KR100956752B1 - Room temperature curing organic-inorganic hybrid coating agents - Google Patents

Abstract

PURPOSE: A room temperature-curable organic/inorganic hybrid coating agent is provided to secure a storage stability, a various color embodiment, and an excellent working ability. CONSTITUTION: A room temperature-curable organic/inorganic hybrid coating agent comprises a 2 liquid type coating agent and a hardener. The liquid type coating agent is formed with metal alkoxide selected from the group consisting of tetramethyl orthosilicate, tetra-ethyl orthosilicate and their mixture, organic modified alkoxy silane, an organic polymer, an organic solvent, water and a catalyst. The hardener is formed with alicyclic denaturation amine, amino-silane, an antifoaming agent, a leveling agent and a solvent.

Description

Room temperature curing organic-inorganic hybrid coating agents

The present invention relates to a two-part coating agent comprising a main body of a room temperature curing type and a curing agent, and for forming a coating having excellent heat resistance, mechanical properties, acid resistance, chemical resistance, and stain resistance on various substrates.

The invention also relates to articles comprising coatings formed by coating with such two-part coatings.

There are approximately three methods for producing a hybrid coating composed of a composite of an inorganic material and an organic material.

The first method is a blending method, which simply mixes inorganic and organic polymers. This method is the easiest and simplest, and it is possible to express the characteristics of the organic-inorganic complex to some extent, but since it is a simple mixture, the high heat resistance, high strength, high hardness, high wear resistance, high chemical resistance, and high durability of the organic-inorganic complex It is difficult to fully express characteristics such as chemical resistance, high water resistance, and strong adhesion to inorganic substances.

In addition, the coating agent prepared by the above method is difficult to uniformly distribute the particles of the organic-inorganic composite, and partially pulled out, and some parts of the organic material and some parts of the inorganic material clearly stand out to provide a uniform coating. There is a disadvantage that is difficult to obtain.

As a second method, there is a method of synthesizing an organic polymer-inorganic polymer, which combines an organic polymer and an inorganic polymer already synthesized to form an organic-inorganic composite, and the characteristics of the hybrid coating prepared by such a method. Is more stably expressed compared to the coating obtained by the first method. However, since the coating agent is prepared by the bonding of polymers that have already been formed, it is difficult to show the properties of an intact hybrid coating partly because the properties of the organic part and the part of the inorganic part partly appear.

Third, there is an organic polymer-inorganic particle synthesis method, which is an ultimate organic-inorganic hybrid that indiscriminately binds inorganic particles of molecular units to the formed organic polymer chain and consequently changes the properties of the organic polymer. It is a method to express the characteristics of the coating agent.

Coatings composed of most organic-inorganic composites produced by the method as described above, when applied, are subjected to more than 200 heat to densify the tissue of the inorganic material. The reason for this is that without heat, the organization is in poor shape and cannot function as a product.

The present invention aims to provide a coating having excellent storage stability, various colors, and excellent workability in order to solve the disadvantages of the conventional organic or inorganic coating.

In the present invention, a hybrid coating agent composed of a complex of inorganic and organic materials, comprising: a subject composed of a metal alkoxide, an organomodified alkoxysilane, an organic polymer, a solvent, water and a catalyst; The object of the present invention is achieved by providing a two-component coating agent comprising a curing agent composed of an alicyclic modified amine, an aminosilane, an antifoaming agent, a leveling agent, a filler and a solvent.

According to the present invention, as a hybrid coating agent composed of a composite of an inorganic material and an organic material, there is provided a coating agent having a room temperature curing type, environmentally friendly and excellent workability. Such coatings also show that the coatings produced therefrom 1) exhibit good abrasion resistance due to high hardness, 2) react with concrete to integrate with the adherend, resulting in high adhesion and long-term adhesion, and 3) thermal stability of conventional epoxy. Unlike urethane-based flooring, it has flame retardancy, 4) stable performance against water, 5) stable to acid and alkali, and 6) excellent pollution resistance, so it is not easily contaminated and long-term durability is very easy to remove after contamination. It is a floor coating to have.

1 is a process diagram for the process of producing the subject matter in the two-part coating of the present invention.
Figure 2 is a photograph of the flame test for the coating according to the invention and the coating according to the prior art.
3 is a result of the wear resistance / hardness test for a coating according to the prior art for a coating according to the prior art.
4 is a water resistance test results for the coating according to the invention and the coating according to the prior art.
5 is a micrograph of the attachment surface when the coating according to the invention is formed on concrete.
6 is a photograph showing that the coating according to the present invention is stain resistant.

The present invention is a two-component coating agent for coating, 15 to 30 selected from the group consisting of tetramethyl orthosilicate (Si (OCH ₃ ) ₄ ), tetraethyl orthosilicate (Si (OC ₂ H ₅ ) ₄ ) and mixtures thereof Wt% metal alkoxide; γ-methacryloxypropyl trimethoxysilane: H ₂ C = CH (CH ₃ ) C (O) OC ₃ H ₆ -Si (OCH ₃ ) ₃ ), γ- Γ-glycidoxypropyl trimethoxysilane (CH ₂ (O) CHCH ₂ OC ₃ H ₆ -Si (OCH ₃ ) ₃ ) and 11 to 28% by weight of an organic modification selected from the group consisting of Alkoxysilanes; Bisphenol A type Epoxy resin, Bisphenol F type Epoxy resin, Hydrogenated Bisphenol A type Epoxy resin, Brominated bisphenol A type Epoxy resin ( 20 to 35% by weight of organic polymer selected from the group consisting of Brominated Bisphenol A type Epoxy resin, Novolac type Epoxy resin, and mixtures thereof; 10 to 40% by weight of organic solvent; A subject consisting of 0.1 to 10 weight percent water and 0.01 to 5 weight percent catalyst; 70 to 90% by weight of an alicyclic modified amine; 0.1 to 10 weight percent aminosilane; 0.001 to 1.0 weight percent antifoaming agent; 0.001 to 1.5% by weight of leveling agent; And it provides a two-component coating comprising a curing agent composed of 5 to 25% by weight of the solvent.

The two-component coating of the present invention, Preferably, the curing agent is 0.01 to 2% by weight of the color separation agent based on the total weight of the curing agent; 0.01-2% by weight of a pigment wetting dispersant; 5 to 40% by weight of inorganic pigments; And 5 to 40% by weight of filler.

The two-part coating agent of the present invention, Preferably, the organic solvent in the subject is anhydrous ethyl alcohol (anhydrous C ₂ H ₅ OH); Propylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ), isopropyl alcohol, cellosolve acetate ( CELLOSOLVE ACETATE), ethyl acetate, propylene glycol monomethyl ether acetate, and mixtures thereof.

The two-part coating agent of the present invention preferably has a weight ratio of the anhydrous ethyl alcohol: auxiliary solvent of 1: 3 to 3: 1 in the organic solvent in the main body.

The two-part coating agent of the present invention, preferably, the catalyst in the main body is itaconic acid (C ₅ H ₆ O ₄ ), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), Hydrochloric acid (HCl) and boric acid (H ₃ BO ₃ ) and mixtures thereof.

The two-component coating of the present invention, Preferably, the curing agent is a cycloaliphatic modified amine is a hydrogenated cycloaliphatic modified amine of Docure KH-816 or Docure KH-818B (Kukdo Chemical); amino silane, γ-aminopropyltriethoxysilane (Silquest A-1100, Momentive Performance Materials Inc.); Fluorosilicone copolymer (Dowcorning FS-1265, 300-10,000 CST), ethylmethyl, methyl (2-phenylpropyl) siloxane (Dowcorning 56 Additive), polydimethylsiloxane (Shin-etsu, KF-96, 10-100,000 CST ) And antifoaming agents selected from the group consisting of; Leveling agents that are dimethyl, methyl (polyethylene oxide acetate-capped) siloxane (Dowcorning 57 Additive); Talc, Barium sulfate, Calcium carbonate, Aluminum Hydroxide, Zinc Oxide, Calcined Kaolin, Magnesium Carbonate and their Filler selected from the group consisting of mixtures; And polyethylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ), and mixtures thereof Contains the selected solvent.

The two-component coating of the present invention, preferably, the color separation agent in the additional component of the curing agent is a carboxylate solution of polyamineamide (ANTI-TERRA-205, BYK-Chemie or ANTI-TERRA-204, BYK-Chemie) Pigment wet dispersant is composed of salt polyamine amide and polyester (DisperBYK-2095, BYK-Chemie), the pigment from the group consisting of TiO ₂ , Iron Oxide, Chromium Oxide and mixtures thereof Is selected.

The two-part coating agent of the present invention, preferably, in the main component, the organic solvent is anhydrous ethyl alcohol (anhydrous C ₂ H ₅ OH), propylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol mono A mixture of auxiliary solvents selected from the group consisting of propyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ), and mixtures thereof; The catalyst is itaconic acid (C ₅ H ₆ O ₄ ), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), hydrochloric acid (HCl), boric acid (H ₃ BO ₃ ) and mixtures thereof It is selected from the group consisting of; Among the curing agent components, the cycloaliphatic modified amine is selected from Docure KH-816 (Kukdo Chemical), Docure KH-818B (Kukdo Chemical) and mixtures thereof; Aminosilane is γ-aminopropyltriethoxysilane (Silquest A-1100, Momentive Performance Materials Inc.); Defoamers include fluorosilicone copolymer (Dowcorning FS-1265, 300-10,000 CST), ethylmethyl, methyl (2-phenylpropyl) siloxane (Dowcorning 56 Additive), polydimethylsiloxane (Shin-etsu, KF-96, 10- 100,000 CST) and mixtures thereof; Leveling agent is dimethyl, methyl (polyethylene oxide acetate-capped) siloxane (Dowcorning 57 Additive); The color separation inhibitor is a carboxylate solution of polyamineamide (ANTI-TERRA-205, BYK-Chemie or ANTI-TERRA-204, BYK-Chemie); The pigment wetting dispersant is selected from the group consisting of salt polyamine amides, polyesters (DisperBYK-2095, BYK-Chemie) and mixtures thereof; Inorganic pigments are selected from the group consisting of TiO ₂ , Iron Oxide, Chromium Oxide and mixtures thereof; Fillers include Talc, Barium sulfate, Calcium carbonate, Aluminum Hydroxide, Zinc Oxide, Calcined Kaolin, Magnesium Carbonate and Selected from the group consisting of mixtures thereof; The solvent is a group consisting of polyethylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ) and mixtures thereof Is selected from.

The two-part coating agent of the present invention is preferably a two-part coating agent composed of the above-mentioned subject: curing agent in a weight ratio of 1.5: 1 to 3.5: 1.

The two-component coating agent of the present invention, preferably, the ring opening reaction of the epoxy group of the organic polymer is caused by the interaction of the organic modified alkoxysilane and the organic polymer in the subject, the organic modified alkoxysilane and the organic polymer by such ring opening Is covalently bonded, and the hydrolysis reaction of the added catalyst and water changes the alkoxy group of the organomodified alkoxysilane into a silanol group, where methanol is generated and a silanol moiety derived from the organomodified alkoxysilane and a metal alkoxide derived The silanol moiety is linked by O-bonds.

The present invention also uniformly mixes the main component of the two-part coating agent of the present invention and the curing agent in a weight ratio of 1.5: 1 to 3.5: 1 weight ratio, applied to the substrate, and then cured for 2 to 7 days at 10 to 30 temperature Thereby providing a coated article formed.

Substrates to which the two-part coatings of the invention can be applied are preferably selected from the group consisting of plastic products, metallic substrates, wood, cement, concrete, and glass.

The coating agent of the present invention is a two-component product consisting of a main body and a curing agent. Among the main components of the subject, metal alkoxides as silica precursors act as precursors of the inorganic silicates of organic-inorganic hybrid coatings, which consist of tetramethylorthosilicate or tetraethylorthosilicate, which are used in the form of monomers, dimmers, or trimers do. Such metal alkoxide has a silanol structure as follows by hydrolysis.

Si (OCH ₃ ) ₄ + 4 H ₂ O-> Si (OH) ₄ + 4 (CH ₃ OH)

The metal alkoxide functions to increase the heat resistance, abrasion resistance, hardness, chemical resistance, solvent resistance, and stain resistance of the two-part coating agent of the present invention, and in particular, functions to increase the bonding strength with the inorganic adherend. The material which hydrolyzed such metal alkoxide can be all natural hardening, thermal hardening, and chemical hardening, and it is possible to control the curing time in use by adjusting the hydrolysis rate. Higher hydrolysis rates result in faster curing and a harder coating, while lower hydrolysis rates result in lower curing rates and softer coatings. The form of the coating is a glassy gloss, and the condensation reaction during curing, the moisture is released to dry shrinkage is likely to occur, and this is a disadvantage that is liable to cracking of the coating.

The organomodified alkoxysilane used in the two-part coating agent of the present invention is used as a coupling agent for chemically bonding a metal alkoxide to an organic polymer. Si (OCH ₃ ) ₃ in such organic modified alkoxysilane reacts with water to form Si (OH) ₃ , and the formed Si (OH) ₃ reacts with the OH group of the metal alkoxide to form an oxygen bond.

R-Si (OH) ₃ + Si (OH) _4- > R-Si (OH) ₂ -O-Si (OH) ₃ + H ₂ O

(Wherein R is an organic moiety having 1 to 12 carbon atoms of the organomodified alkoxysilane used in the present invention)

The organic modified alkoxysilane which forms an oxygen bond with the metal alkoxide gives elasticity to the coating by the action of the organic modification group, and suppresses the occurrence of cracks. In addition, the physical properties such as alkali resistance / water resistance, which are disadvantages of the inorganic system, are partially improved.

The organic polymer used in the subject of the two-part coating of the present invention increases water resistance / alkali resistance, which is a disadvantage of the inorganic system, and imparts toughness to the coating, thereby forming a strong and tough organic-inorganic hybrid coating. The chemical structure of the organic polymer used in the present invention is as follows.

Bisphenol A type epoxy resin

Bisphenol F type epoxy resin

Hydrogenated A Type Epoxy Resin

Brominated Bisphenol A Type Epoxy Resin

Novolak Type Epoxy Resin

The organic polymer used in the present invention is combined with the organic modified group of the organomodified alkoxysilane, thereby imparting toughness to the product, thereby compensating for the weakness of the inorganic system. In addition, it functions to increase the water resistance / alkali resistance of the product. However, since it is weak in heat resistance and not permeable to the coating, it is likely to be lifted due to water pressure when used for a long time.

In the construction of the organic-inorganic composite forming the subject of the two-part coating agent of the present invention, the ratio of the metal alkoxide, organo-modified alkoxysilane and organic polymer is determined according to the respective functions. Metal alkoxides are involved in the formation of minerals. Organomodified alkoxysilanes are involved in the chemical bonding of inorganic and organic polymers. Organic polymers express the properties of organic matter. For this reason, depending on these ratios, the properties of the organic material may be strong or the properties of the inorganic material may be strong.

The metal alkoxide used in the two-part coating of the present invention is used in an amount of 15% to 30% by weight based on the total weight of the main body. When the amount of the metal alkoxide exceeds 30%, the water resistance and alkali resistance of the coating formed by the coating agent are significantly lowered. On the contrary, when it is less than 15 weight%, the characteristic of organic substance is strongly expressed and heat resistance and abrasion resistance will fall remarkably. Organomodified alkoxides are used in amounts of 11 to 28% by weight based on the total weight of the subject. If the amount of the organic modified alkoxide exceeds 28% by weight, it is too weak to reduce the strength of the coating film. If the amount of the organic modified alkoxide is less than 11% by weight, the elasticity and scratch resistance of the coating decreases. On the other hand, the organic polymer is used in an amount of 20 to 35% by weight based on the total weight of the subject. When the amount of the organic polymer exceeds 35% by weight, the heat resistance is weak and there is no air permeability in the coating film, so it is easy to be lifted due to water pressure when used for a long time, and when the amount is less than 20% by weight, the coating agent is liable to become brittle. Difficult to do

The solvent used in the subject of the two-part coating of the present invention uses a solvent to uniformly mix the metal alkoxide, the organomodified alkoxysilane and the organic polymer material and to facilitate the mixing with water during hydrolysis. Such a solvent may be mixed with a solvent having a different boiling point rather than a single substance, thereby controlling the surface drying rate of the coating to suppress cracking during curing or to increase the density of the coating internal structure.

The solvent used for the subject of the two-part coating of the present invention is used in an amount of 10 to 40% by weight based on the total weight of the subject, and when the amount of the solvent exceeds 40% by weight, the curing time is too delayed. It can be absorbed excessively in adherends such as concrete, and using less than 10% by weight can cause cracks in the coating.

The catalyst used in the subject of the two-part coating of the present invention increases the hydrolysis rate of the metal alkoxide and the organo-modified alkoxysilane and improves the storage stability of the finished product.

For this purpose, anhydrous or organic acid-based catalysts are used. The amount of such catalyst is used in an amount of 0.01 to 5% by weight. If the amount of the catalyst exceeds 5% by weight, cracks may occur in the coating, and if the amount of the catalyst is less than 0.01% by weight, the hydrolysis may not proceed sufficiently. You may not.

Water used for the subject of the two-part coating of the present invention is used for the hydrolysis of the metal alkoxide and the organo-modified silane, the addition amount is 0.1 to 10% by weight.

The aliphatic modified amine used in the curing agent of the two-part coating agent of the present invention is a hydrogenated alicyclic amine modified alicyclic modified amine having an amine value of 220 to 320 KOH / g. Aliphatic modified amines crosslink the organic groups of the subject and silanol groups of the inorganic material, which accelerates the curing of the coating and increases the strength. Such aliphatic modified amines are used in an amount of 70 to 90% by weight based on the total weight of the curing agent. If the content exceeds 90% by weight, cracks of the coating film occur, and less than 70% by weight, the curing of the coating film is delayed. have.

When the aminosilane used in the curing agent of the two-part coating agent of the present invention is applied to only the cycloaliphatic modified amine as the curing agent, when the aminosilane is applied as a curing aid, the toughness of the coating after curing is significantly increased. , Wear resistance of the coating is increased. The aminosilane is used in an amount of 0.1 to 10% by weight based on the total weight of the curing agent, but if it exceeds 10% by weight, there is a high possibility of turbidity, if less than 0.1% by weight, there is a disadvantage in the toughness of the coating film .

The antifoaming agent used in the curing agent of the two-part coating agent of the present invention is composed of a surfactant-like structure in which the main material synthesized by the sol-gel method has both a hydrophilic OH group and a hydrophobic CH ₃ group at the same time. In order to break these bubbles, it is used. The amount of antifoaming agent suitable for such blisters is from 0.001 to 1.0% by weight, based on the total weight of the curing agent.

The leveling agent used in the curing agent of the two-part coating agent of the present invention may be used to compensate for the roughening of the coating surface by using an antifoaming agent. The amount of leveling agent suitable to compensate for the roughness of the coating due to the use of antifoaming agents is from 0.001 to 1.5% by weight, based on the total weight of the curing agent.

The solvent used for the hardening | curing agent of the two-part coating agent of this invention is added for the purpose of the improvement of workability at the time of the cleaning and manufacturing convenience, and construction after work. Such a solvent uses a high boiling point to suppress bubble generation. The amount of solvent suitable for such purpose is 5 to 25% by weight.

The curing agent of the two-part coating agent of the present invention may further include a pigment, a filler, a pigment wet dispersant and a color separation agent. Pigments additionally included in the curing agent of the two-component coating of the present invention, there are various kinds of inorganic pigments to express a variety of colors, organic pigments are poor in weather resistance, so do not use as possible because of the possibility of discoloration, discoloration. It is better not to. Such inorganic pigments are used in appropriate amounts taking into account the color of the coating and are used in amounts of 5 to 40% by weight, based on the total weight of the curing agent.

The filler used in the curing agent of the two-part coating agent of the present invention affects the strength and toughness of the formed coating film, and the amount added is 5 to 40% by weight of the total amount of the curing agent.

On the other hand, when an inorganic pigment is used, the pigment wetting dispersant and the color separation agent increase the fluidity of the pigment to facilitate the operation and prevent color separation due to the specific gravity difference between the pigments. Suitable amounts of pigment wetting dispersant and color separation inhibitor for this purpose are 0.01 to 2% by weight and 0.01 to 2% by weight, respectively.

Topic Manufacturing Process

The subject of the two-part coating agent of the present invention is to put the epoxy (organic polymer) and the organic modified silane into the reactor, and after stirring for 30 minutes at 25 to 30 ℃, ethylene glycol solvents are added and stirred for another 30 minutes. Then, distilled water and catalyst mixture are added dropwise, and the temperature is raised to 70 ° C. and stirred for 2 hours. Subsequently, a mixture of the metal alkoxide partially hydrolyzed and the metal alkoxide + ethanol + water + catalyst was added, and stirred at 70 ° C. for 1 hour. Subsequently, distilled water + catalyst mixture is added dropwise to the reactor and stirred at 70 ° C. for 2 hours. Subsequently, boric acid is added and stirred at 70 ° C. for 2 hours to obtain the desired subject matter.

A flowchart of the manufacturing process of the subject matter is shown in FIG.

In one embodiment, the two-part coating agent of the present invention is a silica precursor, wherein the metal alkoxide is tetraethylorthosilicate, and the organomodified alkoxysilane is γ-glycidoxypropyltrimethoxysilane. The organic polymer is an epoxy resin of bisphenol-A type of diglycidyl ether of bisphenol-A type.

It is also possible to use cyclo aliphatic modified Bisphenol A Type epoxy resins instead of epoxy resins of bisphenol-A type diglycidyl ether to increase weather resistance.

Distilled water, ethylene glycol monopropyl ether, or anhydrous ethyl alcohol is used as a medium for hydrolysis, and nitric acid (60-62%), hydrochloric acid (35%), or boric acid (99% <) is used as an acid catalyst. .

The physical properties of the coating prepared with the two-part coating agent of the present invention are mainly determined by the mixing ratio of the metal alkoxide and the organic polymer, and the organic modified alkoxysilane is adjusted in proportion to the amount of the metal alkoxide used.

In one aspect, the subject of the two-part coating of the present invention is, after the reaction as described above, 15-30% by weight of tetraethylorthosilicate (Teos), 11-28% by weight of γ-glycidoxypropyl trimethoxysilane. %, 20 to 35% by weight epoxy resin of diglycidyl ether of bisphenol-A type, 2.5 to 30% by weight ethylene glycol monopropyl ether, 2.5 to 30% by weight anhydrous ethyl alcohol, and 0.01 to 5% by weight acid catalyst do.

The reactor sphere of the main constituents of such a subject is:

In the presence of an epoxy group, the ring opening reaction of the epoxy group occurs by the interaction of the organomodified alkoxysilane and the bisphenol A type epoxy resin, and the organic bond between the organomodified alkoxysilane and the bisphenol A type epoxy resin occurs due to the epoxy ring opening. The added catalyst promotes the ring opening reaction.

In addition, due to the hydrolysis reaction between the added catalyst and water, the alkoxy group of the organomodified alkoxysilane is converted into a silanol group, and methanol is generated at this time.

The silanol portion of the organomodified alkoxysilane and the silanol portion of the hydrolyzed metal alkoxide are linked by O-links.

The compound is molecular weight is increased through a polymerization reaction, and may be present as a partial compound depending on the combination of the epoxy and the organic modified alkoxysilane, metal alkoxide to be added.

<Hardener manufacturing process>

In one embodiment, as a curing agent in the two-component coating of the present invention, a hydrogenated cycloaliphatic amine-modified cycloaliphatic modified amine (Docure KH-816, Docure KH-818B, Kukdo Chemical) is used as a main component, and a curing aid. As the γ-aminopropyltriethoxysilane (Silquest A-1100, Momentive Performance Materials Inc.) is used.

Γ-aminopropyltriethoxysilane, which can be used as a curing aid, serves to increase dry adhesion of coated coatings and to improve adhesion and toughness of coatings while maintaining pot life. do.

Defoamers are, for example, Dow Corning FS-1265, 300-10,000 CST, Dow Corning 56 additive, Shin-etsu KF-96, 10-100,000 CST, and the leveling agent is, for example, Dow Corning 57 to be.

As an optional component, the color separation inhibitor is BYK ANTI-TERRA-205 and the pigment wetting dispersant is DisperBYK-2095. In addition, as an optional component, pigments used in curing agents to express color are suitable inorganic pigments, such pigments include TiO ₂ , Iron Oxide, Chromium Oxide, etc. Materials such as Talc, Barium sulfate, Calcium carbonate, Aluminum Hydroxide, Zinc Oxide, Calcined Kaolin, Magnesium Carbonate This can be used.

The solvent added to the curing agent in the two-part coating agent of the present invention is ethylene glycol monopropyl ether (Eastmann).

Preferably, the curing agent raw material blend in the two-part coating of the present invention is 70 to 90% by weight of KH-816 or KH-818B, 0.1 to 10% by weight of Silquest A-1100, 0.001 to 0.001, based on the total weight of the curing agent. 0.5 wt% FS-1265, 0.001-1.0 wt% Dow Corning 56, 0.001-1.5 wt% Dow Corning 57, 0.001-1.0 wt% KF-96, 5-25 wt% ethylene glycol monopropyl ether .

In addition, 5 to 40% by weight of the inorganic pigment, 5 to 40% by weight of the total weight of the curing agent

Filler, 0.01-2% by weight of DisperBYK-2095, 0.01-2% by weight of ANTI-TERRA-205.

The process of forming a coating using the two-part coating of the present invention is as follows.

Subject of the two-part coating of the present invention: The curing agent is mixed in a weight ratio of 1.5: 1 to 3.5: 1, stirred for at least 3 minutes, and then first applied to the adherend with a roller, a brush, a spray, or the like. After 4 hours after the 1st application, apply by 2nd finish. After at least 24 hours after the second application, a clear, rigid coating is formed.

Hereinafter, the present invention has been described with reference to embodiments, but those skilled in the art may variously modify and modify the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. It will be appreciated that it can be changed.

Example

<Production of Topic>

Example 1

760 g of TEOS and 530 g of anhydrous ethanol were added to a 5 liter round bottom flask, followed by vigorous stirring for 30 minutes while maintaining at 30 ° C. Into the mixture, a solution containing 3.83 g of hydrochloric acid in 87.28 g of distilled water was added dropwise to check the temperature increase, and then stirred for 1 hour while maintaining the temperature of 40 ° C. 7.6 g of boric acid was added to the stirred mixture for 1 hour, and the mixture was stirred for 1 hour while maintaining 40 ° C. A mixture of 1236 g of epoxy resin of bisphenol-A diglycidyl ether, 530.30 g of γ-glycidoxypropyltrimethoxysilane, and 794.58 g of ethylene glycol monopropyl ether was added to the mixture, and the mixture was heated to 30 ° C. Maintain the temperature and stir for 30 minutes. After stirring for 30 minutes, a solution of 4.3 g of nitric acid mixed with 45.82 g of distilled water was added dropwise to the flask to check the temperature increase, and then heated to 70 ° C. for 4 hours, followed by natural cooling.

The reactants were clear and slightly yellowish liquid, and the storage stability was confirmed not to be more than 5 months. When mixed with the curing agent, the workable pot life was as short as 40 minutes and the coating was clear but slightly bite.

 Example 2

750 g of TEOS and 550 g of anhydrous ethanol were added to a 5 liter round bottom flask, followed by vigorous stirring for 30 minutes while maintaining at 30 ° C. To the mixture, a solution of 3.75 g of hydrochloric acid mixed in 60 g of distilled water was added dropwise to confirm the temperature increase, and then stirred for 1 hour while maintaining the temperature of 40 ° C. To the mixture was added a mixture of 1250 g of epoxy resin of bisphenol-A diglycidyl ether, 575 g of gamma -glycidoxypropyltrimethoxysilane, and 825 g of ethylene glycol monopropyl ether, and maintained at 30. After stirring for 60 minutes, the temperature was raised to 70 ° C and stirred for 4 hours. A solution containing 3.25 g of nitric acid in 30 g of distilled water was added dropwise to the flask to check the temperature increase, and then heated to 70 ° C. for 2 hours to react, followed by natural cooling.

The reaction was a clear, slightly yellowish liquid, and after 3 days a cloudy foreign body was formed. When mixed with the curing agent, the working pot life was as short as 30 minutes, the coating was opaque and cracking occurred after curing.

Example 3

A mixture of 290 Kg of cycloaliphatic modified bisphenol-A type epoxy resin, 200 Kg of γ-glycidoxypropyltrimethoxysilane, and 185.3 Kg of ethylene glycol monopropyl ether was added to a 1.2 ton stainless steel reactor at 25 ° C. Stir vigorously for 30 minutes. The mixture of 900 g of nitric acid and 3.6 Kg of distilled water was added to the mixture in a dropwise manner to confirm the temperature increase, and then the temperature was raised to 70 ° C. and stirred for 2 hours. After the mixture was partially hydrolyzed with TEOS 210Kg, anhydrous ethanol 90Kg, distilled water 5.43Kg, and hydrochloric acid 260g, the mixture was stirred at 70 ° C for 1 hour, and the mixture was mixed with distilled water 12.67Kg and 780g hydrochloric acid in the reactor. Into the dropwise addition and stirred at 70 ℃ for 2 hours. 1.06 Kg of boric acid was added to the mixture, followed by reaction at 70 ° C. for 2 hours, followed by natural cooling.

The reaction product prepared as described above was a colorless transparent liquid, which was abnormal even after 6 months or more. When mixed with the curing agent, the working pot life was long as about 4 hours, the state of the coating is transparent, excellent physical properties such as strength and wear resistance, and the surface state was flat.

Example 4

In the formulation of Example 3, an alicyclic modified bisphenol-A type epoxy resin was replaced with a cyclo aliphatic modified Bisphenol A type epoxy resin.

The product had similar physical properties and weather resistance as in Example 3 than in Example 3.

<Production of Hardener>

Example 5

1200 g of KH-816, 40 g of Silquest A-1100 and 100 g of ethylene glycol monopropyl ether were added to a 4-liter PE container and stirred at medium speed. 12 g of DisperBYK-2095, 0.4 g of FS-1265, 4 g of Dow Corning 56 and 0.4 g of KF-96 were diluted in 100 g of ethylene glycol monopropyl ether, and stirred in a PE container for 20 minutes at high speed. Thereafter, 934.4 g of TiO2, 105.2 g of iron oxide (Black), and 280 g of filler were added to the liquid mixture to disperse the pigment at high speed. After confirming that the pigment and the filler are dispersed, the mixture is put into a ring mill of 4 liter capacity to sufficiently pulverize the pigment particles for 1 hour or more. Thereafter, the pigment mixture is transferred to a PE container in a ring mill, followed by high speed stirring, and 12g of Dow Corning 57 and 12g of ANTI-TERRA-205 are sequentially added and stored in a separate storage container after high speed stirring for 20 minutes.

The product had no pigment precipitation, excellent storage stability, no color separation and excellent antifoaming effect.

Example 6

1200 g of KH-816, 40 g of Silquest A-1100 and 100 g of ethylene glycol monopropyl ether were added to a 4-liter PE container and stirred at medium speed. 12 g of DisperBYK-2095, 0.4 g of FS-1265, 4 g of Dow Corning 56 and 0.4 g of KF-96 were diluted in 100 g of ethylene glycol monopropyl ether, and stirred in a PE container for 20 minutes at high speed. Thereafter, 1039.6 g of chromium oxide green and 280 g of filler are added to the liquid mixture to disperse the pigment at high speed. After confirming that the pigment is dispersed, the mixture is put into a ring mill of 4 liter capacity to sufficiently pulverize the pigment particles for 1 hour or more. After moving the pigment mixture from the ring mill to the PE container with high speed stirring, 12g of Dow Corning 57 and 12g of ANTI-TERRA-205 are sequentially added and stored in a separate storage container after high speed stirring for 20 minutes.

The product had no pigment precipitation, excellent storage stability, no color separation and excellent antifoaming effect.

Example 7

In a 4-liter PE container, 2400 g of KH-818B, 160 g of Silquest A-1100, and 160 g of ethylene glycol monopropyl ether were added and stirred at medium speed. Here, FS-1265 5.6g, Dow Corning 56 8g, Dow Corning 57 24g is diluted in 160g of ethylene glycol monopropyl ether, added to PE container, stirred at high speed for 30 minutes, and stored in a separate storage container.

The product was excellent in shelf life, and a transparent and high strength transparent coating was formed.

Example 8 (Application of Coating Agent)

Subject: The hardener was mixed in a weight ratio of 10: 3, stirred for 3 minutes, and then first applied to the wood substrate with a roller. After 4 hours after the first coating, the coating was secondarily finished. 24 hours after the second application, a clear and rigid coating was formed.

<Test of Physical and Chemical Properties>

General physicochemical test data for the coatings prepared in Example 8 are shown in the table below.

As can be seen from the table above, the coating made from the two-part coating of the present invention has high hardness / high strength (pencil hardness of 3H or more). It has high scratch / wear resistance (more than twice as physical properties as epoxy in Taber Abrasion test), and high acid / alkali / water resistance.

<Heat resistance comparison test>

A flame test photograph of the coating prepared in Example 8 and the coating according to the prior art is shown in FIG. 2. As can be seen in Figure 2 the coating according to the invention in terms of heat resistance is significantly superior to the coating according to the prior art.

<H-22, 1,000g, Wear resistance / hardness comparison test under 500 cycles>

The results of the abrasion resistance / hardness test for the coating prepared in Example 8 and the coating according to the prior art are shown in FIG. 3. As can be seen in Figure 3 the coating according to the invention in terms of wear resistance / hardness is significantly superior to the coating according to the prior art.

<Water resistance comparison test>

The water resistance test results for the coating prepared in Example 8 and the coating according to the prior art are shown in FIG. 4. As can be seen in Figure 4 the coating according to the present invention in terms of water resistance is significantly superior to the coating according to the prior art.

<Adhesion test on concrete>

A micrograph of the attachment surface when the coating prepared in Example 8 is formed on concrete is shown in FIG. 5. As can be seen in Figure 5 the coating according to the invention is strongly adhered to the concrete by the hydration reaction with the concrete.

<Pollution resistance test>

6 shows that the coating prepared in Example 8 is not contaminated with oily magic. As can be seen from Figure 6 the coating according to the invention is not contaminated with oily magic.

Claims (12)

As a two-part coating agent for coating, 15 to 30% by weight selected from the group consisting of tetramethyl orthosilicate (Si (OCH ₃ ) ₄ ), tetraethyl orthosilicate (Si (OC ₂ H ₅ ) ₄ ) and mixtures thereof Metal alkoxides; γ-methacryloxypropyl trimethoxysilane: H ₂ C = CH (CH ₃ ) C (O) OC ₃ H ₆ -Si (OCH ₃ ) ₃ ), γ-glycidoxypropyl trimeth Γ-glycidoxypropyl trimethoxysilane (CH ₂ (O) CHCH ₂ OC ₃ H ₆ -Si (OCH ₃ ) ₃ ) and 11 to 28% by weight of an organic modified alkoxysilane selected from the group consisting of a mixture thereof; Bisphenol A type Epoxy resin, Bisphenol F type Epoxy resin, Hydrogenated Bisphenol A type Epoxy resin, Brominated bisphenol A type Epoxy resin ( 20 to 35% by weight of organic polymer selected from the group consisting of Brominated Bisphenol A type Epoxy resin, Novolac type Epoxy resin, and mixtures thereof; 10 to 40% by weight of organic solvent; A subject consisting of 0.1 to 10 weight percent water and 0.01 to 5 weight percent catalyst;
70 to 90% by weight of an alicyclic modified amine; 0.1 to 10 weight percent aminosilane; 0.001 to 1.0 weight percent antifoaming agent; 0.001 to 1.5% by weight of leveling agent; And a two-component coating comprising a curing agent composed of 5 to 25% by weight of the solvent. The method of claim 1, wherein the curing agent is selected from 0.01 to 2% by weight based on the total weight of the curing agent; 0.01-2% by weight of a pigment wetting dispersant; 5 to 40% by weight of inorganic pigments; And 5 to 40 weight percent of a filler; The organic solvent according to claim 1 or 2, wherein the organic solvent in the subject is anhydrous ethyl alcohol (anhydrous C ₂ H ₅ OH); Propylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ), isopropyl alcohol, cellosolve acetate ( CELLOSOLVE ACETATE), ethyl acetate, propylene glycol monomethyl ether acetate, and a mixture of organic co-solvents selected from the group consisting of these two-part coatings. The two-part coating according to claim 3, wherein the mixing ratio of the anhydrous ethyl alcohol and the organic cosolvent is 1: 3 to 3: 1 anhydrous ethyl alcohol: auxiliary solvent. The catalyst of claim 1, wherein the catalyst in the subject is itaconic acid (C ₅ H ₆ O ₄ ), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), hydrochloric acid (HCl). ) And boric acid (H ₃ BO ₃ ), EDTA, oxalic acid and mixtures thereof. The cycloaliphatic modified amine of claim 1, wherein the curing agent is a hydrogenated cycloaliphatic modified amine of Docure KH-816 or Docure KH-818B (Kukdo Chemical); amino silane, γ-aminopropyltriethoxysilane (Silquest A-1100, Momentive Performance Materials Inc.); Fluorosilicone copolymer (Dowcorning FS-1265, 300-10,000 CST), ethylmethyl, methyl (2-phenylpropyl) siloxane (Dowcorning 56 Additive), polydimethylsiloxane (Shin-etsu, KF-96, 10-100,000 CST ) And antifoaming agents selected from the group consisting of; Leveling agents that are dimethyl, methyl (polyethylene oxide acetate-capped) siloxane (Dowcorning 57 Additive); Talc, Barium sulfate, Calcium carbonate, Aluminum Hydroxide, Zinc Oxide, Calcined Kaolin, Magnesium Carbonate and their Filler selected from the group consisting of mixtures; And polyethylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ), and mixtures thereof Two-part coating comprising a selected solvent.
The color separation inhibitor is a carboxylate solution of polyamineamide (ANTI-TERRA-205, BYK-Chemie or ANTI-TERRA-204, BYK-Chemie), and the pigment wet dispersant is a salt polyamine amide and a polyester. (DisperBYK-2095, BYK-Chemie), wherein the pigment is a two-part coating selected from the group consisting of TiO ₂ , iron oxide (Iron Oxide), chromium oxide (Chromium Oxide) and mixtures thereof. The organic solvent according to claim 7, wherein the organic solvent is anhydrous ethyl alcohol (anhydrous C ₂ H ₅ OH), propylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ) and mixtures thereof; The catalyst is itaconic acid (C ₅ H ₆ O ₄ ), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), acetic acid (CH ₃ COOH), hydrochloric acid (HCl), boric acid (H ₃ BO ₃ ) and mixtures thereof in
Selected from the group consisting of;
Among the curing agent components, the cycloaliphatic modified amine is selected from Docure KH-816 (Kukdo Chemical), Docure KH-818B (Kukdo Chemical) and mixtures thereof; Aminosilane is γ-aminopropyltriethoxysilane (Silquest A-1100, Momentive Performance Materials Inc.); Defoamers include fluorosilicone copolymer (Dowcorning FS-1265, 300-10,000 CST), ethylmethyl, methyl (2-phenylpropyl) siloxane (Dowcorning 56 Additive), polydimethylsiloxane (Shin-etsu, KF-96, 10- 100,000 CST) and mixtures thereof; Leveling agent is dimethyl, methyl (polyethylene oxide acetate-capped) siloxane (Dowcorning 57 Additive); The color separation inhibitor is a carboxylate solution of polyamineamide (ANTI-TERRA-205, BYK-Chemie or ANTI-TERRA-204, BYK-Chemie); The pigment wetting dispersant is selected from the group consisting of salt polyamine amides, polyesters (DisperBYK-2095, BYK-Chemie) and mixtures thereof; Inorganic pigments are selected from the group consisting of TiO ₂ , Iron Oxide, Chromium Oxide and mixtures thereof; Fillers include Talc, Barium sulfate, Calcium carbonate, Aluminum Hydroxide, Zinc Oxide, Calcined Kaolin, Magnesium Carbonate and Selected from the group consisting of mixtures thereof; The solvent is a group consisting of polyethylene glycol monomethyl ether (C ₄ H ₁₀ O ₂ ), ethylene glycol monopropyl ether (C ₆ H ₁₄ O ₂ ), ethylene glycol monobutyl ether (C ₆ H ₁₄ O ₂ ) and mixtures thereof Two-part coatings selected from. 3. A two-part coating according to claim 1 or 2, consisting of 1.5: 1 to 3.5: 1 weight ratio subject: curing agent. The ring-opening reaction of the epoxy group of the organic polymer is caused by the interaction of the organic-modified alkoxysilane and the organic polymer in the subject, and the ring-opening reaction of the organic-modified alkoxysilane and the organic polymer is added covalently. Due to the hydrolysis reaction between the catalyst and water, the alkoxy group of the organomodified alkoxysilane is changed into a silanol group, where methanol is generated, and the silanol moiety derived from the organomodified alkoxysilane and the silanol moiety derived from the metal alkoxide are O-linked. Two-part coating connected by. The two-part coating agent of claim 1 or 2 and the curing agent are uniformly mixed in a ratio of 1.5: 1 to 3.5: 1 by weight of the main agent: curing agent, and then applied to the substrate, and then subjected to 2 days to 7 days at a temperature of 10 to 30 ° C. A coated formed article made by curing for days. The article of claim 11, wherein the substrate is selected from the group consisting of plastic products, metallic substrates, wood, cement concrete, and glass.

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