KR20090056610A - A waterproof thermal insulation coating resin composition - Google Patents

Abstract

A waterproof thermal insulation coating resin composition is provided to ensure excellent waterproof property, fast hardening rate, strong adhesive force with a substrate and excellent properties when applied to the substrate such as concrete, cement, and stone. A waterproof thermal insulation coating resin composition comprises silicon aqueous emulsion, water-dispersible polyurethane hybrid emulsion, and at least one unsaturated polymer resin. The silicon aqueous emulsion contains at least one alkyl group, at least one alkoxy group which is bonded with the alkyl group, and an alkyla alkoxy silane where the alkoxy group bonded with the alkyl group is bonded with silicon atom.

Description

A waterproof thermal insulation coating resin composition

The present invention relates to a waterproof insulating coating resin composition, and more particularly, in the composition of a waterproof insulating coating resin composition containing a silicone compound, comprising polyurethane, wherein the polyurethane is one or more selected from acrylic and epoxy The present invention relates to a silicone-based waterproof insulating coating resin composition having a good waterproof insulating performance, a fast curing speed, and excellent physical properties such as strong adhesion to adherends by introducing a compound and synthesizing it into a water dispersion type.

In general, a building structure to which construction materials such as concrete, cement, tile, stone, wood, etc. are applied is exposed to the natural environment and comes into contact with water, which shortens the lifespan. Conventionally, as such a waterproofing agent, a waterproofing agent containing a large amount of nonpolar hydrophobic groups or a waterproofing agent of a synthetic resin such as an epoxy resin has been used. However, such a waterproofing agent is particularly poorly penetrated into the inorganic building materials, lack of breathability, causing corruption of the inorganic building materials, and the waterproof performance was also poor.

Accordingly, in recent years, silicone compounds are mainly used. Silicone-based compounds have excellent weather resistance, chemical stability, water resistance, and the like, and are widely used as treatment agents for glass fibers, water repellents for construction works, water repellents for fibers, surface modifiers for inorganic materials, and silylating agents during synthesis of pesticides. In particular, alkylalkoxysilanes and organopolysiloxanes are known to be useful as waterproofing or permeable water absorption inhibitors for porous inorganic building materials such as concrete. It forms a hydrophobic layer from the surface of the substrate to prevent the penetration of water, salts and alkalis, and has a permeability into the substrate, which is considered to be much better than merely imparting water repellency to the surface. Accordingly, the demand for alkylalkoxysilanes and organopolysiloxanes which form a hydrophobic layer with good permeability and is resistant to chemical reactions is gradually increasing. Such alkylalkoxysilanes and organopolysiloxanes have generally been diluted and used in organic solvents, wherein toluene, xylene, benzene, industrial gasoline, kerosene, and the like have been used. However, silicone-based waterproofing agents diluted in organic solvents do not penetrate deeply into the substrate due to the characteristics of the organic solvents used as diluents, and are highly pollutable, highly flammable, and particularly toxic, injurious to the human body when inhaled. The damage is so severe that its use is limited. In particular, the silicone-based waterproofing agent diluted only with the organic solvent as described above has a problem that it can not be applied to the surface of the wet substrate. On the other hand, a silane-siloxane-containing permeable water absorption inhibitor containing no organic solvent is required in view of environmental problems, but this is disadvantageous in terms of economics.

Accordingly, in recent years, a method has been attempted to convert alkyl alkoxysilanes and organopolysiloxanes into aqueous dispersions and commercialize them into aqueous emulsions or aqueous creams having excellent workability and economy.

For example, Korean Patent No. 0211898 discloses a water-soluble cream of an organosilicon compound for hydrophobization building based on an alkylalkoxysilane and an organopolysiloxane, and Korean Patent Publication No. 10-1998-0024917 An aqueous-based emulsion permeable water absorption inhibitor has been proposed which can confirm whether the application of the dye to the inorganic building material is completed through the color of the dye by mixing an oil-soluble dye with an aqueous-based emulsion containing a silane, an emulsifier and water. . In addition, Korean Patent Laid-Open No. 10-1999-0078673 discloses a compound prepared by adding a chloroplatinic acid catalyst to a mixture of alkylalkoxysilane and silica, and a silicone emulsion aqueous water-repellent and water-resistant compounded with a silicone resin, an emulsifier and water. A condensation inhibitor was presented.

Water repellents are coated on lipids, requiring water resistance as well as durability, weather resistance, elasticity, strength, flexibility and good adhesion to the adherend. In addition, it is required that there be no cracking or lifting phenomenon due to elapse of time after forming the coating film.

However, the silicone-based waterproofing agent according to the prior art is excellent in waterproofness, but the elasticity and flexibility of the coating film is poor, and above all, a problem that is weak in moisture is pointed out. In general, concrete deposits in underground tunnels are sprayed with water for the purpose of removing the surrounding moisture or dust during drilling. However, conventional silicone-based waterproofing agents are inferior in physical properties under the above water environment. There is a problem. That is, under water conditions, there is a problem in that the curing speed is slow and the adhesion to the adherend falls.

The present invention is to solve the conventional problems as described above, in the composition of the silicone-based waterproof insulating coating resin composition containing a silicone compound, comprising a polyurethane, wherein at least one selected from acrylic and epoxy in the polyurethane By introducing a compound and simultaneously incorporating it into a water-dispersible type, it is excellent in waterproof performance, has a fast curing speed in water, and provides a silicone-based waterproof insulating coating resin composition having a strong adhesion to the adherend and excellent physical properties. There is this.

In order to achieve the above object, the present invention provides a silicone aqueous emulsion containing at least one alkyl group having 6 to 20 carbon atoms and at least one alkoxy group selected from methoxy, ethoxy and protoxy; After mixing and stirring polyol and dimethylol propionic acid (DMPA), isocyanate compounds are mixed in the presence of a reaction catalyst to synthesize a prepolymer, and triethylamine (TEA) is added as a neutralizing agent. Neutralizing the COOH group of dimethylol propionic acid (DMPA), and then adding one or more monomers selected from epoxy and acryl as a diluent to obtain a neutralized, diluted prepolymer, and then neutralizing and diluting the prepolymer. Water dispersion is carried out by adding water to a stirred solution at high speed, and at least one chain extender selected from epoxy and acryl is added and stirred to synthesize a water-dispersed polyurethane hybrid emulsion. ;

It provides a waterproof insulating coating resin composition comprising at least one unsaturated polymer resin selected from unsaturated polyester and unsaturated polyvinyl ester.

At this time, the water-dispersed polyurethane hybrid emulsion is a mixture of dimethylol propionic acid (DMPA; Dimethylol Propionic Acid) in the polyol and stirred, and then mixed isocyanate compound in the presence of a reaction catalyst to synthesize a prepolymer, and then tri Ethylamine (TEA) was added to neutralize the COOH group of dimethylol propionic acid (DMPA), and then one or more monomers selected from epoxy and acryl were added thereto as a diluent to obtain a neutralized, diluted prepolymer. A neutralized, diluted prepolymer is introduced into the water being stirred at high speed to perform a water dispersion process, and in this water dispersion process, one or more chain extenders selected from an epoxy-based and acrylic-based compound is added and stirred. The water-dispersed polyurethane hybrid emulsion is also selected from water-dispersed polyurethane-acrylic emulsions, polyurethane-epoxy emulsions and polyurethane-epoxy-acrylic emulsions.

The waterproof insulating coating resin composition according to the present invention is coated on a substrate of concrete, cement, stone, etc., has excellent waterproofing performance, has a fast curing speed in water, and has strong adhesion to the substrate and excellent physical properties.

Hereinafter, the present invention will be described in more detail.

The waterproof insulating coating resin composition according to the present invention comprises at least one silicone aqueous emulsion, a water-dispersed polyurethane (PU) hybrid emulsion, and an unsaturated polymer resin, and on a substrate (concrete, cement, tile, stone, etc.) In coating, it is mixed with a curing agent. At this time, the resin composition according to the present invention is packaged in a container separate from the curing agent and spread to the user. In addition, the resin composition according to the present invention may further comprise a filler selected from waste rubber powder, fibers and inorganic powder.

The silicone aqueous emulsion is an emulsion containing at least alkylalkoxysilane as the silicone compound as an active ingredient for waterproofing. At this time, the alkylalkoxysilane is selected from compounds in which at least one alkyl group having 6 to 20 carbon atoms and at least one alkoxy group selected from methoxy, ethoxy and methoxy are directly bonded to the silicon atom. At this time, when the alkyl group directly bonded to the silicon atom has less than 6 carbon atoms, the alkylalkoxysilane may exhibit extremely high hydrolyticity and volatility, and the alkylalkoxysilane molecule portion may be too short with the substrate surface immediately after application to the substrate surface. Reactions can occur quickly and delay the permeability of the emulsion. Thus, the water repellent component is imparted only to the substrate surface. In addition, when an alkyl group directly bonded to a silicon atom has more than 20 carbon atoms, its molecular weight is so large that it does not easily penetrate into the substrate.

As the alkylalkoxysilane as described above, it is most preferable to use a monoalkyl trialkoxy silane, for example, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxy Silane, undecylethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, One or two or more alkylalkoxysilanes selected from octadecyltriethoxysilane, nonadecyltriethoxysilane and eicosyltriethoxysilane can be used in combination.

In addition, the silicone aqueous emulsion may further contain an organopolysiloxane as the waterproof active ingredient together with the alkylalkoxysilane. The organo polysiloxane is preferably an alkoxy group-containing organo polysiloxane or aminoalkyl group-containing organo polysiloxane, more specifically, the organo polysiloxane may be used, for example, linear polydimethylsiloxane. The chemical formula of the polydimethylsiloxane may be represented by (CH) ₃ SiO [SiO— (CH ₃ ) ₂ ] nSi (CH ₃ ) _3, where n is one or more.

At this time, the silicon compound in which the alkylalkoxysilane and the organopolysiloxane are mixed contains 5 to 80% by weight in 100% by weight of the silicone aqueous emulsion. If the silicone compound, which is a waterproofing active ingredient, is less than 5% by weight, it is difficult to obtain sufficient waterproofness, and when it exceeds 80% by weight, the emulsion particle size in the emulsion cannot be optimized and the stability of the emulsion is reduced. Preferably, the silicone compound is contained 15 to 80% by weight in 100% by weight of the silicone aqueous emulsion. At this time, Preferably the alkylalkoxysilane and organopolysiloxane are not specifically limited, but it is good to mix and use in the weight ratio of 1.2-35: 1.

In addition, the silicone aqueous emulsion may optionally contain an organic solvent as a diluent in the process of obtaining a mixture of the alkyl alkoxysilane and the organopolysiloxane. The organic solvent may be xylene, toluene, toluene, n-hexane, heptane, cyclopentane, cyclopentane, methylcyclopentane, and the like. Although not particularly limited, it may be contained in an amount of 5 to 75% by weight in 100% by weight of the silicone aqueous emulsion.

In addition, the silicone aqueous emulsion contains an emulsifier for emulsification, the emulsifier is contained 0.14 ~ 6.0% by weight in 100% by weight of the silicone aqueous emulsion. When the amount of the emulsifier is less than 0.14% by weight, it is difficult to obtain a stable emulsion. When the amount of the emulsifier is higher than 6.0% by weight, it is difficult to obtain a relatively water-resistant active ingredient and sufficient waterproof performance by the hydrophilic group of the emulsifier (surfactant). That is, when it exceeds 6.0% by weight may be a waterproof performance. Preferably, the emulsifier is contained at 0.2 to 2.94% by weight. The emulsifiers are fatty acid salts, alkyl sulfates, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphorates, sulfonates, polyoxyethylene alkyl ether sulfonates, poly Oxyethylene alkylarylether sulfonate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkylphosphate, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester, ammonium lauryl sulfate, sodium lorate sulfate, polyoxyethylene alkyl ether, polyoxy Ethylene oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, alkylamines, quaternary ammonium salts, alkylpyridinium salts and alkylsIt may be selected from such as imidazole salts.

The waterproof insulating coating resin composition according to the present invention is composed of a water-based polyurethane hybrid emulsion in addition to the silicone aqueous emulsion as described above for fast curing speed and adhesion and physical properties reinforcement in water. The water-dispersed polyurethane hybrid emulsion is an emulsion in which at least one compound selected from acryl and epoxy is introduced into the polyurethane. Specifically, the emulsion is a polyurethane-acrylic resin, a polyurethane-epoxy resin or a polyurethane-epoxy-acrylic resin emulsified in water, which is synthesized in the following manner.

First, a polyol is put in a reactor, and then heated to 80 ° C. to completely dissolve the polyol. Dimethylol propionic acid (DMPA) was dissolved in solvent N-methyl-2-pyrrolidone (NMP; N-methyl-2-pyrrolidone), put it in a reactor, and stirred at the same temperature for 30 minutes. Mix well. Next, dibutyltin dilaurate (DBTL; dibutyltin dilaurate) and an isocyanate compound were added to the reactor as a tin (Sn) -based catalyst, and the final NCO group to be obtained by reacting at 80 ° C. for 150 minutes was obtained. A polyurethane (PU) prepolymer having end groups is synthesized. As such, after the synthesis of the PU prepolymer having an NCO end group, the temperature was lowered to 60 ° C., triethylamine (TEA) was added as a neutralizing agent, and the carboxyl group (COOH group) group of the dimethylol propionic acid (DMPA) was added. Neutralize After neutralization, after 20 minutes, one or more monomers selected from epoxy and acryl are added as diluents and completely diluted for 10 minutes. At this time, the diluent lowers the viscosity of the PU prepolymer to improve the reaction temperature control and flow properties during synthesis, and enables the formation of an emulsion having excellent colloidal stability and water particle size of several tens of nanometers when dispersed.

Apart from the above, while adding water to another reactor and stirring at high speed, the neutralization diluted PU prepolymer is slowly added to carry out the water dispersion process. At this time, the chain extension reaction is carried out to avoid the reaction between the NCO group and water that did not react at the same time as the water dispersion process is completed and to increase the molecular weight. The chain extension reaction was diluted with water at 25 ° C. in a chain extender, and stirred for about 2 hours until the chain extension reaction was completed.

In the reaction process, the polyol may be a polyether-based or polyester-based polyol according to its structure, and according to the present invention, a polyol based polyol may be selected according to its use, but a polyether-based polyol is preferably used for waterproofing. And polyether polyol is more preferable. As the polyether polyol, low molecular weight polytetramethylene ether glycol (PTMG) is preferably used after completely removing moisture using a vacuum oven, and the isocyanate compound is a diisocyanate. Preference is given to using isophorone diisocyanate (IPDI; Isophorone diisocyanate). In addition, the chain extender is preferably selected from epoxy or acrylic, and specifically, at least one selected from epoxy, acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid, acrylamide, acrylnitriyl, and the like. Can be used.

When the above reaction is completed, a water-dispersed polyurethane hybrid emulsion in which at least one compound selected from acrylic and epoxy is introduced into the polyurethane (PU).

In this case, the polyurethane hybrid emulsion may be in the form of a water-dispersed polyurethane-acrylic emulsion, a water-dispersed polyurethane-epoxy emulsion, or a water-dispersed polyurethane-epoxy-acrylic emulsion according to the use of the chain extender and the reaction. (cross linked structure). Preferably synthesized into a polyurethane-epoxy-acrylic emulsion. Such a polyurethane-epoxy-acrylic emulsion exhibits a stronger structure than a polyurethane-acrylic emulsion or a polyurethane-epoxy emulsion at the time of curing and is superior in adhesive strength and strength.

In addition, the waterproof coating resin composition according to the present invention comprises an unsaturated polymer resin. As the unsaturated polymer resin has a double bond, at least one selected from unsaturated polyesters and unsaturated polyvinyl esters is used.

In this case, the water-dispersed polyurethane hybrid emulsion and the unsaturated polymer resin may be copolymerized and then contained in the resin composition of the present invention. Specifically, after preparing the water-dispersed polyurethane hybrid emulsion as described above, by adding and copolymerizing an unsaturated polymer resin therein to prepare a water-soluble hybrid water dispersant copolymerized with an unsaturated polymer resin and a polyurethane hybrid, and then the silicone aqueous The resin composition according to the present invention can be prepared by mixing in an emulsion.

In addition, the present invention may further include a filler according to the present invention, wherein the filler is for strength reinforcement, and may be selected from waste rubber powder, fiber, inorganic powder, and mixtures thereof, and the inorganic powder may be, for example, silicon oxide. (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (FeO, Fe ₂ O ₃ ), calcium oxide (CaO), magnesium carbonate (MgCO ₃ ), calcium carbonate (CaCO ₃ ), fume silica Magnesium oxide (MgO), fly ash (flyed ash) and ceramics (eg, rock, jade, etc.) may be used in one or two or more selected from the group consisting of.

The resin composition according to the invention described above is mixed with a curing agent at the construction site and then coated on a substrate (concrete, cement, stone, etc.), wherein the curing agent is selected from a peroxide side compound, specifically, dibenzoyl peroxide Or methylethyl peroxide may be used.

The resin composition according to the present invention has excellent cross-linked network structure by mixing the curing agent and has excellent waterproof performance and rapid hardening in water, and has excellent adhesion and fixing strength. Specifically, the silicone aqueous emulsion and the water-dispersed polyurethane hybrid emulsion are cured by radical polymerization reaction with an unsaturated polymer resin by mixing of a curing agent, resulting in an exothermic reaction while having excellent waterproofing performance, thereby rapidly curing. In addition, dimethylol propionic acid (DMPA) used in the synthesis of the water-dispersed polyurethane hybrid emulsion improves the adhesion by developing the network structure of the PU prepolymer.

The water-based polyurethane hybrid emulsion may be included in an amount of 10 to 150 parts by weight based on 100 parts by weight of the silicone aqueous emulsion, and the unsaturated polymer resin may be used in 100 parts by weight of the silicone aqueous emulsion. 5 to 200 parts by weight may be included and copolymerized with the water-dispersed polyurethane hybrid emulsion. In addition, the water-dispersed polyurethane hybrid emulsion is preferably made of 20 to 150 parts by weight of the polyurethane hybrid resin emulsified with respect to 100 parts by weight of water in the process of water dispersion. The filler is not particularly limited, but may be included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the silicone aqueous emulsion.

In addition, the resin composition according to the present invention is preferably used by mixing with a curing agent in a weight ratio of 1: 0.005 to 0.2 based on the water-dispersed polyurethane hybrid emulsion (that is, water-dispersed polyurethane hybrid emulsion in a weight ratio: curing agent = 1: 0.005). ~ 0.2).

The resin composition of the present invention described above may be used in a substrate coating such as concrete, cement, tile, stone, wood, metal, etc. by a method of roll coating, spray coating, injection, impregnation, and the like, in particular, on a substrate such as concrete. It can be usefully applied for repair purposes and waterproofing agents to fill cracks. And it is useful in water environment.

Hereinafter, embodiments of the present invention will be described. The following examples are provided only to explain the present invention in more detail, whereby the technical scope of the present invention is not limited.

All reactions were purged with nitrogen (N ₂ ) gas to exclude other side reactions, and the experiment was conducted. The reactor consisted of four 1000 ml round glass spheres equipped with a condenser, a thermocontroller, and a direct stirrer. The reactor was used.

First, the polyol (PTMG-1000, Mw = 1000, OH number = 112) was put in the four-necked reactor, and the temperature was heated to 80 ° C to completely dissolve the polyol. At this time, before the PTMG-1000 was introduced into the reactor, the vacuum oven was used for 6 hours at 120 ° C. to completely remove water. Dimethylol propionic acid (DMPA) was used to introduce a water-soluble group, but it was dried at 60 ° C. to completely remove the moisture of DMPA, and then dissolved in N-Methylpyrrolidone (NMP, manufactured by Aldrich). And the dissolved DMPA was put into the reactor and stirred for 30 minutes at the same temperature and mixed well.

Next, put a tin-based reaction catalyst (DBTL) and IPDI (Isophorone diisocyanate: Bayer Co.) in the reactor and reacted for 150 minutes at 80 ℃ PU prepolymer (PU) having a terminal end NCO group to obtain prepolymer). The content of NCO groups in the synthesized PU prepolymer was measured using the di-n-butylamine back-titration (DBBT) method, and the theoretical amount of residual NCO groups was calculated based on the reaction with all OH groups. As such, after the synthesis of the prepolymer having NCO end groups, the temperature was lowered to 60 ° C., and TEA (produced by Junsei Chemical Co., Ltd.) was added as a neutralizing agent to neutralize the COOH group of DMPA. After 20 minutes of neutralization, acrylic monomer was added as a diluent and completely diluted for 10 minutes.

Water was added to another reactor, and the mixture was slowly added to the PU prepolymer, which was synthesized while stirring at high speed, to perform a water dispersion process. Double-distilled deionized water (DDI water) was used as the water used for water dispersion. At the end of the water dispersion process, the chain extension reaction was performed by adding acrylate as a chain extender to avoid the reaction between the NCO group and water which did not react and to increase the molecular weight. In this case, the chain extension reaction was diluted with water at 25 ° C. in a chain extender, and further stirred for about 2 hours until the chain extension reaction was completed to obtain a water-dispersed polyurethane-acrylic emulsion. Next, the unsaturated polyvinyl ester was thrown in and stirred, and the water-dispersed polyurethane-epoxy emulsion copolymerized with the unsaturated vinyl ester was obtained (water dispersion production).

Then, after mixing magnesium oxide (MgO) and silica (SiO ₂ ) in the water-dispersed polyurethane-acrylic copolymer copolymerized with the unsaturated polyvinyl ester, and then mixing the mixture, the hexyltriethoxysilane emulsified silicone aqueous emulsion Mix and stir (waterproof emulsion preparation).

Dibenzoyl peroxide was mixed as a curing agent in the waterproof emulsion obtained as described above, and then it was applied to a concrete substrate sprayed with water. After about 2 hours after application, it was confirmed that it was completely cured.

Claims (4)

At least one alkyl group having 6 to 20 carbon atoms; At least one alkoxy group selected from the group consisting of methoxy, ethoxy and protoxy bonded to the alkyl group; And an silicone aqueous emulsion containing an alkylalkoxysilane having an alkoxy group bonded to the alkyl group bonded to a silicon atom; Mixing and stirring polyol and dimethylol propionic acid (DMPA); Synthesizing a prepolymer by mixing an isocyanate compound in the presence of a reaction catalyst to the mixture; Neutralizing the COOH group of dimethylol propionic acid (DMPA) by adding triethylamine (TEA) as a neutralizing agent to the prepolymer; Inputting at least one monomer selected from the group consisting of epoxy and acryl as a diluent to the neutralized mixture to obtain a neutralized diluent prepolymer; Putting the neutralized dilution prepolymer into water being stirred at high speed to perform a water dispersion process; And a water-dispersed polyurethane hybrid emulsion synthesized by injecting and stirring one or more chain extenders selected from the group consisting of epoxy and acryl-based in the water dispersion process. And Waterproofing insulation coating resin composition comprising at least one unsaturated polymer resin selected from the group consisting of unsaturated polyesters and unsaturated polyvinyl esters. The method of claim 1, The silicone aqueous emulsion is a waterproof insulating coating resin composition further comprises an organopolysiloxane (Organopolysiloxane). The method according to claim 1 or 2, The water-dispersed polyurethane hybrid emulsion is a water-dissipative polyurethane (acrylic) -acrylic emulsion, polyurethane-epoxy emulsion or polyurethane-epoxy-acrylic emulsion, waterproof coating coating composition. The method according to claim 1 or 2, The reaction catalyst is a waterproof insulating coating resin composition, characterized in that the tin (Sn) -based catalyst.