group, methyl group, glycidoxypropyl group, methacryloxybutyl, methacryloxypropyl, propyl substituted with fluorine, ethyl group substituted with fluorine and hydrogen group, and R2 to R4 are ethoxy It may be selected from the group, butoxy group, hydrogen group and methoxy group. In addition, R1 to R4 are not all hydrogen.

Specific examples of the organosilicon-containing compound include 3-glycidoxypropyltriethoxysilane, 3-aminopropyltributoxysilane, 3-methacryloxybutylsilane, 3-mercaptopropyltriethoxy Silane, 3-mercaptopropylmethoxysilane, 3-methacryloxyethoxysilane, 3-methacryloxybutylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, vinylmethyldimethoxy Silane, methyltriisopropoxysilane, methyltriacetoxysilane, beta-aminoethyl-gamma-aminopropylethoxysilane, fluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane and the like can be used, but not limited thereto. It doesn't work.

In the present invention, the water-soluble epoxy resin composition may include a solvent containing one or more selected from the group consisting of water, celluloid, alcohol, glycol ether, ketone, carbitol.

The alcohol may be an alcohol having 1 to 20 carbon atoms, and more specifically ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol or a mixture thereof.

Specific examples of the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate), ethylene glycol monobutyl ether or mixtures thereof.

The ketone may be a ketone having 1 to 20 carbon atoms, and specific examples thereof include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, or a mixture thereof.

Meanwhile, in the present invention, the copolymer resin may be further included in the water-soluble epoxy resin composition. The copolymer resin includes (i) at least one compound selected from styrene, a-methylstyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, 2-hydroxyethyl (meth) acrylate, (ii) methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, n-pentyl (meth ) Acrylate, n-hexyl (meth) acrylate, n-decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, etc. Alkyl (meth) acrylates containing an alkyl group of alkyl (meth) acrylates containing hydroxyl groups, such as hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate glycidyl (meth) acrylate Alkyl (meth) acryl containing epoxy groups, such as these At least one compound selected from alkyl (meth) acrylates containing amino groups, such as alkyl (meth) acrylates N, N-dimethylaminoethyl (meth) acrylate, including an aryl group such as late benzyl (meth) acrylate The copolymerized resin of may further be included.

If necessary, the water-soluble epoxy resin composition of the present invention may be one or more selected from a colorant, a curing accelerator, an antifoaming agent, a dispersant, a UV stabilizer, a sunscreen agent, an inorganic filler, an emulsifier, a surfactant, a viscosity modifier, an antioxidant, and the like according to a specific use. It may further contain an additive, but is not limited thereto.

As the coloring agent, extender pigments, colored pigments, dyes and the like may be used.For the extender pigments, calcium carbonate, magnesium carbonate, silica, silica-alumina, glass powder, glass beads, mica, graphite, barium equivalent, aluminum hydroxide, talc, kaolin, Acidic clay, activated clay, bentonite, diatomaceous earth, montmorillonite, dolomite and the like can be selected and used, but is not limited thereto. Color pigments include, for example, titanium oxide, zincated, carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), Mitsubishi carbon black MA100, perylene black (BASF K0084. K0086), cyanine black, linol Yellow (CI21090), Linol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI42595), CI PIGMENT RED97, 122, 149, 168, 177, 180, 192, 215 , CI PIGMENT GREEN 7, 36, CI PIGMENT 15: 1, 15: 4, 15: 6, 22, 60, 64, CI PIGMENT 83, 139 CI PIGMENT VIOLET 23 can be selected and used, but It is not limited.

As the curing accelerator, for example, one or more of phenol, nonylphenol, tertiary amine, merethane, dibutyl diacetate, dibutylene dilaurate, monobutylene oxide, monobutylene chloride dihydroxide and the like are selected. Can be used, but is not limited thereto.

As the antifoaming agent used to impart anti-foaming function of water-soluble epoxy resin composition for preventing concrete salting and neutralization, BYK-Chemie's BYK-A501 is used as the main component of bubble-breaking polymer and polysiloxane solution. Also, EFKA's EFKA8203, Impag One or more kinds of perenol E8, etc. may be selected and used, but the present invention is not limited thereto.

In the present invention, as a dispersant used to impart dispersibility of water-soluble epoxy resin composition for preventing concrete salting and neutralization, BYK- # 161, manufactured by BYK-Chemie Co., Ltd. One or more of BYK- # 168, 1-methoxy-2 propylene acetate, EFKA 4048, 4060, etc. of EFKA can be selected and used, but is not limited thereto.

UV stabilizers and sunscreens may be added and used as necessary for UV resistance of the water-soluble epoxy resin composition for preventing concrete salting and neutralization of the present invention.

In the present invention, the inorganic filler is preferably at least one selected from the group consisting of calcium carbonate, talc, bicarbonate, silica, and dolomite, but is not limited thereto.

In the present invention, the emulsifier is preferably at least one selected from the group consisting of a copolymer of polyoxyethylene and polyoxypropylene, a copolymer of polyoxyethylene and polyoctylphenyl ether, and sodium dodecylbenzene sulfide, but is not limited thereto. .

Each component constituting the water-soluble epoxy resin composition for preventing concrete salting and neutralization of the present invention may be used alone or in combination of two or more thereof.

According to one embodiment of the present invention, using a water-soluble epoxy resin composition for preventing concrete salting and neutralization, it is possible to implement a method of forming a coating film applied to the surface of the concrete structure, the surface of the piers.

In addition, according to an embodiment of the present invention, by using a water-soluble epoxy resin composition for preventing concrete salting and neutralization, it is possible to implement a coating film obtained by applying to the surface of the concrete structure, the surface of the piers and the like.

The composition ratio of the water-soluble epoxy resin composition for preventing concrete salting and neutralization will be described. 80 to 200 parts by weight of the water-soluble epoxy resin, 10 to 100 parts by weight of the glycidyl ether-based diluent, 150 to 250 parts by weight of the water dispersible curing agent, and 1 to 15 parts by weight of the organosilicon-containing compound, based on the entire epoxy resin composition. Part, and a residual amount of solvent.

When the amount of the water-soluble epoxy resin is 80 to 200 parts by weight, it is because the adhesive strength after curing is excellent and the water resistance is excellent. It is because an organosilicon containing compound is 1-15 weight part, and the adhesive force of hardened | cured material is excellent in this range. The glycidyl ether-based diluent is 10 to 100 parts by weight, and within this range, the viscosity of the cured product can be lowered, thereby improving the corrosion resistance and chemical resistance. The water-dispersible curing agent is 150 to 250 parts by weight, and within this range, the reaction between the epoxy groups occurs sufficiently, thereby contributing to the durability improvement of the resin composition, and in particular, solvent resistance and salt water resistance can be improved.

In addition, the copolymer resin may be further included with respect to the water-soluble epoxy resin composition, may contain 10 to 80 parts by weight based on the entire water-soluble epoxy resin composition, when it has such a range, corrosion resistance, chemical resistance, etc. Can improve.

Accordingly, the water-soluble epoxy resin composition for preventing concrete salting and neutralization according to the present invention has excellent adhesion to concrete structures, and can sufficiently penetrate into the porous surface of the concrete to secure a certain level of adhesion area and adhesion force. In addition, since long-term durability, long-term water resistance or long-term accelerated weathering resistance can be sufficiently secured, it is possible to prevent deterioration of the structure itself by preventing salting and neutralization of the concrete structure.

On the other hand, when curing the water-soluble epoxy resin composition, the mercury generation amount may be less than 0.01 mg / L. When the amount of mercury generation is 0.01 mg / L or less, it may mean that mercury is not substantially generated when the resin composition is cured.

Specific details for carrying out the present invention will be described in more detail in the following Examples, but the present invention is not limited thereto.

Preparation Example 1 Preparation of Water-Soluble Epoxy Resin

To a 2-liter four-necked flask, a thermometer, condenser, stirrer and heater were attached. Epoxy compounds include 80 g of bisphenol A epoxy resin oligomer (Kukdo Chemical YD-128) having an epoxy equivalent of 187 eq / g, 75 g of polypropylene glycol having a number average molecular weight of 1000, and 250 ppm of triethylammonium chloride used as a catalyst. The temperature was raised to 130 under nitrogen atmosphere. After the reaction was carried out while maintaining the temperature of about 130, as the reaction proceeds, the epoxy equivalent was measured. When the epoxy equivalent was in the range of 300, the temperature was lowered to 60, and then 690 g of deionized water was added for 10 minutes to terminate the reaction.

Preparation Example 2 Preparation of Water-Soluble Epoxy Resin

A water-soluble epoxy resin was prepared in the same manner as in Preparation Example 1, except that 80 g of a bisphenol F-type epoxy resin oligomer (Kukdo Chemical YDF-170) having an epoxy equivalent of 170 g / eq was substituted for the bisphenol A-type epoxy resin oligomer. Prepared.

Preparation Example 3 Preparation of Water-Soluble Epoxy Resin

A water-soluble epoxy resin was prepared in the same manner as in Production Example 1, except that 75 g of polyethyl glycol having a number average molecular weight of 3000 was used instead of polypropylene glycol as polyether glycol.

To prepare a water-soluble epoxy resin composition according to the component and the composition ratio as shown in Table 1.

ingredient (Unit: parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 receptivity
Epoxy
Suzy (One) 100 40 (2) 80 120 40 (3) 80 (4) 80 (5) 80 diluent (6) 20 20 (7) 20 20 30 (8) 30 40 Water-dispersibility
Hardener (9) 200 240 200 200 (10) 160 (11) 220 200 Copolymer resin (12) 10 40 menstruum water 50 50 50 50 50 ethanol 50 50 Organosilicon-Containing Compound (13) 3 1.5 1.5 (14) 1.5 10 3 1.5

(1) Water-soluble Epoxy Resin of Preparation Example 1

(2) Water-soluble Epoxy Resin of Preparation Example 2

(3) Water-soluble Epoxy Resin of Preparation Example 3

(4) Bisphenol A epoxy resin (Kukdo Chemical YD-128)

(5) Bistenol F-type epoxy resin (Kukdo Chemical YDF-170)

(6) Thinner (Huntsman M-2070)

(7) 1,4-butanediol diglycidyl ether

(8) polyethylene glycol diglycidyl ether

(9) isoprondiamine

(10) polyoxypropylenediamine

(11) polyethylenetetraamine

(12) Methyl methacrylate-styrene copolymer (Aldrich, molecular weight: 30000)

(13) 3-aminopropyltributoxysilane (Aldrich)

(14) trifluoropropyltriethoxysilane (Aldrich)

2. Experimental Example

The water soluble epoxy resin compositions obtained in Examples 1 to 5 and Comparative Examples were applied to concrete specimens and then cured, and the results are shown in the following [Table 2].

<Adhesion test method>

Test specimens were prepared by applying water-soluble epoxy resin compositions prepared in Examples 1 to 5 and Comparative Examples to concrete specimens. The adhesion test evaluated the adhesion resistance by 90 peel adhesive force (unit N / 25mm) by the average value which cut out into the rectangle of width 25mm, and tested three times. At this time, the adhesive force is excellent, and the effect of material destruction of the concrete substrate appears.

<Contents Test Method>

The solvent resistance test method calculates the number of rubs when the film is peeled off after immersing the test specimen in xylene on a glass plate based on a dry coating thickness of 50 micrometers. The higher the number of rubs, the better the solvent content.

<Water resistance test method>

Water resistance test method was tested according to the KS M ISO28012-1 method was carried out at 25 using distilled water.

<Salt resistance test method>

Salt resistance test method was tested according to the KS M ISO2812-1 test method was carried out at 25 using a 10wt% NaOH aqueous solution.

Accelerated Weathering Test Method

Accelerated weathering test method was tested according to the KS F2274 test method.

<Mercury, smell>

Odor and mercury were measured according to the sanitary safety standard process test method of tap water and products.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Adhesive Resistance Good Good Good Good Good Bad Good Content-based radish radish radish radish radish radish radish Water resistance ◎ ◎ ◎ ◎ ◎ ○ ○ Saltwater ◎ ◎ ◎ ◎ ◎ △ ○ Accelerated weathering ◎ ◎ ○ ◎ ◎ ◎ △ smell radish radish radish radish radish radish radish Mercury Not detected Not detected Not detected Not detected Not detected Detected Detected

Excellent: ◎

Normal: ○

Insufficient: △

Saline resistance and accelerated weather resistance measurement results indicate that the appearance change or physical property change in the coating layer was not substantially changed after applying the conditions of the experimental items.

As shown in [Table 2], the coating film provided by using the water-soluble epoxy resin composition of the embodiment is not only excellent adhesion to concrete, but also excellent resistance to distilled water or brine, chemical resistance to the solvent It was confirmed that it is possible to prevent salting or neutralization easily due to external factors such as salt water, moisture, external pressure and ultraviolet rays, and to minimize damage of the structure itself.

That is, using the composition of the embodiments, it is possible to form a coating film having excellent long-term durability, long-term water resistance and long-term accelerated weather resistance on the surface of the concrete structure.

In addition, it was confirmed that mercury or other heavy metals were not substantially detected in the coating film using the compositions of the above embodiments, so that no harmful substances were produced.

The present invention relates to a water-soluble epoxy resin composition for preventing concrete salting and neutralization, and a method of forming a coating film using the same, using the water-soluble epoxy resin composition, having excellent adhesive resistance to concrete structures, and having excellent solvent resistance and water resistance. And excellent mechanical properties of accelerated weather resistance and impact resistance. In addition, by applying the water-soluble epoxy resin composition to prevent salt and neutralization of the concrete structure can improve the durability of the concrete structure, and the resin composition does not use a volatile organic solvent, it can be eco-friendly water without volatile organic compounds or harmful components Can provide a coating.

Claims (11)

Water-soluble epoxy resin which adds the polyether glycol represented by General formula (1) of the number average molecular weight in the range of 200-30000 to the epoxy oligomer which has an epoxy equivalent of 100-1000 g / eq;
[Chemical Formula 1]
H- (O- (CH2) m) x-0H
(In Formula 1, m is an integer of 2 to 4, x is an integer satisfying the number average molecular weight.)
Organo silicon-containing compounds represented by Formula 2;
(2)

(In Formula 2, R1 is selected from aminoethyl group, vinyl group, methyl group, glycidoxypropyl group, methacryloxybutyl, methacryloxypropyl, propyl substituted with fluorine, ethyl group substituted with fluorine, hydrogen group, R2 to R4 may be selected from an ethoxy group, a butoxy group, a hydrogen group and a methoxy group, respectively, and R1 to R4 are not all hydrogen.)
Glycidyl ether-based diluents; Water dispersible curing agents; And a solvent comprising at least one selected from the group consisting of water, celluloid, alcohol, glycol ether, ketone, and carbitol;
(i) at least one compound selected from styrene, a-methylstyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, 2-hydroxyethyl (meth) acrylate, and (ii) methyl (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, n-pentyl (meth) acrylate, n Alkyl including alkyl groups of hexyl (meth) acrylate, n-decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecanyl (meth) acrylate (Meth) acrylates, alkyl (meth) acrylates containing hydroxyl groups of hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and epoxy groups of glycidyl (meth) acrylate Alkyl (meth) acrylate, benzyl (meth) acrylate Copolymerized copolymer resin of at least one compound selected from alkyl (meth) acrylates containing amino groups of alkyl (meth) acrylates N, N-dimethylaminoethyl (meth) acrylate containing an aryl group; and,
80 to 200 parts by weight of the water-soluble epoxy resin, 10 to 100 parts by weight of the glycidyl ether-based diluent, 150 to 250 parts by weight of the water dispersible curing agent, and the organosilicon-containing compound represented by the formula (2) based on the entire water-soluble epoxy resin composition. 15 parts by weight, 10 to 80 parts by weight of the copolymer resin, and a residual amount of a water-soluble epoxy resin composition for preventing concrete salt and neutralization.
The method of claim 1,
The epoxy oligomer is glycidyl ether-based epoxy oligomer, glycidyl ester epoxy oligomer, bisphenol A type epoxy oligomer, bisphenol F type epoxy oligomer is at least one selected from water-soluble epoxy resin composition for preventing concrete salting and neutralization.
The method of claim 1,
The glycidyl ether-based diluent is butylglycidyl ether, phenyl glycidyl ether, aliphatic glycidyl ether, carboxylic glycidyl ether, hexanediol diglycidyl ether, ethoxyglycidyl ether, polyethylene A water-soluble epoxy resin composition for preventing concrete salting and neutralization selected from a group consisting of glycol diglycidyl ether, diethylene glycol diglycidyl ether, and 1-4-butanediol diglycidyl ether.
The method of claim 1,
The water-dispersible curing agent is a water-soluble epoxy resin composition for preventing concrete salt and neutralization selected from one or more selected from the group consisting of acyclic polyamines, aliphatic polyamines, aromatic polyamines, and amine adducts.
The method of claim 1,
The compound of Formula 2 is 3-glycidoxypropyltriethoxysilane, 3-aminopropyltributoxysilane, 3-methacryloxybutylsilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylme Methoxysilane, 3-methacryloxyethoxysilane, 3-methacryloxybutylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, vinylmethyldimethoxysilane, methyltriisopropoxysilane Water-soluble epoxy resin for preventing concrete salting and neutralization selected from at least one selected from methyltriacetoxysilane, beta-aminoethyl-gamma-aminopropylethoxysilane, fluoropropyltriethoxysilane and trifluoropropyltrimethoxysilane Composition.
The method of claim 1,
A water-soluble epoxy resin composition for preventing concrete salting and neutralization further comprising at least one additive selected from colorants, curing accelerators, defoamers, dispersants, ultraviolet stabilizers, sunscreen agents, inorganic fillers, emulsifiers, surfactants, viscosity regulators, and antioxidants.
delete delete delete The coating method of the water-soluble epoxy resin for concrete salt prevention and neutralization characterized by apply | coating to the surface of a concrete structure and the surface of a pier using the water-soluble epoxy resin composition in any one of Claims 1-6.
The coating film using the concrete salt salt and neutralization prevention water-soluble epoxy resin composition obtained by apply | coating the concrete salt salt and neutralization prevention water-soluble epoxy resin composition in any one of Claims 1-6.