KR20230054092A - Polyurea composition for frming a lower layer of a water-proof film having pin-hole covering ability and heat insulation ability and method for forming a water-proof structure - Google Patents

Abstract

Disclosed is a polyurea composition for a primer of a water-proof film, which comprises a main ingredient portion and a curing agent portion. The main ingredient portion of the present invention includes 20 to 50 wt% of an amine compound, 5 to 30 wt% of oil-modified polyol, 30 to 50 wt% of propylene carbonate, 1 to 10 wt% of a moisture absorbent, 1 to 5 wt% of a ceramic hollow pigment, and 1 to 10 wt% of a black coloring agent. The curing agent portion includes 10 to 40 wt% of urethan prepolymer, 10 to 40 wt% of an isocyanate compound, 30 to 50 wt% of a diluent, 1 to 10 wt% of a moisture absorbent, and 0.1 to 3 wt% of a moisture barrier.

Description

Polyurea composition for undercoating waterproofing film with improved pinhole cover performance and insulation performance and method for constructing a waterproof structure using the same FORMING A WATER-PROOF STRUCTURE}

The present invention relates to construction of a waterproof structure, and more particularly, to a polyurea composition for undercoating a waterproof film and a method of construction of a waterproof structure using the same.

Waterproof construction is performed to form an impermeable waterproof layer on the surface of the structure to prevent moisture from permeating into the inside and outside of the building, the bottom of the ship, parking lot, playground, outdoor plaza, outdoor structure, etc. all.

In order to improve the problems of the existing waterproofing method, a method using polyurea as a waterproofing material has recently been widely used. Polyurea has excellent tensile strength and elongation, excellent chemical resistance, and excellent durability, so it is widely used in the field of waterproofing such as construction, industry, and ships. In addition, polyurea has a fast curing speed, so the construction period can be shortened, and unlike polyurethane or epoxy, it has hydrophobicity with low affinity for water, so it can be sprayed directly on surfaces with moisture or low temperatures. Heat is also very strong, and its application range is gradually expanding.

However, although the waterproofing method using polyurea shows excellent waterproofing performance, it is greatly affected by the material or state of the substrate because it is a method of fully adhering to the floor. In particular, when polyurea is directly applied to a substrate such as concrete, there is a problem in that a pin-hole is generated because the surface is not flat due to material separation of concrete, voids, and the like.

In order to solve this problem, the current waterproofing construction method is painting a total of four times with one-component urethane undercoat / two-component urethane background adjustment process (process of filling concrete micro-voids) / polyurea / top coat. However, this process has problems in that the original feature of polyurea (quick curing) is discolored, air is delayed, which increases the burden of labor costs for workers, and interfacial peeling often occurs due to lack of compatibility between urethane and urea. there is.

One object of the present invention, to solve the above problems, is to provide a polyurea composition for waterproofing film undercoating that is environmentally friendly and has primer performance that can greatly improve work efficiency by omitting the urethane background adjustment process. .

Another object of the present invention is to provide a method for constructing a waterproof structure using the polyurea composition.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, and may be expanded in various ways without departing from the spirit and scope of the present invention.

The polyurea composition for undercoating a waterproofing film according to exemplary embodiments of the present invention for achieving the above-described object of the present invention includes a main part and a curing agent part. The main part is 4-4-methylenebis (2-dichloroaniline), tetrakis (2-hydroxypropyl) ethylenediamine, 4,4-methylenebis [N-methylpropyl] cyclohexanamine and tetraethyl N, N 20% to 50% by weight of an amine compound containing at least one selected from the group consisting of '-(methylenedi-4,1-cyclohexanediyl)bis(aspartate), 5% to 30% by weight of an oil-modified polyol , 30% to 50% by weight of propylene carbonate, 1% to 10% by weight of a moisture absorbent, 1% to 5% by weight of ceramic hollow pigment and 1% to 10% by weight of a black colorant. The curing agent part, urethane prepolymer 10% to 40% by weight, isocyanate compound 10% to 40% by weight, diluent 30% to 50% by weight, moisture absorbent 1% to 10% by weight, and moisture barrier 0.1% to 3% by weight contains %.

According to one embodiment, the moisture absorbent includes at least one selected from the group consisting of calcium oxide, zeolite, and magnesium oxide.

According to one embodiment, the moisture barrier includes at least one selected from the group consisting of 4-methylbenzenesulfonyl isocyanate and oxazolidine.

According to one embodiment, the black colorant includes at least one of carbon black and iron oxide.

According to one embodiment, the main part further includes 1% to 5% by weight of a phosphorus-based flame retardant.

A waterproof structure construction method according to exemplary embodiments of the present invention includes the steps of directly coating the polyurea composition on a concrete surface to form an undercoat layer; Forming an intermediate layer by coating a polyurea composition for intermediate coating on the undercoat; and forming a top coat layer on the middle coat layer.

As described above, according to exemplary embodiments of the present invention, when the polyurea coating system is applied to concrete, the pinhole cover performance of the undercoat itself is excellent, so the urethane background adjustment process is omitted and the curing time is fast, so the construction time can be shortened. . In addition, the undercoating film formed of the composition of the present invention has no compatibility problem in the same series as the polyurea to be coated subsequently, and it can form a waterproof film with excellent interlayer bonding strength with the polyurea to be subsequently painted by suppressing the yellowing phenomenon.

In addition, since the composition of the present invention includes a black colorant and whitening occurs during a normal urea reaction, it can be visually confirmed whether or not the composition has a normal reaction (whether a normal mixing ratio is maintained). Therefore, immediate repair is possible in the event of a defect.

In addition, the undercoat may have improved thermal insulation performance.

1 to 3 are cross-sectional views illustrating a waterproof structure construction method according to an embodiment of the present invention.

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, or combination thereof described in the specification, but one or more other features or numbers However, it should be understood that it does not preclude the presence or addition of steps, operations, components, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

Polyurea composition for undercoating waterproofing film

The polyurea composition according to an embodiment of the present invention may be a two-component composition including a main part and a curing agent part.

The main part contains at least an amine compound (polyamine) and a polyol. According to one embodiment, the subject part may further include a moisture absorbent and a diluent.

According to one embodiment, the amine compound may include a non-yellowing (or low-yellowing) polyamine having no aromatic ring structure. For example, the amine compound is 4-4-methylenebis (2-dichloroaniline), tetrakis (2-hydroxypropyl) ethylenediamine, 4,4-methylenebis [N-methylpropyl] cyclohexanamine, tetra ethyl N,N'-(methylenedi-4,1-cyclohexanediyl)bis(aspartate) or combinations thereof. These amine compounds can prevent or reduce yellowing, and can increase interlayer bonding strength due to their high compatibility with polyurea. Preferably, the amine compound may include tetrakis (2-hydroxypropyl) ethylenediamine.

The polyol may include an oil-modified polyol, a polyethylene/polypropylene glycol copolymer polyol, or a combination thereof. The oil-modified polyol is obtained by reacting natural oil obtained from flowers or seeds such as castor oil and sunflower seed oil with an alcohol compound or by modifying (epoxylation, ring-opening reaction, transesterification reaction, ethoxylation, propoxylation, etc.) Since it is a vegetable-derived component, it can have excellent eco-friendliness.

The polyurea composition according to an embodiment of the present invention may further include a diluent to adjust the curing speed and improve pinhole cover performance (increase smoothness). According to one embodiment, the diluent may include propylene carbonate, 2,2,4-trimethyl-1,3 pentanediol diisobutyrate, or a combination thereof. In one embodiment, the diluent may be propylene carbonate.

In addition, a moisture absorbent may be further included in order to prevent side effects (surface migration) caused by the addition of the diluent. According to one embodiment, the moisture absorbent may include calcium oxide, zeolite, magnesium oxide, or a combination thereof.

The subject part may further include additives such as a dispersant and a thickener, if necessary.

In addition, the subject part may further include a black colorant. The polyurea composition according to one embodiment may be sprayed using painting equipment. For example, the painting equipment includes a storage unit for mixing and storing the subject part and the hardener part, respectively. The subject part and the curing agent part may be mixed and sprayed at a volume ratio of about 1:1 from a spray gun. In the polyurea composition of the present invention, when curing is completed, the coating film is whitened. Therefore, a coating film cured by mixing the main part and the curing agent part normally may appear uniformly gray. However, when an appropriate discharge ratio is not maintained due to an abnormality of the coating equipment, the portion where the whitening phenomenon does not progress appears in black. Therefore, after the coating film is cured, the worker quickly checks whether the coating film is defective only with the surface color of the coating film, so that immediate repair is possible. For example, the black colorant may include carbon black, iron oxide, and the like.

For example, the main part may include 20 wt % to 50 wt % of the amine compound and 5 wt % to 30 wt % of the polyol. According to one embodiment, the subject part may further include 30% to 50% by weight of the diluent and 1% to 10% by weight of the moisture absorbent. In addition, the subject part may further include 1% to 10% by weight of the black colorant. If the content of the diluent is too small, the pinhole cover performance may be deteriorated, and if the content of the diluent is excessive, the curing speed may be reduced and the bonding force with the intermediate layer may be deteriorated.

According to one embodiment, the main part includes 30% to 40% by weight of the amine compound, 10% to 20% by weight of the polyol, 35% to 45% by weight of the diluent, 3% to 7% by weight of the moisture absorbent, and 3 wt% to 7 wt% of the black colorant may be included.

According to one embodiment, the main part includes 20% to 50% by weight of the amine compound, 5% to 30% by weight of the polyol, 30% to 50% by weight of the diluent, 1% to 10% by weight of the moisture absorbent, 1 to 10% by weight of the black colorant and 1 to 5% by weight of the hollow ceramic pigment may be further included.

The ceramic hollow pigment can increase the heat insulating performance (thermal insulating performance) of the waterproof membrane. Accordingly, it is possible to reduce heating and cooling costs of houses and the like.

If the content of the ceramic hollow pigment is too small, it is difficult to improve the heat insulation performance, and if the content of the ceramic hollow pigment is excessive, the pinhole cover performance of the composition may deteriorate. Therefore, the content of the ceramic hollow pigment is preferably 1% to 5% by weight, preferably 3% to 5% by weight.

According to one embodiment, the subject part may further include 1 wt % to 5 wt % of a phosphorus-based flame retardant. The flame retardant may impart flame retardancy to the coating film. For example, the phosphorus-based flame retardant may include TCPP (trichloropropyl phosphate).

The curing agent unit may include a urethane prepolymer and an isocyanate compound, and may further include a moisture absorbent and a diluent. In addition, the curing agent unit may further include additives such as a dispersing agent and a thickening agent, if necessary.

The urethane prepolymer may be obtained by reacting an aromatic diisocyanate and a polyol. For example, the aromatic diisocyanate may include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), or a combination thereof. For example, the polyol may include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyols, alkyd polyols, or combinations thereof.

According to one embodiment, the urethane prepolymer may be obtained by reacting methylene diphenyl isocyanate, polyoxyalkylene glycol, and 1,3-butylene glycol, and may have an isocyanate group at a terminal. For example, the urethane prepolymer may be obtained by reacting 15 to 30 parts by weight of methylenediphenyl diisocyanate, 5 to 10 parts by weight of polyoxyalkylene glycol, and 0.1 to 5 parts by weight of 1,3-butylene glycol. The reaction may proceed at about 50 °C. The residual isocyanate content of the urethane prepolymer may be 15% to 30%, and the weight average molecular weight may be about 2,000 to about 4,000.

According to one embodiment, the isocyanate compound is an aliphatic isocyanate such as 1,6-hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), or toluene diisocyanate, methylene diphenyl diisocyanate, or polymethylene polyphenyl isocyanate. aromatic isocyanates such as cinate and the like.

The moisture absorbent and the diluent may be the same as those used in the main part. According to one embodiment, it may be preferable to add a moisture absorbent and a diluent to each of the curing agent part and the main part of the polyurea composition. When the diluent is injected into only one of the curing agent part or the main part, an imbalance in discharge ratio may occur due to a difference in viscosity. In addition, when a moisture absorbent is added only to either the curing agent part or the main part, powder precipitation may occur due to an excessive increase in the moisture absorbent content.

According to one embodiment, the curing agent unit may further include a moisture blocking agent (a pre-reactive agent) to improve storage stability. When the curing agent part further includes a moisture absorbent, the isocyanate group may react with moisture in the air to form a gel as it is exposed to the air during the stirring process. According to the present invention, storage stability may be improved by adding a moisture blocking agent that reacts with moisture before the isocyanate component of the curing agent part. For example, the moisture barrier may include 4-methylbenzenesulfonyl isocyanate, oxazolidine, or a combination thereof.

For example, the curing agent part may include 10 wt % to 40 wt % of the urethane prepolymer and 10 wt % to 40 wt % of the isocyanate compound. According to one embodiment, the curing agent part may further include 30% to 50% by weight of the diluent, 1% to 10% by weight of the moisture absorbent, and 0.1% to 3% by weight of the moisture barrier.

According to one embodiment, the curing agent unit comprises 10% to 30% by weight of the urethane prepolymer, 20% to 40% by weight of the isocyanate compound, 40% to 50% by weight of the diluent, 1% to 10% by weight of the moisture absorbent, and 0.5 wt % to 2 wt % of the moisture barrier may be included.

How to construct a waterproof structure

1 to 3 are cross-sectional views illustrating a waterproof structure construction method according to an embodiment of the present invention.

Referring to FIG. 1 , a coating film 22 is formed by providing a polyurea composition on the base surface of a substrate 10 . The substrate 10 may be concrete or the like. Before providing the polyurea composition, foreign substances and laitance present on the substrate 10 may be removed by a grinding process or cleaned by high-pressure water spray (water jet) at 200 bar or more. The concrete substrate may have fine voids (PH, pinholes) resulting from material properties.

The polyurea composition is the same as the previously described two-component polyurea composition.

According to one embodiment, the polyurea composition may be sprayed onto the substrate 10 by a coating device dedicated to polyurea.

For example, the polyurea composition may be sprayed under low-temperature low-pressure conditions or high-temperature and high-pressure conditions. For example, the low temperature and low pressure condition may be about 30 ° C to about 50 ° C and the discharge pressure may be about 100 psi to about 500 psi, and the high temperature and high pressure condition is about 60 ° C to about 70 ° C and the discharge pressure is about 1,500 psi to about 2,000 psi.

For example, the polyurea composition may be sprayed under low temperature and low pressure conditions to control the curing speed or to minimize scattering dust. In addition, it is possible to suppress fine floating matters that may occur during painting (minimize the impact on worker safety and surrounding structures), have high airtightness between the substrate and the substrate, and form a flat upper surface to finish the polyurea intermediate layer that is subsequently painted. It can keep the surface beautiful. However, embodiments of the present invention are not limited thereto, and the polyurea composition can form an excellent undercoat even under high temperature and high pressure conditions.

According to one embodiment, the curing agent part and the main part of the polyurea composition may be sprayed after collision mixing at high temperature and high pressure in the spray gun 30 . However, the present invention is not limited thereto, and the curing agent part and the main part of the polyurea composition may be screw-mixed by a static mixer in a low-temperature and low-pressure state.

For example, the mixing ratio of the main part and the curing agent part may be about 1:1 in volume ratio, and the molar ratio between the reactive group (amine group and hydroxyl group) of the main part and the isocyanate group of the curing agent part is about 1.0:1.1 to about 1.0:1.2. can be

The polyurea composition can sufficiently fill the fine pores (PH) of the substrate 10 by having a low curing rate and high fluidity. Therefore, an undercoating layer can be formed without a conventional polyurethane ground control layer.

Referring to FIG. 2 , the cured undercoating layer 23 may show a gray color due to a whitening phenomenon and a black colorant included in the subject part. When the mixing discharge ratio of the curing agent part and the main part part is different, a black part or a white part may appear. Accordingly, since the operator quickly recognizes whether or not the undercoating layer 23 is defective, immediate repair is possible.

Referring to FIG. 3 , after forming a middle layer 24 on the lower layer 23 , a top layer 26 is formed on the middle layer 24 .

The intermediate layer 24 may be formed of a polyurea composition. The polyurea composition for the middle coating layer may be prepared to have higher curing speed and higher coating film hardness than the polyurea composition for the lower coating layer. For example, the middle layer 24 may be formed of a polyurea composition for a middle layer or a base layer known in the art.

In addition, the intermediate layer 24 may be formed under a high-temperature and high-pressure condition by a coating device dedicated to polyurea.

For example, the top coat layer 26 may be formed using a urethane resin, an acrylic resin, a urethane acrylic resin, an epoxy resin, or a combination thereof.

According to the present invention, the undercoat layer 23 has excellent pinhole cover performance, is formed of a polyurea composition, and has excellent adhesion to the middle coat layer 24 . In addition, since painting can be done with polyurea painting equipment (spraying device), the quality of the coating film is superior to that of general hand-type painting, which depends on the work ability of the operator.

Hereinafter, the effect of the polyurea composition according to the present invention and a waterproof structure using the same will be described in detail through specific examples and experiments.

According to Tables 1 and 2 below, the main part and the curing agent part of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared. (Content: % by weight)

Elements of the subject part Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Oil Modified Polyol: HS 3G-100M
(Japan, Hokoku corporation)
10
15
25
10
5
15
25 Amine (low yellowing/medium cure): 4-4-methylenebis(2-dichloroaniline)
40 - - - - - - Amine (non-yellowing/medium cure): tetrakis (2-hydroxypropyl) ethylenediamine -
35 - - - - - Amine (non-yellowing/fast curing): 4,4-methylenebis[N-methylpropyl]cyclohexanamine - -
25 - - - - Amine (non-yellowing/slow cure): tetraethyl N,N'-(methylenedi-4,1-cyclohexanediyl)bis(aspartate) - - -
40 - - - Amine: 4,4'-bis-sec-butyl amino diphenyl methane - - - -
45 - - Amine: Dimethyl Thio-toluenediamine - - - - -
35 - Amine: diethyltoluenediamine - - - - - -
25 Dispersant: EFKA-5065
(Germany, EFKA)
0.5 Diluent: Propylene carbonate
39.5 Desiccant: Zeolite 5 Black pigment: BAYFERROX 303T (Korea, LANXESS KOREA)
5

In Table 2, the urethane prepolymer was obtained by reacting 15 to 30 parts by weight of methylenediphenyl diisocyanate, 5 to 10 parts by weight of polyoxyalkylene glycol, and 0.1 to 5 parts by weight of 1,3-butylene glycol at about 50 ° C. The isocyanate content can be 15% to 30%, and the weight average molecular weight is about 2,000 to about 4,000.

The coating film hardness (Shore D) measurement of the coating film specimens obtained from the compositions of Examples 1 to 4, adhesion to the background, and adhesion to the subsequent intermediate coat were tested, and additionally, whether or not the purpose of the development product of shortening the period was met. After measuring the curing time (touch drying, curing drying, solidifying drying) to look at, the results are shown in Table 3 below. In addition, the degree of pinhole occurrence was compared to compare the pore covering ability when coating on a porous concrete surface. The adhesion strength was tested according to the ASTM D-4541 method.

[Method for determining adhesion with subsequent intermediates] Judgment situation ◎ Excellent adhesion with subsequent polyurea when peel off. Non-peeling during forced peeling ○ Excellent adhesion with subsequent polyurea when peel off. Difficult peeling occurs during forced peeling, and many adhesive areas with subsequent polyurea. △ Excellent adhesion with subsequent polyurea when peel off. Peeling occurs during forced peeling, but many adhesive areas with subsequent polyurea. X to △ When peel off, adhesion to subsequent polyurea is normal. Peeling occurs during forced peeling, and there is almost no adhesion area with subsequent polyurea. X Poor adhesion with subsequent polyurea when peel off. No adhesion area with subsequent polyurea

The coating films were coated using a polyurea coating equipment (GRACO HXP3) (pressure condition: 1,500 ~ 2,000 psi, temperature condition: 60 ~ 70 ℃), and the touch drying, hardening drying, and hardening drying were measured at 25 ℃. In addition, the subsequent intermediate coat was formed using ultra fast curing pure polyurea (Superdeck U-285).

Referring to the experimental results in Table 3, when using a single molecule (4,4-methylenebis[N-methylpropyl]cyclohexanamine) with a fast curing rate among polyamines, curing is fast, resulting in insufficient fluidity flowing into the concrete micropores. It was confirmed that many pinholes were generated during polyurea coating.

In addition, when painting on the background (concrete), the adhesion to the background was confirmed at the level of 3.5 to 5.0 Mpa of adhesion strength without a significant difference in Examples 1 to 4 and Comparative Examples 1 to 3, but there is a difference in adhesion with the subsequent intermediate , It was confirmed that the slower the curing speed of the undercoating, the more the concrete micropores were filled, thereby significantly reducing the occurrence of pinholes in the subsequent coating material. In addition, according to the experimental results, it can be seen that the more the yellowing of the undercoat is suppressed (the more the surface structure is deformed or the chromophore is not formed), the higher the adhesion performance with the subsequent coating material (middle coat).

As described above, it has been described with reference to exemplary embodiments of the present invention, but those skilled in the art can make the present invention various without departing from the spirit and scope of the present invention described in the claims below. It will be understood that it can be modified and changed accordingly.

The coating composition according to exemplary embodiments of the present invention can be used for waterproof construction of various concrete structures.

Claims (9)

Including a main part and a curing agent part,
The main part is 4-4-methylenebis (2-dichloroaniline), tetrakis (2-hydroxypropyl) ethylenediamine, 4,4-methylenebis [N-methylpropyl] cyclohexanamine and tetraethyl N, N 20% to 50% by weight of an amine compound containing at least one selected from the group consisting of '-(methylenedi-4,1-cyclohexanediyl)bis(aspartate), 5% to 30% by weight of an oil-modified polyol , 30% to 50% by weight of propylene carbonate, 1% to 10% by weight of a moisture absorbent, 1% to 5% by weight of ceramic hollow pigment and 1% to 10% by weight of a black colorant,
The curing agent part includes 10 wt% to 40 wt% of a urethane prepolymer, 10 wt% to 40 wt% of an isocyanate compound, 30 wt% to 50 wt% of a diluent, 1 wt% to 10 wt% of a moisture absorbent, and 0.1 wt% to 3 wt% of a moisture barrier. Containing, a polyurea composition for undercoating a waterproofing film. The polyurea composition for undercoating a waterproofing film according to claim 1, wherein the moisture absorbent comprises at least one selected from the group consisting of calcium oxide, zeolite and magnesium oxide. The polyurea composition according to claim 1, wherein the moisture barrier comprises at least one selected from the group consisting of 4-methylbenzenesulfonyl isocyanate and oxazolidine. The polyurea composition according to claim 1, wherein the black colorant comprises at least one of carbon black and iron oxide. The polyurea composition for undercoating a waterproofing film according to claim 1, wherein the main part further comprises 1% to 5% by weight of a phosphorus-based flame retardant. Forming an undercoat layer by directly coating a polyurea composition selected from any one of claims 1 to 5 on a concrete surface;
Forming an intermediate layer by coating a polyurea composition for intermediate coating on the undercoat; and forming a top coat layer on the middle layer. [Claim 7] The waterproof structure construction method according to claim 6, wherein the polyurea composition of the undercoating layer is directly sprayed onto the concrete surface using a painting equipment including a spray gun. 8. The waterproof structure construction method according to claim 7, wherein the polyurea composition of the undercoating layer is sprayed at a pressure of 1,500 psi to 2,000 psi and a temperature of 60 ° C to 70 ° C. 8. The waterproof structure construction method according to claim 7, wherein the polyurea composition of the undercoating layer is sprayed at a pressure of 100 psi to 500 psi and a temperature of 30 ° C to 50 ° C.

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