KR101125845B1 - SILICONE BASED TWO LIQUID TYPE ORGANIC·INORGANIC HYBRID COATINGS AND MANUFACTURAL METHODS - Google Patents

Abstract

PURPOSE: A silicon-based two-component type organic/inorganic hybrid coating agent and a manufacturing method thereof are provided to improve surface strength, abrasion resistance, and alkali resistance. CONSTITUTION: A silicon-based two-component type organic/inorganic hybrid coating agent comprises base material and a hardener. The base material comprises 10-20weight% of solvent, 15-30weight% of epoxy-modified silane coupling agent, 20-30weight% of epoxy resin, alcoxysilane, alcohol, 1-10weight% of hydrolysis agent, and nano silica sol. The hardener is a mixture of 50-70weight% of modified cycloaliphatic amine, bifunctional amine-modified silane coupling agent, 0.01-1weight% of hydroxide based alkali catalyst, 15-40weight% of solvent, 0.1-3weight% of leveling agent, and 0.1-2weight% of defoaming agent.

Description

SILICONE BASED TWO LIQUID TYPE ORGANIC INORGANIC HYBRID COATINGS AND MANUFACTURAL METHODS

The present invention is a silicone-based two-component organic-inorganic hybrid coating agent composed of a main agent and a hardener, and forms a coating film having excellent surface strength, abrasion resistance, acid and alkali resistance, chemical resistance, and water resistance on the surface of inorganic building materials such as cement and concrete. It relates to a silicone-based two-component organic-inorganic hybrid coating agent.

Conventional inorganic coating agents for improving durability on the surface of inorganic building materials such as cement and concrete have excellent strength and abrasion resistance, but are poor in water resistance, alkali resistance, and shrinkage during hardening reaction during coating film formation. There is this. On the other hand, the organic coating agent is excellent in alkali resistance, tensile strength and coating film forming ability, but the strength and wear resistance, acid resistance, heat resistance and the like of the coating film itself has a weak problem.

Organic / inorganic hybrid coating agent is a coating agent that greatly improves physical and chemical properties by mutually supplementing the strengths and weaknesses of inorganic and organic coating agents by combining inorganic and organic components. Recently, the blending method of the organic polymer and the inorganic polymer and the sol-gel method have been introduced as such a compounding method.

First, Norman R. Mowrer et al. Published US Patent 5,618,860 “Epoxy Polysiloxane coating and Flooring Compositions” as a blending method of organic polymer and inorganic polymer. This method is an organic / inorganic hybrid coating agent consisting of a bisphenol-A type epoxy resin and a polysiloxane (inorganic polymer) blended with an alkoxy group, and a curing agent mixed with a bifunctional amine-modified silane coupling agent and a solvent. More excellent weather resistance, chemical resistance, etc. are exhibited. Therefore, the manufacturing method is very simple, but the wear resistance is lowered by the use of highly flexible polysiloxane, there is a problem in the perfect mixing of the epoxy resin and polysiloxane.

Next, in the sol-gel method, M. Ochi et al. Described the bisphenol-A based epoxy resin and epoxy modified silane coupling agent in "Phase structure and mechanical and adhesion properties of epoxy / silica hybrids" (Polymer 42 (2001) 5151 ~ 5158). Organic-inorganic hybrid coating agent composed of Tetraethylenepentamine (TEPA) curing agent and Tetraethylenepentamine (TPA) using Tetramethylorthosilicate (TMOS) Was developed, and the results showed that the bond strength was greatly improved. Meanwhile, Park, Jung-Hoon et al., "Preparation and Characterization of Silica-Epoxy Hybrid Materials" (Theory and Application of Chemical Engineering, Vol. 9, No. 2, pp.2726 ~ 2729) and "Silica / GPTMS / Epoxy Composites Abrasion Characteristics of Film ”(Theory and Application of Chemical Engineering, Vol. 10, No. 2, 2004, pp.2091 ~ 2094), and the epoxy ring was stirred at 70 ° C for 4 hours after mixing epoxy resin and epoxy modified silane coupling agent. After mixing the solution prepared by the ring-opening reaction with TEOS: ethanol: H ₂ O = 1: 2: 2 molar ratio, adding a small amount of HCl acid catalyst, and stirring for 1 hour to prepare a silica solution at the same time, the two solutions The mixture was mixed and a small amount of HCl and H ₂ O were added for an additional 1 hour to develop an organic-inorganic hybrid coating composed of Jeffamine D-230 and methyltetrahydrophathalic anhydride curing agent. The organic-inorganic hybrid coating agent prepared by the sol-gel method is a coating film is formed by heat curing at a temperature of 80 ℃ or more, abrasion resistance, adhesion strength and the like has been greatly improved. However, it is not practical because it is difficult to use a heat curing system for construction purposes.

As an advanced method in the sol-gel method, a domestic patent registration 10-0956752 "A room temperature hardening type organic-inorganic hybrid coating agent" has been developed. In this method, a bisphenol-A epoxy resin and an epoxy-modified silane coupling agent are mixed and heated to 70 ° C., and H ₂ O and an acid are added to the epoxy ring of the bisphenol-A epoxy resin and an epoxy-modified silane coupling agent. Tetraethoxyorthosilicate (TEOS) and tetramethoxyorthosilicate (TMOS) were added to the polymerized product by chemically reacting by ring-opening the epoxy ring, followed by continuous heating and polymerization at 70 ° C. We have developed a room temperature-curable organic-inorganic hybrid coating agent composed of a curing agent mixed with a modified alicyclic amine having a total amine value in the range of 220 to 320, a monofunctional amine modified silane coupling agent, and other additives. As a result, the wear and flame retardancy is superior to the conventional epoxy and urethane-based flooring materials, has high adhesion, waterproof, acid and alkali resistance, pollution resistance and the like. Since the above method uses a tetrafunctional metal alkoxide having a low solids content in preparing the main body, the hydrolysis and polymerization reactions are delayed, resulting in a very long process time of 6 hours or more. In addition, in the case of forming the coating film by mixing the main material and the curing agent, the TAV (total amine value) is low as the curing agent, there is a problem that the strength expression is slowed because the monofunctional amine-modified silane coupling agent is used.

The present invention synthesized nanosilica sol in order to further improve the surface strength and flame retardancy of the coating by increasing the content of the inorganic component in the composite prepared by the sol-gel method to complement the disadvantages of the conventional inorganic and organic coating agent, It provides two-component organic / inorganic hybrid coatings that can be mass-produced in less than 3 hours. The modified alicyclic amine and bifunctional amine-modified silane having a TAV (total amine value) of 330 to 400 in the curing agent. It is an object of the present invention to provide a two-part organic / inorganic hybrid coating agent having strength expression characteristics that can be promoted by use of a coupling agent and an alkali catalyst and which can walk within 8 hours after the second coating.

In the present invention, silanol and bisphenol-A epoxy resins obtained by partially hydrolyzing an epoxy-modified silane coupling agent by using two kinds of hydrolysis catalysts of inorganic acid and dibutyltin dilaurylate (DBTDL) are used. In order to increase the content of inorganic components, the reaction time is reduced to less than 3 hours by adding nanosilica and a catalyst having a specific surface area of 90 to 300 m ² / g modified with two or more alkoxysilanes. At the same time, the composition of the two-component organic / inorganic hybrid coating agent that maximizes the inorganic content is mixed, and a modified alicyclic amine having a total amine value (TAV) of 330 to 400, a bifunctional amine modified silane coupling agent, and an alkali catalyst are mixed. It is composed of one curing agent and has very good physicochemical properties such as wear resistance, adhesive strength and flame retardancy, and can walk within 8 hours after the second coating. U-shaped and provides an inorganic hybrid coating to achieve the object of the present invention.

The two-component organic / inorganic hybrid coating agent according to the present invention improves the surface strength, abrasion resistance, flame retardancy, etc. of the coating film by increasing the content of the inorganic component compared to the conventional organic / inorganic hybrid coating agent in complexing with the sol-gel method. (Total amine value) in the range of 330 ~ 400 using a modified alicyclic amine, a bifunctional amine modified silane coupling agent and an alkali catalyst to provide a coating that promotes the strength expression of the coating film. In particular, it has excellent adhesion strength to inorganic building materials such as cement and concrete, excellent waterproofness, acid and alkali resistance, and excellent flame retardancy than existing organic coatings, so it is expected to be useful in the field of interior coatings. do.

The technical terms and scientific terms used in the present invention can be construed as meaning ordinary meanings understood by those of ordinary skill in the art without departing from the scope of the present invention.

The present invention relates to a silicone-based two-part organic / inorganic hybrid coating agent composed of a main agent and a curing agent. Specifically, the present invention provides a hydrolysis epoxy modified silane coupling agent (GPTMS) by adding a hydrolysis catalyst to a homogeneously mixed solvent and an epoxy modified silane coupling agent, and reacts the hydrolyzed GPTMS with an epoxy resin to react with a hybrid polymer. After synthesized, the mixture of nanosilica, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane and alkoxysilane selected from the group consisting of a mixture of alcohol and alcohol, and then added a hydrolysis catalyst Prepared by adding the nanosilica sol to the hybrid polymer with a hydrolysis catalyst at 70 ℃
Silicone-based two-part organic / inorganic hybrid coating agent comprising a main body prepared by further polymerization and a curing agent composed of a modified alicyclic amine, a bifunctional amine modified silane coupling agent, a solvent, a barium hydroxide alkali catalyst, a leveling agent and an antifoaming agent. And it relates to a manufacturing method thereof.

In the present invention, the two-component organic / inorganic hybrid coating agent is composed of a main agent and a curing agent, and a main agent is prepared by the steps as shown in the following figure.

The subject of the two-part organic / inorganic hybrid coating of the present invention is 15 to 30% by weight epoxy modified silane coupling agent (GPTMS), 20 to 35% by weight epoxy resin, 30 to 50% by weight nanosilicasol, 10 to 20 Weight percent solvent, 1 to 10 weight percent hydrolysis catalyst. The curing agent of the two-component organic / inorganic hybrid coating agent of the present invention is a modified alicyclic amine having a total amine value (TAV) of 50 to 70 wt% in the range of 330 to 400, and a difunctional amine modified silane coupling agent of 1 to 10 wt%. 15 to 40 wt% solvent, 0.01 to 1 wt% barium hydroxide based alkali catalyst, 0.1 to 3 wt% leveling agent and 0.1 to 2 wt% antifoaming agent.

Preferably, the present invention uniformly mixes 10 to 20% by weight of solvent with 15 to 30% by weight of epoxy modified silane coupling agent based on the total weight of the subject, and adds and adds a hydrolysis catalyst to mix the hydrolyzed epoxy modified A silane coupling agent (GPTMS) was prepared, 20-35 wt% epoxy resin was added to the prepared hydrolyzed GPTMS based on the total weight of the subject, and stirred for 1 hour and 30 minutes to synthesize a hybrid polymer, followed by nanosilica and , Tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, and alkoxysilane selected from the group consisting of a mixture of these, and the alcohol is mixed uniformly, and then prepared by reacting for 1 hour with the addition of a hydrolysis catalyst The hydrolyzed catalyst to the synthesized hybrid polymer in the amount of 30 to 55% by weight based on the total weight of the subject. The subject produced by carrying out further polymerization at 70 ℃ added to; And 50 to 70% by weight of modified alicyclic amine, 1 to 10% by weight of bifunctional amine modified silane coupling agent, 15 to 40% by weight of solvent, 0.01 to 1% by weight of barium hydroxide alkali catalyst, 0.1 to 3 Provided is a two-part organic / inorganic hybrid coating comprising a curing agent composed of a weight percent leveling agent and 0.1 to 2 weight percent antifoaming agent.

Preferably, in the two-part organic / inorganic hybrid coating of the present invention, the amount of the hydrolysis catalyst used to polymerize the hybrid polymer and the final subject matter is 1 to 10% by weight based on the total weight of the subject matter.

Further, preferably, in the two-component organic / inorganic hybrid coating agent of the present invention, the epoxy resin is selected from bisphenol-A type having an epoxy resin equivalent of 180 to 250.

Further, preferably, in the two-component organic / inorganic hybrid coating agent of the present invention, the nanosilica sol has a specific surface area of 90 to 300 m ² / g, and 5 to 15 wt% of weakly acidic nano silica having a pH of 3 to 6, tetra 25 to 40% by weight of ethoxysilane (Si (OC ₂ H ₅ ) ₃ ), methyltrimethoxysilane (CH ₃ -Si (OCH ₃ ) ₃ ) and phenyltrimethoxysilane (C ₆ H ₅ -Si (OCH ₃ ) 20 to 35% by weight alkoxysilane selected from the group consisting of ₃ ) and mixtures thereof, 25 to 35% by weight alcohol selected from the group consisting of ethyl alcohol, isopropyl alcohol and mixtures thereof, and 5 to 15 hydrolysis catalysts Weight percent.

Also preferably, in the two-component organic / inorganic hybrid coating agent of the present invention, the solvent is 2-methoxyethanol (CH ₃ OCH ₂ CH ₂ OH), 2-ethoxyethanol (CH ₃ CH ₂ OCH ₂ CH ₂ OH). ), 2-propoxyethanol (CH ₃ CH ₂ CH ₂ OCH ₂ CH ₂ OH), 2-butoxyethanol (CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OH), dimethylcarbonate (CH ₃ C (O) CH ₃ ) and mixtures thereof.

Also preferably, in the two-component organic / inorganic hybrid coating agent of the present invention, the modified alicyclic amine is a modified alicyclic amine having a total amine value (TAV) of 330 to 400.

Preferably, in the two-component organic / inorganic hybrid coating agent of the present invention, the bifunctional amine-modified silane coupling agent is aminoethylaminopropyltrimethoxysilane (H ₂ NC ₂ H ₄ NHC ₃ H ₆ -Si (OCH). ₃ ) ₃ ).

Further, preferably, in the two-component organic / inorganic hybrid coating agent of the present invention, the weight ratio of the main agent to the curing agent is 3 to 4: 1.

The present invention also provides an article having a coating film prepared by applying the silicone two-component organic / inorganic hybrid coating agent of the present invention to a cement concrete product and curing at room temperature for 1 to 7 days.

Preferably, the article prepared according to the present invention is an article having a film coated with the two-component organic / inorganic hybrid coating agent of the present invention composed of a ratio of 3 to 4: 1 weight ratio of the subject: curing agent.

In the subject of the two-component organic / inorganic hybrid coating agent of the present invention, the epoxy-modified silane coupling agent is glycidoxypropyltrimethoxysilane (GPTMS, CH ₂ (O) CHCH ₂ OC ₃ H ₆ -Si (OCH ₃ ) ₃ ), The amount of use is from 15 to 30% by weight. If the amount of the epoxy-modified silane coupling agent is less than 15% by weight, the content of epoxy resin is relatively increased, resulting in insufficient compatibility with nanosilica sol, resulting in poor physical properties of the coating film. Can't expect More preferably, 18 to 27% by weight is used.

It is preferable to use bisphenol-A whose epoxy resin equivalent is 180-250, and the use amount of epoxy resin is 20-35 weight%. If the amount of the epoxy resin is less than 20% by weight, the coating film may not be formed well due to the lack of the coating film forming ability of the coating agent, and when the amount is more than 35% by weight, the inorganic component is relatively decreased, thereby reducing the strength, abrasion resistance, and flame resistance of the coating film. More preferably, it is preferable to use 22-30 weight%.

The hydrolysis catalyst is distilled water whose pH is adjusted to 1 using an acid selected from the group consisting of inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and mixtures thereof, and the dibutyltin dilaurylate (DBTDL) based catalyst is 0.01 to 0.5% by weight. Included in quantity. The amount of the hydrolysis catalyst used for the hydrolysis of the epoxy modified silane coupling agent is preferably 1 to 5% by weight. If the amount of the hydrolysis catalyst used for the hydrolysis of the epoxy-modified silane coupling agent is less than 1% by weight, the hydrolysis of the epoxy-modified silane coupling agent is insufficient, so that it cannot react with the epoxy resin. It occurs abruptly and hydrolysis and polymerization of silane coupling agents occur, which is undesirable. More preferably, 2 to 5% by weight is preferable. On the other hand, the amount of the hydrolysis catalyst required to polymerize the hybrid polymer + nanosilica sol is preferably 1 to 4% by weight. When the amount of the hydrolysis catalyst required to polymerize the hybrid polymer + nanosilica sol is less than 1% by weight, the commercialization of the hybrid polymer and the nano silica is insufficient, and when the amount is 4% by weight or more, gelation of the nano silica is caused. More preferably, 1.5 to 3% by weight is preferable.

On the other hand, the nanosilica sol has a specific surface area of 90 ~ 300m ² / g, 5 to 15% by weight of nano silica, characterized in that the pH is 3 to 6, tetraethoxysilane (Si (OC ₂ H ₅ ) ₃ ) 25 to 40% by weight of methyltrimethoxysilane (CH ₃ -Si (OCH ₃ ) ₃ ), phenyltrimethoxysilane (C ₆ H ₅ -Si (OCH ₃ ) ₃ ) and mixtures thereof 20 to 35 weight percent alkoxysilane selected from the group, 25 to 35 weight percent alcohol selected from the group consisting of ethyl alcohol, isopropyl alcohol and mixtures thereof, and 5 to 15 weight percent hydrolysis catalyst. In preparing the nanosilica sol, the amount of the nanosilica used is 5 to 15% by weight. If the content of nanosilica is less than 5% by weight, the content of inorganic components is too small. Therefore, it does not contribute to the improvement of strength, abrasion resistance and flame retardancy of the organic / inorganic hybrid coating agent. Surface modification does not proceed uniformly. More preferably 6 to 10% by weight is preferred. The amount of tetraethoxysilane (Si (OC ₂ H ₅ ) ₃ ) used is 25 to 40% by weight. When the amount of tetraethoxysilane (Si (OC ₂ H ₅ ) ₃ ) is less than 25% by weight, the strength of the coating film is reduced due to the lack of inorganic network structure formation. It will decrease, causing cracks in the coating. More preferably 28 to 38% by weight is preferred. The amount of the alkoxysilane selected from the group consisting of methyltrimethoxysilane (CH ₃ -Si (OCH ₃ ) ₃ ) and phenyltrimethoxysilane (C ₆ H ₅ -Si (OCH ₃ ) ₃ ) and mixtures thereof is 20 To 35% by weight. If the amount of the alkoxysilane used is less than 25% by weight, it is difficult to uniformly mix with the epoxy resin, so that the physical properties of the coating film become poor, and when the amount of the alkoxysilane is 35% by weight or more, the hydrolysis reaction proceeds rapidly, and gelation cannot be used. More preferably, 27 to 33 weight% is preferable. The amount of alcohol used as the solvent is 25 to 35% by weight. If the amount of alcohol used as the solvent is less than 25% by weight, the content of the solvent is low, so that the hydrolysis is not uniform. If the amount of the alcohol is greater than 35% by weight, the reduction of the inorganic component adversely affects the physical properties of the coating film. More preferably, it is preferable to use 28-32 weight%. The amount of the hydrolysis catalyst used is 5 to 15% by weight. Gelation during storage time because the amount of the hydrolysis catalyst is less than 5% by weight going to hydrolysis is not sufficient, because there is little amount of H ₂ O and the acid catalyst required for the hydrolysis, the high H ₂ O and an acid catalyst content of the at least 15% by weight Occurs. More preferably 6 to 12% by weight is preferred. In particular, the amount of DBTDL (dibutyltin dilaurylate) catalyst used in the hydrolysis catalyst is 0.01 to 0.5% by weight. If the amount of DBTDL-based catalyst used is 0.01% by weight or less, the effect of promoting hydrolysis is insufficient, and at 0.5% by weight or more, the effect of promoting the hydrolysis is no longer expressed. More preferably 0.02 to 0.3% by weight is preferred.

The amount of the nanosilica sol as described above is 30 to 55% by weight. If the amount of the nanosilica sol is less than 30% by weight, the amount of the inorganic component may not be sufficient, thereby reducing the strength and abrasion resistance of the coating film, and the amount of the inorganic component may be so high that the workability is poor. More preferably 35 to 50% by weight is preferred.

The solvent is 2-methoxyethanol (CH ₃ OCH ₂ CH ₂ OH), 2-ethoxyethanol (CH ₃ CH ₂ OCH ₂ CH ₂ OH), 2-propoxyethanol (CH ₃ CH ₂ CH ₂ OCH ₂ CH ₂ OH), 2-butoxyethanol (CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OH), dimethylcarbonate (CH ₃ C (O) CH ₃ ), and mixtures thereof. The amount of the solvent used is 10 to 20% by weight. If the amount of the solvent used is less than 10% by weight, the viscosity of the main body is too high, resulting in insufficient workability, and when the amount of the solvent is 20% by weight or more, the solid content of the main body is reduced, resulting in insufficient formation of the coating film. More preferably, 12 to 18% by weight is preferable.

In the curing agent of the two-part organic / inorganic hybrid coating agent of the present invention, the modified alicyclic amine is preferably a modified alicyclic amine having a total amine value (TAV) of 330 to 400. The bifunctional amine-modified silane coupling agent is preferably aminoethylaminopropyltrimethoxysilane (H ₂ NC ₂ H ₄ NHC ₃ H ₆ -Si (OCH ₃ ) ₃ ). As the alkali catalyst, it is preferable to use barium hydroxide. The solvent is used the same as the solvent used in the above topic. Leveling agents and defoamers used as other additives typically use additives used in epoxy resin coatings.

In the curing agent, the amount of the modified alicyclic amine is 50 to 70% by weight. When the amount of modified alicyclic amine is less than 50% by weight, the curing speed is delayed too much and the curing is insufficient, so that the coating film of the coating is poor. When the amount is 70% by weight or more, the curing speed is too fast. Not secured. More preferably 55 to 65% by weight is preferred. The usage-amount of a bifunctional amine modified silane coupling agent is 1 to 10 weight%. When the amount of the bifunctional amine-modified silane coupling agent is less than 1% by weight, there is no effect of using the coupling agent, and when it is 10% by weight or more, the main hydrogel and the curing agent are accelerated due to the rapid gelation of the partially hydrolyzed alkoxysilane contained in the main body. After mixing, the working time is not secured enough. More preferably, 1.5 to 8.0 weight% is preferable. The amount of the barium hydroxide alkali catalyst used is 0.01 to 1% by weight. If the amount of the barium hydroxide-based alkali catalyst is less than 0.01% by weight, the hydrolysis of the partially hydrolyzed alkoxysilane contained in the main material is not sufficiently performed, resulting in a decrease in the water resistance of the coating film and no effect even when the content is 1% by weight or more. Do not. More preferably 0.02 to 0.8% by weight is preferred. The amount of the solvent used is 15 to 40% by weight. When the amount of the solvent used is not more than 15% by weight, no uniform mixing is performed, and when the amount is 40% by weight or more, the content of the curing agent component is relatively insufficient, so that the curing reaction of the coating film is not sufficiently performed. Especially preferably, 20 to 35 weight% is preferable.

The main body and the hardening | curing agent of the silicone type two-component organic-inorganic hybrid coating agent by this invention are used by mixing main: hardening | curing agent as 3-4: 1. In addition, the inorganic pigment is generally used to add 10 to 30 parts by weight based on the weight of the main agent and the curing agent to prepare a colored silicone-based two-component organic-inorganic hybrid coating agent.

<Method production method>

The subject of the two-component organic-inorganic hybrid coating agent of the present invention is to homogeneously mix the solvent and the epoxy-modified silane coupling agent as shown in the figure, and the hydrolysis catalyst is mixed to prepare a hydrolyzed GPTMS while raising the temperature to 70 ℃ for 30 minutes. When the temperature reaches 70 ° C., the epoxy resin is added to the hydrolyzed GPTMS and stirred for 1 hour and 30 minutes to synthesize a hybrid polymer.

On the other hand, nano-silica sol is a mixture of nano-silica, tetraethoxysilane and methyltrimethoxysilane, phenyltrimethoxysilane and alkoxysilane selected from the group consisting of a mixture of alcohol and alcohol after adding a hydrolysis catalyst Prepared by reacting for 1 hour. Nanosilazole and a hydrolysis catalyst are added to the hybrid polymer to further polymerize at 70 ° C., and then cooled to room temperature to prepare a target subject.

In the above, the hydrolysis reaction of the silane coupling agent having a reactive organic group proceeds as follows.

Wherein R- = CH ₂ (O) CHCH ₂ OC ₃ H ₆ -or H ₂ C = CH-.

The reaction between the hydrolyzed silane coupling agent and the epoxy resin is carried out by ring opening reaction of the epoxy resin at 70 ° C. and silanol (-OH) of the silane coupling agent as described below.

The partial hydrolysis reaction of tetraethoxysilane proceeds as in Scheme 3, and the partial hydrolysis reaction of methyl and phenyltrimethoxysilane proceeds as in Scheme 4.

Wherein R = CH ₃ or C ₆ H ₅ .

On the other hand, the product of Scheme 3 and the product of Scheme 4 is polymerized to generate H ₂ O as in Scheme 5.

C-OH of the product of Scheme 2 and Si-OH of the product of Scheme 5 react to produce the following products.

Wherein R ₁ = CH ₂ (O) CHCH ₂ OC ₃ H ₆ -or H ₂ C = CH-,

R ₂ = CH ₃ or C ₆ H ₅ .

<Method for producing hardener>

As the modified cycloaliphatic amine, KH-831 having a total amine value (TAV) in the range of 330 to 400 is uniformly mixed with the same solvent as the solvent used in the above-mentioned preparation, and the amino as a bifunctional amine-modified silane coupling agent After addition of ethylaminopropyltrimethoxysilane (H ₂ NC ₂ H ₄ NHC ₃ H ₆ -Si (OCH ₃ ) ₃ ) and barium hydroxide, the leveling agent and the antifoaming agent used as other additives are commonly used in epoxy resin coatings. It is prepared by mixing uniformly using the additive used.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely for illustrative purposes, and the scope of the present invention is not limited to these examples.

Examples 1 to 3 silicone-based two-component hybrid coating

Example 1

At room temperature, 200 g of epoxy-modified silane coupling agent was uniformly mixed with 125 g of 2-ethoxyethanol, and 16 g of a hydrolysis catalyst was added thereto, followed by hydrolysis while heating at 70 ° C. for 30 minutes, followed by epoxy resin having an epoxy resin equivalent of 184 (Kukdo 280 g of Chemistry, YD-128) was added and reacted for 1 hour 30 minutes. Here, 364 g of nanosilica sol and 15 g of a hydrolysis catalyst were mixed and reacted for 1 hour, and then cooled to room temperature to prepare 1 kg of a silicone-based two-component hybrid coating agent of Example 1. In preparing the nanosilica sol, 50 g of nano silica, 350 g of tetraethoxysilane, 260 g of methyltrimethoxysilane, and 260 g of ethyl alcohol were uniformly mixed at room temperature. 80 g of a hydrolysis catalyst was added thereto, followed by partial hydrolysis for 1 hour, thereby preparing 1 kg.

Example 2

After homogeneously mixing 200 g of glycidoxy propyl methoxysilane to 120 g of 2-ethoxyethanol at room temperature, 16 g of a hydrolysis catalyst was added and hydrolyzed while heating at 70 ° C. for 30 minutes, and then an epoxy resin having an epoxy resin equivalent of 184. 250 g of (Kukdo Chemical, YD-128) was added and reacted for 1 hour 30 minutes. 399 g of the nanosilica sol and 15 g of the hydrolysis catalyst were mixed and reacted for 1 hour, followed by cooling to room temperature to prepare 1 kg of the silicone-based two-component hybrid coating agent of Example 2. In preparing the nanosilica sol, 50 g of nano silica, 350 g of tetraethoxysilane, 260 g of methyltrimethoxysilane, and 260 g of ethyl alcohol were uniformly mixed at room temperature. 80 g of a hydrolysis catalyst was added thereto, followed by partial hydrolysis for 1 hour.

Example 3

After homogeneously mixing 200 g of glycidoxy propyl methoxysilane to 110 g of 2-ethoxyethanol at room temperature, 16 g of a hydrolysis catalyst was mixed and then hydrolyzed while heating at 70 ° C. for 30 minutes, and then an epoxy resin equivalent of 184 220 g of phosphorus epoxy resin (Kukdo Chemical, YD-128) was added and reacted for 1 hour 30 minutes. 439 g of the nanosilica sol and 15 g of the hydrolysis catalyst were mixed and reacted for 1 hour, and then cooled to room temperature to prepare 1 kg of the silicone-based two-component hybrid coating agent of Example 3. In preparing the nanosilica sol, 50 g of nano silica, 350 g of tetraethoxysilane, 260 g of methyltrimethoxysilane, and 260 g of ethyl alcohol were uniformly mixed at room temperature. 80 g of a hydrolysis catalyst was added thereto, followed by partial hydrolysis for 1 hour.

On the other hand, the curing agent of the two-component organic-inorganic hybrid coating agent of Examples 1 to 3 is 300 g of 2-ethoxyethanol, modified alicyclic amine, 600H KH-831, bifunctional type having a total amine value (TAV) of 330 to 400 75 g of aminoethylaminopropyltrimethoxysilane, 5 g of barium hydroxide, 10 g of BYK-530, and 10 g of leveling agent BYK-388 were prepared as an amine-modified silane coupling agent.

The physical and chemical properties of the two-part organic / inorganic hybrid coating agent prepared in Example 1 to 3 and the curing agent prepared as described above in the main body: curing agent = 7: 2 are shown in Table 1 below. It was.

Table 1: Physical and chemical properties of silicone two-component organic-inorganic hybrid coatings

As can be seen from the above table, the coating film prepared from the two-component organic-inorganic hybrid coating agent of the present invention has a hardness of 3H or more pencil hardness is very high, the wear resistance test results were 40mg or less, acid resistance, alkali resistance, water resistance This was excellent.

In the present invention, after forming a coating film on a 20mm × 20mm iron plate, the width of the silicon-based two-component organic-inorganic hybrid coating for the nonflammability and flame retardancy test, and then stored at room temperature for 7 days and then heated for 20 minutes in a furnace maintained at 750 ℃ After cooling to room temperature, the weight reduction rate is measured. The weight loss ratio was calculated as follows.

Table 2: 750 ° C weight loss rate of silicone two-component organic-inorganic hybrid coatings

As shown in Table 2, the weight loss rate is very excellent, which is 30% by weight or less.

The above description is merely illustrative of the technical spirit of the present patent, and those skilled in the art to which the present patent belongs may make various modifications and changes without departing from the essential characteristics of the present patent.

In addition, the embodiments disclosed in the present patent are not intended to limit the technical spirit of the present patent but to describe the technical spirit of the present patent.

Therefore, the protection scope of the present patent should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present patent.

Claims (10)

10-20% by weight of solvent and 15-30% by weight of epoxy-modified silane coupling agent are uniformly mixed and the hydrolysis catalyst is added and mixed to form a hydrolyzed epoxy-modified silane coupling agent (GPTMS). After preparing 20 to 35% by weight based on the total weight of the subject epoxy resin prepared in the prepared hydrolyzed GPTMS and stirred for 1 hour and 30 minutes to synthesize a hybrid polymer, and then nano silica, tetraethoxysilane, methyl The main subject of the nanosilica sol prepared by homogeneously mixing the alkoxysilane selected from the group consisting of trimethoxysilane, phenyltrimethoxysilane and mixtures thereof with alcohol, and then reacting for 1 hour by adding a hydrolysis catalyst 30 to 55% by weight, based on weight, was added to the synthesized hybrid polymer with a hydrolysis catalyst and added at 70 ° C. A subject produced by carrying out the polymerization, and
50 to 70% by weight of modified alicyclic amine, 1 to 10% by weight of bifunctional amine modified silane coupling agent, 15 to 40% by weight of solvent, 0.01 to 1% by weight of barium hydroxide alkali catalyst, 0.1 to 3% by weight A two-component organic-inorganic hybrid coating agent comprising a curing agent composed of% leveling agent and 0.1 to 2% by weight antifoaming agent. The two-part organic-inorganic hybrid coating agent according to claim 1, wherein the amount of the hydrolysis catalyst used to polymerize the hybrid polymer and the final subject matter is 1 to 10% by weight based on the total weight of the subject matter. The two-component organic-inorganic hybrid coating agent according to claim 1, wherein the epoxy resin is selected from bisphenol-A type having an epoxy resin equivalent of 180 to 250. The method of claim 1, wherein the nanosilica sol has a specific surface area of 90 ~ 300m ² / g, 5-15% by weight of weakly acidic nanosilica having a pH of 3-6, tetraethoxysilane (Si (OC ₂ H ₅ ) ₃ ) 25 to 40% by weight, from the group consisting of methyltrimethoxysilane (CH ₃ -Si (OCH ₃ ) ₃ ) and phenyltrimethoxysilane (C ₆ H ₅ -Si (OCH ₃ ) ₃ ) and mixtures thereof A two-component oil comprising 20 to 35% by weight of the selected alkoxysilane, 25 to 35% by weight of alcohol selected from the group consisting of ethyl alcohol, isopropyl alcohol and mixtures thereof, and 5 to 15% by weight of the hydrolysis catalyst. Inorganic hybrid coatings. The method of claim 1, wherein the solvent is 2-methoxyethanol (CH ₃ OCH ₂ CH ₂ OH), 2-ethoxyethanol (CH ₃ CH ₂ OCH ₂ CH ₂ OH), 2-propoxyethanol (CH ₃ CH ₂ CH ₂ OCH ₂ CH ₂ OH), 2-butoxyethanol (CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OH), dimethylcarbonate (CH ₃ C (O) CH ₃ ) and mixtures thereof A two-part organic / inorganic hybrid coating agent selected from the group. The two-component organic-inorganic hybrid coating agent according to claim 1, wherein the modified alicyclic amine has a total amine value (TAV) of 330 to 400. The two-component oil according to claim 1, wherein the bifunctional amine-modified silane coupling agent is aminoethylaminopropyltrimethoxysilane (H ₂ NC ₂ H ₄ NHC ₃ H ₆ -Si (OCH ₃ ) ₃ ). Inorganic hybrid coatings. The two-component organic-inorganic hybrid coating agent according to claim 1, which is composed of a 3: 4: 1 weight ratio subject: curing agent. An article having a coating film prepared by applying the silicone two-component organic / inorganic hybrid coating agent of claim 1 to a cement concrete product and curing at room temperature for 1 to 7 days. 10. The article of claim 9 wherein the two-part organic / inorganic hybrid coating agent is comprised of a ratio of 3 to 4: 1 weight ratio subject: curing agent.