KR102324995B1 - Primer composition having excellent water proof and adhesion property and water-proof construction method for concrete constructions - Google Patents

Abstract

The present invention relates to a primer composition having excellent waterproof and adhesive performance and a waterproof construction method of a concrete structure using the same. The primer composition having excellent waterproof and adhesive performance comprises, with respect to 100 parts by weight of a water-dispersed polyurethane resin having a solid content of 35 to 60% by weight, 30 to 50 parts by weight of a polyester copolymer containing a sulfonate group of Chemical Formula 1 below, 10 to 30 parts by weight of an isocyanate-based silane-modified epoxy resin, 10 to 30 parts by weight of polyvinyl alcohol, 0.1 to 10 parts by weight of 2-acrylamido-2-methylpropane sulfonic acid, 0.1 to 10 parts by weight of an epoxy-based silane coupling agent, 0.01 to 5 parts by weight of a ketimine curing agent, and 0.01 to 5 parts by weight of an adhesion promoter. With the excellent waterproof performance, it is possible to provide a primer layer as a primary waterproofing layer when waterproofing a concrete structure, as well as provide excellent adhesion and durability between the concrete structure and a waterproofing film and waterproofing sheet.

Description

Primer composition having excellent waterproof and adhesive performance and waterproof construction method of concrete structure using the same

The present invention can provide not only a primer layer as a primary waterproofing layer when waterproofing a concrete structure with excellent waterproofing performance, but also excellent adhesion and durability between a concrete structure and a waterproofing film and waterproofing sheet. It relates to a primer composition having excellent waterproof performance and adhesive performance, and a method for waterproofing a concrete structure using the same.

Recently, interest in improving materials and construction quality for waterproofing construction is increasing in order to secure and maintain safety and durability for interlayer, roof or basement waterproofing of concrete structures.

In general, the waterproof construction method mainly used in Korea can be divided into a coating method, a sheet type, and a composite waterproofing construction method. The coating type is to use various coating film waterproofing materials, the sheet type is to use a waterproof sheet, and the composite waterproofing construction method is to apply the coating type and the sheet type in combination.

The coating-type waterproofing construction method is relatively easy to install in narrow or complex areas. In addition, seamless construction is possible and maintenance is relatively easy. However, the coating-type waterproof construction method has a disadvantage in that it is difficult to maintain a uniform thickness of the coating film depending on the condition of the floor surface or the work site. The sheet-type waterproofing construction method has great advantages in that it is easy to install and can reduce labor costs, but has disadvantages in that it is difficult to construct complex areas and difficult to repair parts. In addition, the sheet-type waterproofing construction method has a problem in that the watertightness at the joint between the sheets is lowered. Therefore, in recent years, interest in waterproof construction methods that can compensate for the shortcomings of each construction method and shorten the construction period as well as make the construction method simpler.

On the other hand, in the case of the conventional primer, there have been many studies for improving the adhesion between the waterproof coating film and the waterproof sheet, but there is a problem that the effort to improve the waterproof function is insufficient.

In addition, in the case of repairing a concrete structure, waterproofing should be carried out after removing the deteriorated parts and foreign substances from the concrete structure. There was a problem in that adhesion with the waterproofing material was not performed well.

Therefore, there is an urgent need to develop a primer composition capable of providing excellent waterproof performance and durability while providing excellent adhesion between the concrete structure and the waterproof coating film and waterproof sheet, and a method for waterproofing a concrete structure using the same.

Republic of Korea Patent No. 10-1236733 Republic of Korea Patent No. 10-1714473 Republic of Korea Patent Registration No. 10-1791653

The present invention has been devised to solve the above problems, and an embodiment of the present invention can provide a primer layer as a primary waterproofing layer when waterproofing a concrete structure with excellent waterproofing performance, and a concrete structure and a waterproofing film And it is an object of the present invention to provide a primer composition having excellent waterproof performance and adhesive performance that can provide excellent adhesion and durability with the waterproof sheet.

In addition, another embodiment of the present invention is to provide a waterproof construction method of a concrete structure using the primer composition having the excellent waterproof performance and adhesive performance.

Various problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention is a primer composition having excellent waterproof performance and adhesive performance, based on 100 parts by weight of a water-dispersed polyurethane resin having a solid content of 35 to 60% by weight, a polyester containing a sulfonate group represented by the following formula (1) 30 to 50 parts by weight of the copolymer, 10 to 30 parts by weight of an isocyanate-based silane-modified epoxy resin, 10 to 30 parts by weight of polyvinyl alcohol, 0.1 to 10 parts by weight of 2-acrylamido-2-methylpropane sulfonic acid, an epoxy-based silane couple It provides a primer composition having excellent waterproof performance and adhesive performance comprising 0.1 to 10 parts by weight of a ring agent, 0.01 to 5 parts by weight of a ketimine curing agent, and 0.01 to 5 parts by weight of an adhesion promoter.

[Formula 1]

In the above formula, m is an integer of 0 to 10, and n is an integer of 1 or more.

The water-dispersed polyurethane resin is

A prepolymer prepared by reacting 1 to 5 parts by weight of dimethylolpropionic acid, 15 to 30 parts by weight of a diisocyanate compound, 10 to 20 parts by weight of inorganic particles, and 5 to 10 parts by weight of an aminosilane compound to 100 parts by weight of the polyol to prepare a prepolymer manufacturing steps; Neutralizing the prepolymer by adding 1 to 5 parts by weight of a neutralizing agent, 50 to 90 parts by weight of acetone, and 100 to 300 parts by weight of water to the prepared prepolymer and dispersing in water; and reacting 0.5 to 1 parts by weight of a chain extender and 300 to 500 parts by weight of water to the neutralized prepolymer to prepare an aqueous dispersion polyurethane resin having a solid content of 35 to 60% by weight. have.

The inorganic particles are titanium carbonitride having an average particle diameter of 10 nm to 50 μm;

The titanium carbonitride is a step of preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at a temperature of 1300 to 1500 ° C. Heat treatment for 2 to 5 hours; may be prepared by a method comprising.

The expanded graphite is prepared by mixing 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15° C. and depositing the graphite for 24 to 36 hours, washing and drying the deposited graphite to obtain graphite before expansion, and the graphite before expansion is expanded at a temperature of 500 to 800 ° C. for 10 to 30 minutes so that the expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) is 450 It may be prepared by a method comprising the step of producing high-expansion graphite to 600 times.

In addition, another embodiment of the present invention is a waterproof construction method of a concrete structure using the primer composition having the excellent waterproof performance and adhesive performance,

After removing the deteriorated part and foreign substances of the construction target of the concrete structure, the base surface treatment step of washing and drying the surface of the construction target; applying a primer composition having the excellent waterproof performance and adhesive performance to the surface of the construction target on which the base surface treatment is completed; attaching the waterproof sheet to the surface of the construction target on which the application of the primer composition having the excellent waterproof performance and adhesive performance is completed; forming a waterproofing layer by applying and drying a coating film waterproofing material on the surface of the waterproofing sheet; and forming a surface protection layer by applying and drying a top coating material for surface protection on the surface of the waterproof layer.

According to the primer composition having excellent waterproof performance and adhesive performance according to an embodiment of the present invention and the waterproofing construction method of a concrete structure using the same, a primer layer as a primary waterproofing layer is provided when waterproofing a concrete structure with excellent waterproofing performance There is an effect that can be done. At the same time, it is possible to improve adhesive properties such as initial adhesion, state adhesion, heat-resistance adhesion, and water-resistant adhesion, thereby providing excellent adhesion between the concrete structure and the waterproof coating film and the waterproof sheet. In addition, there is an effect of providing durability such as abrasion resistance and weather resistance.

1 shows a schematic construction flow diagram of a method for waterproofing a concrete structure using a primer composition having excellent waterproofing performance and adhesive performance according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

One embodiment of the present invention is a primer composition having excellent waterproof performance and adhesive performance, based on 100 parts by weight of a water-dispersed polyurethane resin having a solid content of 35 to 60% by weight, a polyester containing a sulfonate group represented by the following formula (1) 30 to 50 parts by weight of the copolymer, 10 to 30 parts by weight of an isocyanate-based silane-modified epoxy resin, 10 to 30 parts by weight of polyvinyl alcohol, 0.1 to 10 parts by weight of 2-acrylamido-2-methylpropane sulfonic acid, an epoxy-based silane couple It provides a primer composition having excellent waterproof performance and adhesive performance comprising 0.1 to 10 parts by weight of a ring agent, 0.01 to 5 parts by weight of a ketimine curing agent, and 0.01 to 5 parts by weight of an adhesion promoter.

[Formula 1]

In the above formula, m is an integer of 0 to 10, and n is an integer of 1 or more.

According to the primer composition having excellent waterproof performance and adhesive performance according to an embodiment of the present invention and the waterproof construction method of a concrete structure using the same, when waterproofing a concrete structure with excellent waterproof performance, a primer layer as a primary waterproofing layer is used. effect that can be provided. At the same time, it is possible to improve adhesive properties such as initial adhesion, state adhesion, heat-resistance adhesion, and water-resistant adhesion, thereby providing excellent adhesion between the concrete structure and the waterproof coating film and the waterproof sheet. In addition, there is an effect of providing durability such as abrasion resistance and weather resistance.

More specifically, the water-dispersible polyurethane resin having the solid content of 35 to 60% by weight serves to provide excellent waterproof performance and adhesive performance.

The water-dispersed polyurethane resin contains 1 to 5 parts by weight of dimethylolpropionic acid, 15 to 30 parts by weight of a diisocyanate-based compound, 10 to 20 parts by weight of inorganic particles, and 5 to 10 parts by weight of an aminosilane-based compound based on 100 parts by weight of the polyol. A prepolymer preparation step of preparing a prepolymer by reacting the parts; Neutralizing the prepolymer by adding 1 to 5 parts by weight of a neutralizing agent, 50 to 90 parts by weight of acetone, and 100 to 300 parts by weight of water to the prepared prepolymer and dispersing in water; and reacting 0.5 to 1 parts by weight of a chain extender and 300 to 500 parts by weight of water to the neutralized prepolymer to prepare an aqueous dispersion polyurethane resin having a solid content of 35 to 60% by weight. have. Thereby, there is an effect that can provide better adhesion performance not only with the concrete structure, but also with the waterproof coating film and the waterproof sheet.

At this time, the polyol is generally used in the art, and the type is not particularly limited, but for example, polycarbonate polyol, polyester polyol, polyether polyol, poly(meth)acrylic polyol, polydiene polyol, and these At least one selected from the group consisting of a mixture of can be preferably used.

More preferably, in consideration of the excellent waterproof and adhesive properties of the primer composition having excellent waterproof and adhesive performance according to an embodiment of the present invention, and whether or not coating film performance defects such as pinholes occur, polycarbonate polyol and poly A mixture of the ester polyol in a ratio of 1: 1 to 3 by weight can be used more preferably.

In addition, dimethylol propionic acid functions to further improve the adhesive performance together with the polyol.

In addition, the diisocyanate-based compound is generally used in the art, and the type thereof is not particularly limited. For example, toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, hexanedi At least one selected from the group consisting of isocyanate, hexamethylene diisocyanate, and mixtures thereof may be preferably used.

In addition, the inorganic particles reinforce the strength of the concrete structure by increasing the hardness of the primer, and can provide better adhesion performance with not only the concrete structure but also the waterproof coating film and the waterproof sheet, as well as abrasion resistance, weather resistance, etc. It has the effect of improving durability.

One or more selected from the group consisting of titanium dioxide, titanium carbonitride, and mixtures thereof may be preferably used as the inorganic particles.

In particular, the above-described effect can be further improved by using titanium carbonitride having an average particle diameter of 10 nm to 50 μm as the inorganic particles.

More specifically, the titanium carbonitride is a titanium oxide (TiO ₂ ) step of preparing a mixture of a powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at 1300 to 1500 ° C. It is prepared by a method comprising; a heat treatment at a temperature of 2 to 5 hours; the composition may be in _{the range of TiC 0.3} N _0.7 to TiC _0.7 N _0.3 , and the average particle diameter may be 10 nm to 50 μm.

At this time, the expanded graphite is mixed with 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. and depositing the graphite for 24 to 36 hours, washing the deposited graphite And drying to obtain graphite before expansion, and expanding the graphite before expansion at a temperature of 500 to 800 ° C. for 10 to 30 minutes to expand the ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) It may be a high-expansion graphite prepared by a method comprising the step of preparing high-expansion graphite that is 450 to 600 times. At this time, drying of the deposited graphite may be performed at a temperature of 85 to 105 °C for 2 to 10 hours.

In addition, the aminosilane-based compound is generally used in the art, and the type thereof is not particularly limited. For example, N-(aminoethyl)-3-aminopropyltrimethoxysilane, (3-aminopropyl ) At least one selected from the group consisting of triethoxysilane, (3-aminopropyl)trimethoxysilane, and mixtures thereof may be preferably used.

In addition, the neutralizing agent is generally used in the art, and the type is not particularly limited. For example, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanol At least one selected from the group consisting of amine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine, and mixtures thereof may be preferably used.

In addition, the chain extender is generally used in the art, and the type thereof is not particularly limited. For example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-Butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane , xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine, and at least one selected from the group consisting of mixtures thereof is preferably used can

Hereinafter, the content of the components constituting the primer composition having excellent waterproof performance and adhesive performance is based on 100 parts by weight of the water-dispersible polyurethane resin.

The polyester copolymer including the sulfonate group of Formula 1 functions to further improve the excellent adhesive performance.

The polyester copolymer including the sulfonate group of Formula 1 is preferably contained in an amount of 30 to 50 parts by weight based on 100 parts by weight of the water-dispersed polyurethane resin. When the content of the polyester copolymer is too small, there is a problem that the above-described improvement effect may be weak, and when the content of the polyester copolymer is too large, the viscosity increases and the solubility decreases, and the existing adhesive properties and There is a problem that the coatability may be deteriorated.

The isocyanate-based silane-modified epoxy resin functions to further improve waterproof performance as well as adhesive performance.

The isocyanate-based silane-modified epoxy resin may further improve the above-described effects by using a chemical reaction between a bisphenol A-type epoxy resin and an isocyanate-based silane. In this case, as the isocyanate-based silane, at least one selected from the group consisting of 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and mixtures thereof may be preferably used.

The isocyanate-based silane-modified epoxy resin is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the water-dispersed polyurethane resin.

When the content of the isocyanate-based silane-modified epoxy resin is too small, there is a problem that the above-described improvement effect may be weak, and when the content of the isocyanate-based silane-modified epoxy resin is too large, the increase rate of the effect compared to the amount used is insufficient. There are problems that can be economical.

The polyvinyl alcohol functions to further improve the excellent adhesive performance.

The polyvinyl alcohol is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the water-dispersed polyurethane resin. When the content of the polyvinyl alcohol is too small, there is a problem that the above-described improvement effect may be weak, and when the content of the polyvinyl alcohol is too large, the increase rate of the effect compared to the amount used is insufficient, which may be uneconomical. have.

The 2-acrylamido-2-methylpropane sulfonic acid functions to further improve waterproof performance as well as adhesive performance. In particular, it functions to further improve durability such as abrasion resistance and weather resistance.

The 2-acrylamido-2-methylpropane sulfonic acid is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the aqueous dispersion polyurethane resin. When the content of 2-acrylamido-2-methylpropane sulfonic acid is too small, there is a problem that the improvement effect may be weak, and when the content of 2-acrylamido-2-methylpropane sulfonic acid is too large There is a problem in that the viscosity increases, the solubility decreases, and the existing adhesive properties and applicability may decrease.

The epoxy-based silane coupling agent functions to further improve waterproof performance as well as adhesive performance.

The epoxy-based silane coupling agent is 3-glycidoxypropyl trimethoxysilane (GPTMS), 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane (2- (3,4-) epoxycyclohexyl)ethyltrimethoxysilane), 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, and mixtures thereof The above can be used preferably.

The epoxy-based silane coupling agent is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the water-dispersed polyurethane resin. When the content of the epoxy-based silane coupling agent is too small, there is a problem that the above-described improvement effect may be weak, and when the content of the epoxy-based silane coupling agent is too large, the viscosity increases and solubility decreases, and the existing adhesion There is a problem in that physical properties and coating properties may be deteriorated.

The ketimine curing agent functions to further improve adhesive performance by accelerating the curing reaction.

The ketimine curing agent is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the water-dispersed polyurethane resin. When the content of the ketimine curing agent is too small, there is a problem that the above-described improvement effect may be weak, and when the content of the ketimine curing agent is too large, the curing reaction rate is excessively fast, and work performance and storage stability may be reduced. there is a problem with

The adhesion promoter functions to further improve adhesion performance.

The adhesion promoter may preferably use at least one selected from the group consisting of alkylphenol resins, alkylphenolformaldehyde resins, rosin and rosin ester resins, coumaronindine resins, and mixtures thereof.

The adhesion promoter is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the water-dispersed polyurethane resin. When the content of the adhesion promoter is too small, there is a problem that the improvement effect may be weak, and when the content of the adhesion promoter is too large, there is a problem that the waterproof performance may be reduced.

In addition, another embodiment of the present invention is a waterproof construction method of a concrete structure using the primer composition having the excellent waterproof performance and adhesive performance,

After removing the deteriorated part and foreign substances of the construction target of the concrete structure, the base surface treatment step of washing and drying the surface of the construction target; applying a primer composition having the excellent waterproof performance and adhesive performance to the surface of the construction target on which the base surface treatment is completed; attaching the waterproof sheet to the surface of the construction target on which the application of the primer composition having the excellent waterproof performance and adhesive performance is completed; forming a waterproofing layer by applying and drying a coating film waterproofing material on the surface of the waterproofing sheet; and forming a surface protection layer by applying and drying a top coating material for surface protection on the surface of the waterproof layer.

1 is a schematic construction flowchart of a method for waterproofing a concrete structure using a primer composition having excellent waterproofing performance and adhesive performance according to an embodiment of the present invention.

The waterproof sheet is generally used in the art, and the type is not particularly limited, but, for example, a butyl rubber sheet-based, asphalt compound sheet-based, PVC composite sheet-based or uritan sheet-based waterproofing sheet is preferably used. can

In addition, the coating film waterproofing material is generally used, and the type thereof is not particularly limited, but, for example, a polyurethane-based, polyurea-based or epoxy-based coating film waterproofing material may be preferably used.

According to the primer composition having excellent waterproof performance and adhesive performance according to an embodiment of the present invention and the waterproofing construction method of a concrete structure using the same, a primer layer as a primary waterproofing layer is provided when waterproofing a concrete structure with excellent waterproofing performance There is an effect that can be done. At the same time, it is possible to improve adhesive properties such as initial adhesion, state adhesion, heat-resistance adhesion, and water-resistant adhesion, thereby providing excellent adhesion between the concrete structure and the waterproof coating film and the waterproof sheet. In addition, there is an effect of providing durability such as abrasion resistance and weather resistance.

As mentioned above, although a preferred embodiment of the present invention has been described in detail, the present invention is not limited to the above embodiment, and various modifications can be made by those skilled in the art within the scope of the technical spirit of the present invention. This is possible.

<Production Example 1>

Preparation of water-dispersible polyurethane resin

Based on 100 parts by weight of the polyester polyol, 3.5 parts by weight of dimethylolpropionic acid, 19 parts by weight of a diisocyanate-based compound (isophorone diisocyanate and hexamethylene diisocyanate are mixed in a 1: 1 weight ratio), 11.7 parts by weight of titanium dioxide and N -(aminoethyl)-3-aminopropyltrimethoxysilane reacting 8.2 parts by weight to prepare a prepolymer; neutralizing the prepolymer by adding 1.9 parts by weight of triethanolamine, 74 parts by weight of acetone, and 245 parts by weight of water to the prepared prepolymer and dispersing in water; and 0.7 parts by weight of a chain extender (1,4-hexamethylenediamine, adipoylhydrazide and hydrazine mixed in a 1: 1: 1 weight ratio) and 388 parts by weight of water were reacted with the neutralized prepolymer to obtain a solid content of 43 weight % of the water-dispersed polyurethane resin was prepared by a method comprising the step of preparing a water-dispersed polyurethane resin.

<Production Example 2>

Preparation of water-dispersible polyurethane resin

2.8 parts by weight of dimethylolpropionic acid, 2.8 parts by weight of dimethylolpropionic acid, a diisocyanate-based compound (isophorone diisocyanate and hexamethylene diisocyanate, 1:1 (mixed in a weight ratio) 27 parts by weight, 16 parts by weight of titanium carbonitride, and 7 parts by weight of (3-aminopropyl)trimethoxysilane to prepare a prepolymer by reacting a prepolymer preparation step; neutralizing the prepolymer by adding 2.5 parts by weight of triethylamine, 65 parts by weight of acetone, and 180 parts by weight of water to the prepared prepolymer and dispersing in water; and 0.5 parts by weight of a chain extender (1,4-hexamethylenediamine, adipoylhydrazide and hydrazine mixed in a 1: 1: 1 weight ratio) and 395 parts by weight of water were reacted with the neutralized prepolymer to have a solid content of 47 weight % of the water-dispersed polyurethane resin was prepared by a method comprising the step of preparing a water-dispersed polyurethane resin.

In this case, the titanium carbonitride is _{prepared by mixing titanium oxide (TiO 2} ) powder and carbon black so that a molar ratio of Ti: C is 1: 1 to prepare a mixed mixture, pulverizing the mixture, and pulverizing the pulverization Heat-treating the treated mixture at a temperature of 1400 ° C. for 5 hours in a nitrogen gas atmosphere; prepared by a method including, an average particle diameter of 19 μm was used.

<Production Example 3>

Preparation of water-dispersible polyurethane resin

It was carried out in the same manner as in Preparation Example 2, but the titanium carbonitride prepared by the following manufacturing method was used.

The titanium carbonitride is _{prepared by mixing titanium oxide (TiO 2} ) powder and expanded graphite so that the molar ratio of Ti: C is 1: 0.7 to prepare a mixture, pulverizing the mixture, and the pulverized mixture Heat treatment at a temperature of 1400 ° C. for 3 hours in a nitrogen gas atmosphere; prepared by a method including, and an average particle diameter of 12 μm was used. At this time, the expanded graphite is mixed with 100 parts by weight of sulfuric acid, 2.5 parts by weight of graphite, and 7.5 parts by weight of hydrazine at a temperature of 5° C. and depositing graphite for 24 hours, washing the deposited graphite several times to remove sulfuric acid, 90 Drying at a temperature of ℃ for 7 hours to obtain graphite before expansion, and expanding the graphite before expansion for 20 minutes at a temperature of 700 ℃ to the expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion) )) of high expansion graphite prepared by a method including the step of preparing 507 times high expansion graphite was used.

<Example 1>

Based on 100 parts by weight of the water-dispersed polyurethane resin prepared in Preparation Example 1, 39 parts by weight of a polyester copolymer including a sulfonate group of Formula 1-1, a bisphenol A epoxy resin, and 3-isocyanatopropyl 19 parts by weight of an isocyanate-based silane-modified epoxy resin prepared by reacting triethoxy silane in a 1: 1 molar ratio, 14 parts by weight of polyvinyl alcohol, 3 parts by weight of 2-acrylamido-2-methylpropane sulfonic acid, 3-gly By mixing 1.7 parts by weight of cidoxypropyltrimethoxysilane, 0.9 parts by weight of a ketimine curing agent and 1.3 parts by weight of an adhesion promoter (rosin ester resin) prepared by reacting 1.7 parts by weight of diethyltoluenediamine and methylethylketone in a molar ratio of 1: 3, A primer composition having excellent waterproof performance and adhesive performance was prepared.

[Formula 1-1]

In the above formula, m is 1 and n is 7.

<Example 2>

Based on 100 parts by weight of the water-dispersed polyurethane resin prepared in Preparation Example 2, 47 parts by weight of a polyester copolymer including a sulfonate group of Formula 1-1, a bisphenol A-type epoxy resin, and 3-isocyanatopropyl 11 parts by weight of an isocyanate-based silane-modified epoxy resin prepared by reacting triethoxy silane in a 1: 1 molar ratio, 17 parts by weight of polyvinyl alcohol, 8 parts by weight of 2-acrylamido-2-methylpropane sulfonic acid, 2-( 3 parts by weight of 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 0.5 parts by weight of a ketimine curing agent prepared by reacting 3 parts by weight of diethyltoluenediamine and methylethylketone in a molar ratio of 1:3 and an adhesion promoter (rosin ester resin) By mixing 3.5 parts by weight, a primer composition having excellent waterproof performance and adhesive performance was prepared.

<Example 3>

Based on 100 parts by weight of the water-dispersed polyurethane resin prepared in Preparation Example 3, 32 parts by weight of a polyester copolymer including a sulfonate group of Formula 1-1, a bisphenol A epoxy resin, and 3-isocyanatopropyl 18 parts by weight of an isocyanate-based silane-modified epoxy resin prepared by reacting triethoxy silane in a 1: 1 molar ratio, 11 parts by weight of polyvinyl alcohol, 3 parts by weight of 2-acrylamido-2-methylpropane sulfonic acid, 2-( 3,4-epoxycyclohexyl) ethyltrimethoxysilane 2.5 parts by weight, diethyltoluenediamine and methyl ethyl ketone in a 1: 3 molar ratio: 0.7 parts by weight of a ketimine curing agent and adhesion promoter (rosin ester resin) By mixing 2 parts by weight, a primer composition having excellent waterproof performance and adhesive performance was prepared.

<Comparative Example 1>

With respect to 100 parts by weight of the water-dispersed polyurethane resin prepared in Preparation Example 1, 10 parts by weight of an adhesion promoter (rosin ester resin) was mixed to prepare a primer composition for comparison.

<Test Example 1>

test specimen preparation

It was intended to evaluate the adhesive performance and waterproof performance of the primer composition having excellent waterproof performance and adhesive performance according to the present invention to a waterproof coating film and a waterproof sheet.

On each separately prepared PVC substrate, the primer composition having excellent waterproof performance and adhesive performance prepared in Examples 1 to 3 and the comparative primer composition prepared in Comparative Example 1 were respectively applied, dried naturally for 5 minutes, and then By applying and drying a separately prepared polyurethane-based waterproofing film, a test body for physical property evaluation was prepared.

Evaluation items and methods

go. Initial Adhesion Evaluation: Based on ASTM D3359 (Cross-hatch test), adhesive strength was evaluated for the prepared test body.

me. State adhesion evaluation: After the prepared test body was left at room temperature for 24 hours, adhesion was evaluated according to ASTM D3359 (Cross-hatch test).

all. Evaluation of heat-resistant adhesive strength: After leaving the prepared specimen at 80° C. for 168 hours, adhesive strength was evaluated according to ASTM D3359 (Cross-hatch test).

La. Water-resistant adhesive strength evaluation: After leaving the prepared test body at 50° C. and 95% humidity for 168 hours, the adhesive strength was evaluated according to ASTM D3359 (Cross-hatch test).

mind. Water resistance evaluation: After leaving the prepared test specimen immersed in a water depth of 15 cm to 1 m for 30 minutes according to the IPX7 (water resistance test) standard, the adhesion state was measured, and waterproofness was evaluated.

bar. Abrasion resistance evaluation: Using a Taber abraser (manufacturer: Gardoco company, device name: 5135), the prepared specimen was abraded 500 times under a CS-10F wear wheel and a load of 500 g. The haze difference (ΔHaze, unit: %) before and after abrasion was measured using a haze meter (Haze-meter, manufactured by Nippon Denshoku, device name: NDH 5000) to evaluate the abrasion resistance.

buy. Weather resistance evaluation: After storing the prepared test specimen under SAE J1960 standard conditions for 1,000 hours using a weatherometer (weatherometer, manufacturer: Atlas company, device name: Ci4000), appearance evaluation and yellow index change (ΔYI) were measured. In the appearance evaluation, it was determined that the case where delamination or cracking did not occur at all on the entire surface of the specimen was OK, and the case where even a little occurred was found to be a crack. In addition, the yellow index change is measured by using a Spectrophotometer (manufacturer: Konica-Minolta, device name: CM-3600d) to measure the yellow index (YI) value of the specimen before and after the light resistance test, and calculate the difference in the yellow index before and after the light resistance test got it

Ah. Storage stability evaluation: After leaving the primer composition having excellent waterproof and adhesive performance prepared in Examples 1 to 3 and the comparative primer composition prepared in Comparative Example 1 at 60° C. for 168 hours, using a Gardner viscometer , the viscosity was measured, and storage stability was evaluated.

Good (◎): Viscosity increase rate within 10%

Normal (○): Viscosity increase rate within 20%

Defect (×): Viscosity increase rate over 20%

Evaluation results

Results according to the evaluation items and evaluation methods are shown in Table 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 initial adhesion 5B 5B 5B 2B state adhesion 5B 5B 5B 3B heat-resistant adhesion 5B 5B 5B 1B waterproof adhesion 5B 5B 5B 1B waterproof ◎ (excellent) ◎ (excellent) ◎ (excellent) × (Insufficient) wear resistance
(ΔHaze) 1.8 2.0 2.4 7.3 weather resistance
(Appearance/ △ YI) OK/
0.9 OK/
0.7 OK/
0.3 Crack/
5.4 storage stability ◎ (good) ◎ (good) ◎ (good) ○ (Normal)

As can be seen in Table 1, in the case of the test body using the primer composition having excellent waterproof performance and adhesive performance prepared in Examples 1 to 3, compared with the test body using the comparative primer composition prepared in Comparative Example 1 , it was confirmed that the adhesive properties of the initial adhesion, state adhesion, heat-resistant adhesion, and water-resistant adhesion were excellent. In addition, in the case of the test body using the primer composition having excellent waterproof performance and adhesion performance prepared in Examples 1 to 3, compared to the test body using the comparative primer composition prepared in Comparative Example 1, excellent abrasion resistance, weather resistance and storage It was confirmed that it has stability.

Therefore, the primer composition having excellent waterproof performance and adhesive performance according to an embodiment of the present invention is expected to be able to implement excellent waterproof performance and adhesive performance with respect to a waterproof coating film and waterproof sheet.

<Test Example 2>

It was intended to evaluate the adhesive performance and waterproof performance of the primer composition having excellent waterproof performance and adhesive performance according to the present invention to a concrete test body.

By applying the primer composition having excellent waterproof performance and adhesive performance prepared in Examples 1 to 3 and the comparative primer composition prepared in Comparative Example 1 on each separately prepared concrete test body, respectively, and drying them naturally for 5 minutes, the physical properties were evaluated A test specimen was prepared for

For the prepared specimens, according to the Korean Industrial Standards KS F 4925 test method, the physical properties were measured, respectively, and are shown in Table 2 below.

In addition, after waterproofing the prepared test specimen, immersing it in water at about 20° C. to a depth of about 2 to 10 mm, and measuring the change in mass (absorption) of the test specimen at intervals of a certain time before and after immersion in water, Table 2 shown in At this time, the water attached to the surface of the specimen was measured after removing it using a wet cloth or the like.

division Example 1 Example 2 Example 3 Comparative Example 1 Compressive strength (N/㎟) 21 23 25 15 Adhesive strength (N/㎟) 0.8 1.1 1.2 0.3 pitching ratio 0.25 0.21 0.19 0.57 Absorption (after 1 hour) 0.04 0.02 0.01 2.35 Absorption (after 2 hours) 0.08 0.02 0.01 2.77 Absorption (after 3 hours) 0.13 0.02 0.02 2.89 Absorption (after 4 hours) 0.14 0.03 0.02 3.08 Absorption (after 18 hours) 0.40 0.03 0.02 4.12

As can be seen in Table 2, in the case of the test body using the primer composition having excellent waterproof performance and adhesive performance prepared in Examples 1 to 3, compared to the test body using the comparative primer composition prepared in Comparative Example 1 , it was confirmed that it has excellent compressive strength, adhesion strength, water permeability ratio, and low water absorption.

Therefore, the primer composition having excellent waterproof performance and adhesive performance according to an embodiment of the present invention is expected to be able to implement excellent waterproof performance and adhesive performance to a concrete structure.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential characteristics thereof. Therefore, it should be understood that all of the embodiments described above are illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalents.

Claims (5)

As a primer composition having excellent waterproof performance and adhesive performance,
A prepolymer prepared by reacting 1 to 5 parts by weight of dimethylolpropionic acid, 15 to 30 parts by weight of a diisocyanate compound, 10 to 20 parts by weight of inorganic particles, and 5 to 10 parts by weight of an aminosilane compound to 100 parts by weight of the polyol to prepare a prepolymer manufacturing steps; Neutralizing the prepolymer by adding 1 to 5 parts by weight of a neutralizing agent, 50 to 90 parts by weight of acetone, and 100 to 300 parts by weight of water to the prepared prepolymer and dispersing in water; and reacting 0.5 to 1 parts by weight of a chain extender and 300 to 500 parts by weight of water to the neutralized prepolymer to prepare a water-dispersed polyurethane resin having a solid content of 35 to 60% by weight, solid content With respect to 100 parts by weight of the water-dispersed polyurethane resin having a content of 35 to 60% by weight,
30 to 50 parts by weight of a polyester copolymer containing a sulfonate group of Formula 1, 10 to 30 parts by weight of an isocyanate-based silane-modified epoxy resin, 10 to 30 parts by weight of polyvinyl alcohol, 2-acrylamido-2-methylpropane A primer composition having excellent waterproof and adhesive performance, comprising 0.1 to 10 parts by weight of sulfonic acid, 0.1 to 10 parts by weight of an epoxy-based silane coupling agent, 0.01 to 5 parts by weight of a ketimine curing agent, and 0.01 to 5 parts by weight of an adhesion promoter .
[Formula 1]

In the above formula, m is an integer of 0 to 10, and n is an integer of 1 or more.
delete According to claim 1,
The inorganic particles are titanium carbonitride having an average particle diameter of 10 nm to 50 μm;
The titanium carbonitride is
Preparing a mixture in which titanium oxide (TiO ₂ ) powder and expanded graphite are mixed, grinding the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at a temperature of 1300 to 1500 ° C. for 2 to 5 hours A primer composition having excellent waterproof performance and adhesive performance, characterized in that it is prepared by a method comprising the step of heat-treating.
4. The method of claim 3,
The expanded graphite is
A step of depositing graphite for 24 to 36 hours by mixing 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. Washing and drying the deposited graphite to obtain graphite before expansion The expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) is 450 to 600 times by expanding the graphite before expansion at a temperature of 500 to 800 ° C for 10 to 30 minutes to obtain a A primer composition having excellent waterproof performance and adhesive performance, characterized in that it is prepared by a method comprising the step of preparing expanded graphite.
As a waterproofing construction method of a concrete structure using the primer composition having excellent waterproofing performance and adhesive performance according to any one of claims 1, 3 and 4,
After removing the deteriorated part and foreign substances of the construction target of the concrete structure, the base surface treatment step of washing and drying the surface of the construction target; applying a primer composition having the excellent waterproof performance and adhesive performance to the surface of the construction target on which the base surface treatment is completed; attaching the waterproofing sheet to the surface of the construction target on which the application of the primer composition having the excellent waterproofing performance and adhesive performance is completed; forming a waterproofing layer by applying and drying a coating film waterproofing material on the surface of the waterproofing sheet; and forming a surface protection layer by applying and drying a top coating material for surface protection on the surface of the waterproof layer.

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