KR101371222B1 - The solventless coating composition and method of forming a coating film using the same - Google Patents

Abstract

The present invention an environment-friendly solventless coating composition, a film using the same, and a method for forming the film, and more particularly, to the environment-friendly solventless coating composition having excellent interfacial properties for a surface such as an apartment structure, an steel structure, a concrete structure, a steel water pipe, a drinking water tank, a swimming pool facility, a simple water supply facility, a catchment area, a water-cleaning facility and the like, and excellent adhesiveness resistance and accelerated weathering, and in particular, not requiring a volatile organic solvent as an environment-friendly solventless composition, and thereby, allowing the use in enclosed space. The coating composition has: (a) a principal member comprising i) a solventless epoxy resin having an epoxy equivalence of 1150-550 g/eq, ii) a polymeric compound, iii) a polymeric resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with an ester compound of a hydroxyl group of a novolak-type epoxy compound and an unsaturated monocarboxylic acid, iv) a coloring agent, and v) a compound containing organo silicone; and (b) a hardening agent comprising i) an amine-based hardening agent ii)a hardening accelerator, and iii) a polymeric agent.

Description

Solventless Coating Composition and Method of Forming a Coating Film Using the Same

The present invention relates to an environmentally friendly solvent-free coating composition, and a method for forming a coating film and a coating film using the same, and more particularly, has excellent adhesion resistance to concrete structures, apartment structures, steel structures, water purification plant, It is also suitable for use in swimming pools, and has excellent chemical and weathering properties. In particular, it is an eco-friendly solvent-free type that provides an eco-friendly solvent-free coating composition that can be used even in a confined space without using a volatile organic solvent. In addition, when the environmentally friendly solvent-free coating composition is applied to the surface of concrete structures, water purification plants, swimming pools, etc., the curing speed of these coatings is high, and the excellent mechanical properties such as promoting weather resistance and durability of the coating itself can be improved. have.

Specifically, the present invention is an environmentally friendly solvent-free coating composition for improving durability and preventing pollution of various apartment structures, steel structures, concrete structures, water pipes, drinking water tanks, swimming pool facilities, simple water supply facilities, water sources, water purification facilities, and the like. It is environmentally friendly, free of volatile organic substances or harmful components, and excellent in fouling resistance and neutralization resistance, and also excellent in adhesion to concrete structures, fast curing speed upon application, and accelerated weather resistance which is a mechanical property of the coating film. It is excellent in durability.

Various surfaces, such as concrete, a metal, a water tank, a water purification plant, and a swimming pool, fall durability, adhesiveness, etc. by ultraviolet rays, external pressure, carbon dioxide, and moisture. Therefore, in general, walls or floors based on concrete or mortar surface are usually finished in consideration of insulation, soundproofing, anticorrosion, antirust, flame retardant, or anti-slip, and various finishing materials can be applied according to the required performance. have. In addition, since most steel structures including steel are exposed to a corrosive environment, a method of coating a resin as a finishing agent on the surface of the steel structure is mainly applied to enhance durability.

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. Among them, the resin which makes up the main species of coating resin is known as an epoxy resin.

In particular, epoxy resins are widely used as adhesives and coating agents for structures because of excellent adhesiveness and chemical resistance. Bisphenol A type epoxy resins, bisphenol F type epoxy resins, and polyfunctional epoxy resins are most commonly used as binders for epoxy resins. Resins, novolac epoxy resins and the like. In the case of using the epoxy resin, while having excellent chemical resistance, mechanical properties, and the like, there is a problem of causing environmental pollution, deterioration of working environment, explosion, etc. due to the organic solvent used for spraying the epoxy resin.

Therefore, various coating agents for protecting the surface of concrete, steel, swimming pool, etc. have been developed as a way to solve the above problems. Looking at the contents of the patent application of the developed technologies, Korean Patent Publication No. 0723775 Waterproof construction method of concrete structure using room temperature type polyurea and domestic registered patent publication No. 0875589 for epoxy modified polyurea repair material for cross section repair of concrete structure and cross section repair method of concrete structure using same and domestic registered patent publication No. 0906416 However, various patents are known, such as concrete anticorrosive method and anticorrosive coating, and Korean Patent Publication No. 0397812, such as a method for treating a concrete surface for polyurea spray coating, but in the case of the above patents, a two-component oil-soluble polyurea composition I use it, They have harmful components, which are not environmentally friendly, and still have problems in durability and adhesion resistance.

The present invention relates to an environmentally friendly solvent-free coating composition, and to a method of forming a coating film and coating using the same, more specifically, apartment structure, steel structure, concrete structure, water pipe, drinking water tank, swimming pool facility, simple water supply facility, water source It has excellent adhesion and accelerated weather resistance, which has excellent interfacial properties on the surface of water, water purification facilities, etc. It is an eco-friendly solvent-free coating composition that can be used even in confined spaces without using volatile organic solvents. The coating composition is saturated with hydroxyl groups of (a) i) a solvent-free epoxy resin having an epoxy equivalent of 150 to 550 g / eq, ii) a polymerizable compound, and iii) an esterified product of a novolak-type epoxy compound with an unsaturated monocarboxylic acid. Or a polymerizable resin obtained by reacting an unsaturated polybasic acid anhydride, i) a colorant, i) a main body comprising an organo silicone-containing compound represented by the formula (1), (b) i) an amine curing agent, ii) a curing accelerator, i) polymerization It has a curing agent comprising a compound, thereby providing an environmentally friendly solvent-free coating composition. Another object of the present invention is to form a dense coating film on the surface of the coating material from them using an eco-friendly solvent-free coating composition, the coating film does not contain an organic solvent, it is environmentally friendly, and the applied coating film is a fast drying speed It can have excellent mechanical properties such as accelerated weather resistance, durability.

According to one aspect of the invention, (a) i) a solvent-free epoxy resin having an epoxy equivalent of 150 to 550 g / eq, ii) a polymerizable compound, and iii) an esterified product of a novolak-type epoxy compound with an unsaturated monocarboxylic acid. Polymerizable resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group of iii) a coloring agent, iii) a main body comprising an organo silicone-containing compound represented by the formula (1), (b) amine) curing agent, ii) curing accelerator And iii) an environmentally friendly solvent-free coating composition having a curing agent comprising a polymerizable compound.

[Chemical Formula 1]

R1 is selected from aminoethyl group, vinyl group, methyl group, glycidoxypropyl group, methacryloxybutyl, methacryloxypropyl, propyl substituted with fluorine, ethyl group substituted with fluorine, and R2 to R4 are ethoxy groups, butok It can be selected from the timing, hydrogen group, methoxy group, respectively.

[Solvent-free epoxy resin]

The solvent-free epoxy resin used in the present invention is an epoxy alicyclic epoxy resin having an epoxy equivalent weight of 150 to 550 g / eq. The epoxy resin used in the present invention may be selected from an epoxy resin which is liquid and insoluble in water, and an epoxy resin having a low viscosity and water permeability. Preferred epoxy resins include special glycidyl ether epoxy resins such as bisphenol A, bisphenol AD, novolac, bisphenol F and brominated bisphenol A, and special epoxy resins such as glycidyl ester epoxy resins. Papers, glycidylamine-based epoxy resins and alicyclic epoxy resins and various modified epoxy resins, etc., but their epoxy equivalent should be 150 to 550g / eq.

The bisphenol-based epoxy resin most used among the solvent-free epoxy resins exemplified above will be described in detail. Bisphenol A type epoxy resin is manufactured by reaction between 2, 2-bis (4-hydroxyphenyl) propane, ie, bisphenol A, and a haloperoxide, such as epichlorohydrin or (beta) -methyl epichlorohydrin. Bisphenol AD-based epoxy resins are prepared by the reaction between 1,1-bis (4-hydroxyphenyl) ethane, i.e., bisphenol AD and haloperoxides such as epichlorohydrin or β-methyl epichlorohydrin. Bisphenol F-based epoxy resins are prepared through the reaction between bis (4-hydroxyphenyl) methane, that is, bisphenol F and epichlorohydrin or β-methyl epichlorohydrin. In this invention, it is most preferable to use a bisphenol AD system, a bisphenol A system, and a bisphenol F system epoxy resin.

[Polymerizable Compound]

In the present invention, a polymerizable compound may be used to adjust the viscosity of the solvent-free coating composition. The polymerizable compound may be classified into a polymerizable compound having an epoxide group and a non-polymerizable compound which participates in the reaction with the curing agent but does not participate in the reaction but remains in the coating film and affects physical properties. In the present invention, the organic compound does not use any non-reactive compound for the environment. The polymerizable compound used in the present invention may be, for example, monoepoxide, glycidyl ester, phenylglycidyl ether, 2-ethylhexyl glycidyl, such as cresyl glycidyl ether and alkyl glycidyl ether. Versatic acid, such as ether and parabutyl butylphenyl glycidyl ether, neopentyl diglycidyl ether, 1, 4- butane diglycidyl ether, cyclohexane dimethanol diglycidyl ether, resorcinol diglyc One kind or two or more kinds selected from diepoxides such as cydyl ether, diethylene glycol diglycidyl ether, and 1,4-butanediol diglycidyl ether can be used. The polymerizable compound uses 10 to 100 parts by weight, the mechanical properties may be lowered below the use range, and when the use range is exceeded, the coating film properties such as hardness are lowered and the curing rate is lowered.

[Polymerizable resin]

In this invention, polymeric resin obtained by making a saturated or unsaturated polybasic acid anhydride react with the hydroxyl group of the ester compound of a novolak-type epoxy compound and unsaturated monocarboxylic acid can be used.

First, the said polymeric resin esterifies and reacts the (a) epoxy group of a novolak-type epoxy compound, (b) the carboxyl group of unsaturated monocarboxylic acid, and (c) saturated or unsaturated polybasic acid anhydride to the produced hydroxyl group further. It is obtained by. As the novolak-type epoxy compound (a), for example, epichlorohydrin and methyl epichlorohydrin to novolacs obtained by reacting phenols such as phenol, cresol, halogenated phenol and alkyl phenol with formaldehyde under an acidic catalyst. The thing obtained by making epihalohydrin, such as a drin, react is mentioned. As a commercial item, Tohto Chemical Co., Ltd. make YDCN-701, YDCN-704, YDPN-638, YDPN-602; Dow Chemical Co., Ltd. DEN-431, DEN-439; EPN-1138, EPN-1235, and EPN-1299 manufactured by Ciba Specialty Chemicals; Dai Nippon Ink Chemical Co., Ltd. make N-730, N-770, N-865, N-665, N-673, N-695, VH-4150, VH-4240, VH-4440; Nippon Gunpowder Co., Ltd. EOCN-120, EOCN-104, BRRN-1020; Asahi Chemical Co., Ltd. make ECN-265, ECN-293, ECN-285, ECN-299, etc. are mentioned.

In addition, a part of the novolac type epoxy compound is, for example, emulsified cell epoxy manufactured by Epicoat 828, Epicoat 1007, Epicoat 807 (Epicoat is a registered trademark); Epiclon 840, Epiclon 860, Epiclon 3050, Epiclon 830 (Epiclon is a registered trademark) manufactured by Dainippon Ink Chemical Co., Ltd .; Dow Chemical Co., Ltd. DER-330, DER-337, DER-361, the Daicel Chemical Industry Co., Ltd. celloside (2021), celloside side 3000 (Celokiside is a registered trademark); Mitsubishi Gas Chemical Co., Ltd. product TETRADX, TETRAD-C ,; Nippon Procurement Co., Ltd. manufacture EPB-13, EPB-27; Doto Chemical Co., Ltd. YD-116, YD-128, YD-013, YD-020, YDG-414, ST-3000, ST-110, YDF-190, YDF-2004, YDF-2007; Chiba Specialty Chemicals GY-260, GY-255, and XB-2615; Glycy such as bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, brominated bisphenol A type, amino group-containing, alicyclic, or polybutadiene modified such as DER-332, DER-662, DER-542 manufactured by Dow Chemical It may be substituted with a dill ether type epoxy compound. Therefore, although the adhesiveness of a cured film improves, when there are many ratios of these epoxy compounds, the mechanical property of a coating film will worsen.

Subsequently, examples of the unsaturated monocarboxylic acid (b) used for the synthesis of the polymerizable resin include acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfuryl acrylic acid, α-cyano cinnamic acid, Semi esters, such as cinnamic acid and reactants of saturated or unsaturated dibasic anhydrides with (meth) acrylates having one hydroxyl group in the molecule, or reactants of saturated or unsaturated dibasic acids with unsaturated monoglycidyl compounds For example, saturation, such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, itaconic anhydride, methylene methylene tetrahydro phthalic anhydride Or unsaturated dibasic acid anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth ) Acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylic Half esters obtained by reacting (meth) acrylates having one hydroxyl group in a molecule such as (meth) acrylate of phenylglycidyl ether at the same molar ratio, or saturated or unsaturated dibasic acids (for example, And semi-esters obtained by reacting succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, itaconic acid, and the like with an unsaturated monoglycidyl compound (for example, glycidyl (meth) acrylate) in the same molar ratio. These can be mentioned, These can be used individually or in combination of 2 or more types.

Examples of the saturated or unsaturated polybasic acid anhydride (c) used for the synthesis of the polymerizable resin include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride and methylhexahydro anhydride. Dibasic acid anhydrides such as phthalic acid, endmethylenetetrahydro phthalic anhydride, methylene methylenetetrahydro phthalic anhydride, chloric anhydride, methyltetrahydro phthalic anhydride trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride Aromatic polyhydric carboxylic anhydrides, such as, for example, polyhydric carbohydrates such as 5- (2,5-dioxotetrahydropril) -3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride A main acid anhydride derivative etc. can be used.

[coloring agent]

As the colorant, extender pigments, colored pigments, dyes and the like can be used.For the extender pigments, calcium carbonate, magnesium carbonate, silica, silica-alumina, glass powder, glass beads, mica, graphite, barium sulfate, 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. Known dyes can also be used.

[Organosilicon-containing Compound]

In the present invention, an organosilicon-containing compound represented by Formula 1 may be used to improve adhesion.

[Chemical Formula 1]

R1 is selected from aminoethyl group, vinyl group, methyl group, glycidoxypropyl group, methacryloxybutyl, methacryloxypropyl, propyl substituted with fluorine, ethyl group substituted with fluorine, and R2 to R4 are ethoxy groups, butok It can be selected from the timing, hydrogen group, methoxy group, respectively.

Specific examples of the formula 1 include 3-glycidoxypropyltriethoxysilane, 3-aminopropyltributoxysilane, 3-methacryloxybutylsilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethoxysilane, 3-methacryloxyethoxysilane, 3-methacryloxybutylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, vinylmethyldimethoxysilane, Methyltriisopropoxysilane, methyltriacetoxysilane, beta-aminoethyl-gamma-aminopropylethoxysilane, fluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane, but are not limited thereto.

[Amine Curing Agent]

Although linear aliphatic polyamines, aromatic polyamines, acid anhydrides, and imidazoles are well known as curing agents, the curing agents used in the present invention include an amine curing agent 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.

As a curing accelerator that can be used in the composition to maintain reactivity and storage stability at room temperature, an amine derivative is preferable, and examples thereof include diethyl triamine (DETA), ethylene diamine (EDA), and triethylene tetraamine ( Aliphatic diamines such as TETA), tetraethylene pentaamine (TEPA), diethyl aminopropylamine (DEAPA), methanediamine (MDA), N-aminoethylpiperadine (N-AEP), m-xylenediamine (m -XDA), 1,3-bisamino methylcyclohexane (1,3-AC) isophoronediamine, diamino cyclohexane, 4-4bispara amino-cyclohexylmethane, diethylpropanediamine (N, N, -Diethyl-1,3-propanediamine), hydroxyethylpentanediamine (N- (2-Hydroxyethyl) -1,3-pentanediamine), dibutylpropanediamine (N, N-di-n-butyl-1,3- Propanediamine).

[additive]

If necessary, the eco-friendly solvent-free coating composition of the present invention may be prepared by using one or more additives selected from antifoaming agents, dispersants, UV stabilizers, sunscreen agents, inorganic fillers, emulsifiers, surfactants, viscosity modifiers, antioxidants, and crosslinking agents, depending on the specific application. It may contain more, but is not limited thereto.

As the antifoaming agent used for imparting the anti-foaming function of the composition in the present invention, BYK-A501 manufactured by BYK-Chemie, the main component of which is a bubble breaking polymer and a polysiloxane solution. Moreover, EFKA8203 by EFKA, Perenol E8 by Impag, etc. can be used. In the present invention, such an antifoaming agent is used in an amount of 0.1 to 1 parts by weight based on the total weight of the main material. The antifoaming agent does not exhibit a defoaming function at 0.1 parts by weight or less, and at least 1 part by weight causes deterioration and blushing of the coating film.

As a dispersant used to impart dispersibility of the composition in the present invention, BYK- # 161 manufactured by BYK-Chemie, which has a high molecular weight block copolymer solution having a pigment affinity group as a main component, is used. In addition, 1-methoxy-2-propylacetate may be used, and EFKA 4048, 4060, etc. of EFKA Corporation may also be used. In the present invention, such a dispersant is used in an amount of 0.1 to 1 parts by weight. The dispersant may not function to disperse the pigment in the polymer resin at 0.1 parts by weight or less, and at least 1 part by weight causes deterioration and blushing of the coating film.

UV stabilizers and sunscreens may be added and used as necessary for UV resistance of the water-soluble epoxy resin composition 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. .

In the present invention, for example, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, reactive surfactants, and the like can be used. As the surfactant, those having an alkyl group, an alkenyl group, an alkylaryl group or an alkenylaryl group having 4 or more carbon atoms as a hydrophilic group are generally used. As nonionic surfactant, polyoxyethylene acetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, monolauric acid polyoxyethylene sorbitan, etc. are mentioned, for example. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate and the like. As cationic surfactant, stearyl trimethyl ammonium chloride, acetyl trimethyl ammonium bromide, etc. are mentioned, for example. Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine and the like. Moreover, what is called a reactive surfactant etc. which have a radically polymerizable functional group can be used for the said surfactant, and when the reactive surfactant is used, the accelerated weather resistance of the film formed using this resin dispersion can be improved. Representative commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd.) and Latex S-180 (manufactured by Kao Corporation).

Moreover, in order to further improve various coating-film performances, such as solvent resistance, as a crosslinking agent, the crosslinking agent which has self-crosslinking property, the compound which has several functional groups which react with a carboxyl group in a molecule, the metal complex which has a polyvalent coordination position, etc. can be used. Of these, at least one of an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, a carbodiimide compound, an oxazoline group-containing compound, and a zirconium salt compound can be selected and used.

Each component of the eco-friendly solvent-free coating composition of the present invention may be used alone or in combination of two or more thereof.

According to an embodiment of the present invention using an environmentally friendly solvent-free coating composition, obtained by applying to the surface of the apartment structure, steel structure, concrete structure, water steel pipe, drinking water tank, swimming pool facility, simple water supply facility, water source, water purification facility, etc. The formation method of a coating film can be implemented.

In addition, according to an embodiment of the present invention, by applying to the surface of the apartment structure, steel structure, concrete structure, water steel pipe, drinking water tank, swimming pool facility, simple water supply facility, water source, water purification facility, etc. using an eco-friendly solvent-free coating composition The coating film obtained can be implemented.

The composition ratio of the eco-friendly solvent-free coating composition will be described. (A) iii) 80 to 200 parts by weight of a solvent-free epoxy resin having an epoxy equivalent of 150 to 550 g / eq, ii) 10 to 100 parts by weight of a polymerizable compound, and iv) a novolak type, based on the entire eco-friendly solventless coating composition. 10 to 100 parts by weight of a polymerizable resin obtained by reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group of an esterified product of an epoxy compound and an unsaturated monocarboxylic acid, i) 10 to 100 parts by weight of a colorant, i) organo represented by the formula (1) A main body comprising 1 to 15 parts by weight of a silicone-containing compound, (b) iii) 50 to 200 parts by weight of an amine curing agent, ii) 10 to 50 parts by weight of a curing accelerator, and iii) a curing agent containing 10 to 100 parts by weight of a polymerizable compound. The mixing ratio of the main material and the curing agent has a mixing ratio of 10 parts by weight to 100 parts by weight based on 100 parts by weight of the main material.

When the amount of the non-solvent type epoxy resin is 80 to 200 parts by weight, it is because the adhesion resistance after curing is excellent and the accelerated weather resistance is excellent. A polymeric compound is 10-100 weight part, and the viscosity of hardened | cured material can be reduced in such a range, and durability and accelerated weather resistance can be improved. 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 amine curing agent is 50 to 200 parts by weight, and within this range, the reaction between the epoxy groups may occur sufficiently, thereby contributing to the durability improvement of the coating composition. In addition, the polymerizable resin obtained by reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group of an esterified product of a novolak-type epoxy compound and an unsaturated monocarboxylic acid has 10 to 100 parts by weight, and the solvent resistance of the coating film can be improved within this range. Can be. The curing accelerator has 10 to 50 parts by weight, which brings about an improvement in the curing rate of the environmentally friendly solvent-free coating composition within this range.

Therefore, when applied to the surface of apartment structures, steel structures, concrete structures, water steel pipes, drinking water tanks, swimming pool facilities, simple water supply facilities, water sources, water purification facilities, etc. using the eco-friendly solvent-free coating composition according to the present invention The adhesion is very good at, and the coated film has a fast drying speed, and can improve the excellent mechanical properties such as accelerated weather resistance and durability.

The present invention relates to an environmentally friendly solvent-free coating composition, and a method for forming a coating film and a coating film using the same, and more particularly, has excellent adhesion resistance to concrete structures, apartment structures, steel structures, water purification plant, It is also suitable for use in swimming pools, and has excellent chemical and weathering properties. In particular, it is an eco-friendly solvent-free type that provides an eco-friendly solvent-free coating composition that can be used even in a confined space without using a volatile organic solvent. In addition, when the environmentally friendly solvent-free coating composition is applied to the surface of concrete structures, water purification plants, swimming pools, etc., the curing speed of these coatings is high, and the excellent mechanical properties such as promoting weather resistance and durability of the coating itself can be improved. have.

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

1. Synthesis Example 1 Resin

Cresol novolac type epoxy resin (manufactured by Dainippon Ink Chemical Co., Ltd., registered trademark "Epiclon" N-695, epoxy equivalent: 220 parts into four flasks with an agitator and a reflux condenser, 214) parts were added and dissolved by heating, 0.1 parts of hydrokinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine were added as a reaction catalyst.The mixture was heated to 95 to 05 ° C, and 72 parts of acrylic acid were slowly added dropwise. The reaction product was cooled to 80-90 ° C., tetrahydrophthalic anhydride 106 was added, the reaction was carried out for 8 hours, and then taken out after cooling.

Synthesis Example 1 A resin produced from a resin is a synthesis example of a polymerizable resin obtained by reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group of an esterified product of a novolak type epoxy compound and an unsaturated monocarboxylic acid.

2. Examples and Comparative Examples

Next, environmentally friendly solvent-free coating compositions were prepared according to the components and composition ratios as shown in Table 1 below.

ingredient ingredient (Unit: parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 residence Solvent-free epoxy resin (One) 100 150 100 50 100 (2) 100 100 50 100 Polymerizable compound (3) 20 20 20 (4) 20 20 30 20  Synthesis Example 1 Resin (5) 10 50 100 150 100 coloring agent (6) 10 20 10 30 20 20 20 Organosilicon-Containing Compound (7) 10 20 50 50 30 Organic solvent (8) 100 100 Hardener Amine Curing Agent (9) 50 100 50 75 100 (10) 50 100 100 100 Hardening accelerator (11) 50 50 50 50 50 50 50 Polymerizable compound (3) 20 20 20 (4) 20 20 30 20

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

(2) Bisphenol F type epoxy resin (Kukdo Chemical YDF-170)

(3) 1,4-butanediol diglycidyl ether (Aldrich)

(4) diethylene glycol diglycidyl ether (Aldrich)

(5) Synthesis Example 1 Resin

(6) TiO2 (white pigment)

(7) 3-aminopropyltributoxysilane (Aldrich)

(8) ethanol (Aldrich)

(9) isoprondiamine (Aldrich)

(10) m-xylenediamine (Aldrich)

(11) Polyethylenetetraamine (Aldrich)

3. Experimental Example

The results of the test results obtained by applying the cured material to the concrete specimen after preparing the environmentally friendly solvent-free coating composition having the weight ratio of 1: 1 with the main material and the hardener obtained in Examples 1 to 5 and the comparative examples are shown in the following table.

<Adhesion test method>

Test specimens were prepared by applying the prepared eco-friendly solvent-free coating composition to concrete specimens. The adhesion test evaluated the adhesion resistance by the 90 degree peeling adhesive force (unit N / 25mm) by the average value cut out three times by the rectangle of 25 mm width. At this time, the adhesive force is excellent, and the effect of material destruction of the concrete base material appears, and if it is good, the material destruction of the coating resin layer is judged to be defective.

<Resolution Resistance Test Method>

The solvent resistance test method calculates the number of rubs when the film is peeled off by immersing the test specimen in xylene on a glass plate with a thickness of 50 micrometers on a glass plate. 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.

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.

<Curing time>

The coating composition was applied to a glass plate of 25 mm × 25 mm × 2 m using an eco-friendly solvent-free coating composition prepared at 400 μm, and the radius and time were measured by using a coating film dryness tester.

<Workability>

It was applied using a spray and the ease of operation, leveling, defoaming and the like were observed.

<Film Appearance>

The gloss and color separation of the coated film, and the occurrence of cracking were observed.

<Durability>

An eco-friendly solvent-free coating composition was applied to a 300 mm x 300 mm x 3.2 mm plate at a thickness of 40 μm to form a coating film, which was kept at room temperature for 2 days and then subjected to an impact test. (KS M 5000)

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Adhesive Resistance Good Good Good Good Good Bad Bad Solvent resistance radish radish radish radish radish radish radish Accelerated weathering ◎ ◎ ◎ ◎ ◎ ○ ○ Water resistance ◎ ◎ ○ ◎ ◎ ◎ △ smell radish radish radish radish radish U U Mercury Not detected Not detected Not detected Not detected Not detected Detected Detected Semi-hardening time 5.1 5.6 3.8 4.5 4 6.2 6.4 Workability Good Good Good Good Good Good Good Coating appearance ◎ ◎ ○ ◎ ○ ○ △ durability ◎ ◎ ◎ ◎ ◎ ○ ○

Excellent: ◎

Normal: ○

Insufficient: △

As shown in Table 2, the coating film provided using the eco-friendly solvent-free coating composition of the embodiment is not only very excellent adhesion to the concrete, but also can form a dense coating coating on the surface of the workpiece, the coating coating film It does not contain an organic solvent, which is environmentally friendly, and the coated film has a fast drying speed, and can improve excellent mechanical properties such as accelerated weather resistance and durability. 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.

Claims (13)

(a) a solvent-free epoxy resin having an epoxy equivalent of 150 to 550 g / eq, ii) a polymerizable compound, and iii) a saturated or unsaturated polybasic anhydride in the hydroxyl group of an esterified product of a novolak-type epoxy compound with an unsaturated monocarboxylic acid. A polymerizable resin obtained by reacting the polymer, i) a colorant, i) a main body comprising an organo silicone-containing compound represented by the formula (1), (b) i) an amine curing agent, ii) a curing accelerator, and i) a polymerizable compound. Eco-friendly solvent-free coating composition having a curing agent.
[Chemical Formula 1]

R1 is selected from aminoethyl group, vinyl group, methyl group, glycidoxypropyl group, methacryloxybutyl, methacryloxypropyl, propyl substituted with fluorine, ethyl group substituted with fluorine, and R2 to R4 are ethoxy groups, butok It can be selected from the timing, hydrogen group, methoxy group, respectively.
The method of claim 1,
(A) iv) 80 to 200 parts by weight of a solvent-free epoxy resin having an epoxy equivalent of 150 to 550 g / eq, ii) 10 to 100 parts by weight of a polymerizable compound, and iv) a novolac epoxy based on the entire eco-friendly solvent-free coating composition. 10 to 100 parts by weight of a polymerizable resin obtained by reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group of an esterified product of a compound and an unsaturated monocarboxylic acid, i) 10 to 100 parts by weight of a colorant, i) organosilicon represented by the formula (1) (B) iii) 50 to 200 parts by weight of an amine curing agent, ii) 10 to 50 parts by weight of a curing accelerator, and iii) a curing agent containing 10 to 100 parts by weight of a polymerizable compound. Eco-friendly solvent-free coating composition, characterized in that.
3. The method of claim 2,
The mixing ratio of the main material and the curing agent is an environmentally friendly solvent-free coating composition, characterized in that it has a mixing ratio of 10 parts by weight to 100 parts by weight based on 100 parts by weight of the main material.
The method of claim 1,
The solvent-free epoxy resin having an epoxy equivalent of 150 to 550g / eq is an environmentally friendly solvent-free coating, characterized in that at least one selected from bisphenol A-based, bisphenol AD-based, novolak-based, bisphenol F-based and brominated bisphenol A-based Composition.
The method of claim 1,
The polymerizable compounds include monoepoxides of glycylglycidyl ether and alkyl glycidyl ethers, glycidyl esters, phenylglycidyl ethers, 2-ethylhexyl glycidyl ethers and parabutylbutylphenylglycols. Versatic acid type of cyl ether, neopentyl diglycidyl ether, 1, 4- butane diglycidyl ether, cyclohexane dimethanol diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol di Eco-friendly solvent-free coating composition, characterized in that at least one selected from the diepoxide system of glycidyl ether, 1,4-butanediol diglycidyl ether.
The method of claim 1,
The organo silicon-containing compound represented by the formula (1) is 3-glycidoxypropyltriethoxysilane, 3-aminopropyltributoxysilane, 3-methacryloxybutylsilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethoxysilane, 3-methacryloxyethoxysilane, 3-methacryloxybutylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, vinylmethyldimethoxysilane, Eco-friendly dancing selected from one or more selected from methyltriisopropoxysilane, methyltriacetoxysilane, beta-aminoethyl-gamma-aminopropylethoxysilane, fluoropropyltriethoxysilane, and trifluoropropyltrimethoxysilane Formulation coating composition.
The method of claim 1,
Eco-friendly solvent-free coating composition further comprises one or more additives selected from antifoaming agent, dispersant, UV stabilizer, sunscreen, inorganic filler, emulsifier, surfactant, viscosity control agent, antioxidant, crosslinking agent.
The method of claim 1,
The colorant is an environmentally friendly solvent-free coating composition, characterized in that at least one selected from extender pigments, coloring pigments, dyes.
The method of claim 1,
The amine-based curing agent is an environmentally friendly solvent-free coating composition, characterized in that at least one selected from the amine-based curing agent selected from the group consisting of acyclic polyamine, aliphatic polyamine, aromatic polyamine, and amine adducts.
The method of claim 1,
As a hardening accelerator, aliphatic diamine which is any of diethyl triamine (DETA), ethylene diamine (EDA), triethylene tetraamine (TETA), tetraethylene pentaamine (TEPA), and diethyl aminopropylamine (DEAPA). Methanediamine (MDA), N-aminoethylpiperadine (N-AEP), m-xylenediamine (m-XDA), 1,3-bisamino methyl cyclohexane (1,3-AC) isophoronediamine ， Diaminocyclohexane ， 4-4bisparaamino-cyclohexylmethane, diethylpropanediamine (N, N, -Diethyl-1,3-propanediamine), hydroxyethyl pentanediamine (N- (2-Hydroxyethyl)- Eco-friendly solvent-free coating composition, characterized in that at least one selected from 1,3-pentanediamine, dibutyl propanediamine (N, N-di-n-butyl-1,3-Propanediamine).
delete delete The coating film obtained by apply | coating the environmentally friendly solvent-free coating composition of any one of Claims 1-10.