KR101755528B1 - Waterproof composition comprising polyurea and process of waterproof coating by using the same - Google Patents

Abstract

The present invention relates to a waterproof polyurea composition useful as a waterproof coating material for a roof, a parking lot floor, a tank inner / outer wall, an inner / outer wall of a water tank, and a waterproof coating method using the waterproofing paint.

Description

TECHNICAL FIELD The present invention relates to a waterproof polyurea composition and a waterproof coating method using the waterproof composition.

The present invention relates to a waterproof polyurea composition used for waterproof painting and a waterproof coating method using the same.

Generally, in the case of concrete buildings such as houses and buildings, when moisture such as rainwater permeates, a part of the water does not evaporate and penetrates into the building to adversely affect the durability of the structure such as corrosion or breakage. It is required to perform waterproofing work on structures such as a roof, a roof, an outer wall, and a floor.

Conventionally, a method of applying a coating material such as asphalt or a coal tar pitch to a surface requiring painting and then carrying out a protection work with mortar or concrete has been used. However, asphalt or coal tar pitch is easy to construct and is inexpensive If cracks occur in the structure, the waterproof layer is destroyed and the waterproof effect is lost. In order to solve these problems, a polyurea waterproofing method has recently been proposed in which a polyurea resin is used as a waterproof coating material to construct a building roof, a parking lot floor, or an outer wall. Such a polyurea waterproofing method has an advantage of excellent waterproofing performance, but when the polyurea resin is directly sprayed on the concrete, the watertightness of the concrete is not good, so that pinholes are generated and the surface is not flat.

In order to solve such a problem, Korean Patent No. 0565908 discloses a method of coating a polyurethane resin after applying a cementitious base adjusting agent to the surface of a concrete as a base member. Korean Patent No. 0844367 discloses a polyurea- Korean Patent No. 1196330 discloses a method of coating a polyurea resin after an adjustment agent is applied and introducing fluorine alcohol into the polymer molecule to improve the stain resistance of the finally completed polyurea so as not to lower the physical properties Discloses a polyurea coating film waterproofing material. Despite much research and development, it is required to develop a novel waterproofing composition that can paint on the roof, parking lot floor, inside / outside wall of the tank, inside / outside wall of the water tank due to improved waterproof effect without occurrence of pinholes.

The object of the present invention is to provide a waterproof polyurea composition capable of maximizing a waterproof effect, having a fast curability and having improved durability, and a waterproof coating method using the waterproof polyurea composition.

In order to achieve the above object, the present invention provides an isocyanate-based compound; Silane-based compounds; Titania-based compounds; Oxidant; And an amine compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

X is alkyl, alkylene, aryl or arylene having a valence n,

R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each independently selected from hydrogen, C _{1 - 20} alkyl and aryl, and the adjacent R ₁ and R ₂ are bonded to each other to form a ring Can,

R ₃ is C _{1 - 20} alkyl or aryl group,

Wherein said aryl is phenyl or naphthyl,

n is an integer of 1 or more.

The present invention also relates to (A) an isocyanate compound; Silane-based compounds; Mixing an A agent comprising a titania compound and an oxidizing agent and a B agent comprising an amine compound represented by the following formula (1); And (A) an isocyanate-based compound; Silane-based compounds; Mixing an A agent comprising a titania compound and an oxidizing agent and a B agent comprising an amine compound represented by the following formula (1); And (B) heating the mixture to 70 to 80 占 폚.

[Chemical Formula 1]

In the above formula (1), X, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined above.

The present invention also relates to (A) an isocyanate compound; Silane-based compounds; Mixing an A agent comprising a titania compound and an oxidizing agent and a B agent comprising an amine compound represented by the following formula (1); (B) heating the mixture to 70 to 80 占 폚; (C) spraying the mixture at a discharge pressure of 1,500 to 2,000 psi while maintaining the temperature of the mixture at 70 to 80 to form a waterproof film; And (D) cooling the formed waterproof film to room temperature, reheating it again to 50 to 60, and cooling to room temperature.

INDUSTRIAL APPLICABILITY The waterproof polyurea composition according to the present invention is excellent in waterproof effect, durability, and curability so that it is useful as a waterproof coating material for roofs, parking lots, tank inner / outer walls, and inner / outer walls of water tanks. The polyurea composition according to the present invention has a useful shelf life of at least 2 years, preferably at least 3 years.

One aspect of the present invention relates to an isocyanate-based compound; Silane-based compounds; Titania-based compounds; Oxidant; And an amine compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

X is alkyl, alkylene, aryl or arylene having a valence n,

R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each independently selected from hydrogen, C _1-20 alkyl and aryl, and adjacent R ₁ and R ₂ are bonded to each other to form a ring Can,

R ₃ is C _{1 - 20} alkyl or aryl group,

Wherein said aryl is phenyl or naphthyl,

n is an integer of 1 or more.

According to the present invention, the aryl is unsubstituted or substituted by C _{1 -} may be one substituted with a substituent selected from the group consisting of ₆ alkyloxy, hydroxy, nitro, amino, and _{halogen-6-alkyl,} C _1.

According to the present invention, the amine compound represented by the formula (1) may be added as a curing agent.

According to the present invention, the composition may further comprise a saccharide powder selected from glucose, sucrose, fructose, and a mixture of two or more thereof.

According to the present invention, the composition may further comprise a water-soluble metal salt powder selected from sodium chloride, potassium chloride, sodium hydrogencarbonate, or a mixture of two or more thereof.

According to the present invention, the composition may further comprise a water-soluble polymer powder selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, and mixtures thereof.

According to the present invention, the composition may include both the saccharide powder, the water-soluble metal salt powder and the water-soluble polymer powder. The addition of these components serves to greatly improve the waterproof performance and durability of the polyurea.

According to the present invention, according to the present invention, the composition comprises 1 to 10 parts by weight of a silane-based compound per 100 parts by weight of an isocyanate-based compound; 1 to 10 parts by weight of a titania compound; 50 to 20 parts by weight of an oxidizing agent; And 80 to 130 parts by weight of an amine compound. Preferably, the composition contains 1 to 2 parts by weight of a saccharide flour based on 100 parts by weight of an isocyanate compound; 2 to 3 parts by weight of a water-soluble metal salt powder; And 1 to 2 parts by weight of a water-soluble polymer powder. It was confirmed that when the composition according to the present invention is added at the above ratio, the water resistance is particularly excellent and the durability is greatly improved.

The present invention also relates to (A) an isocyanate compound; Silane-based compounds; Mixing an A agent comprising a titania compound and an oxidizing agent and a B agent comprising an amine compound represented by the following formula (1); And (B) heating the mixture to 70-80 占 폚; (C) spraying the mixture at a discharge pressure of 1,500 to 2,000 psi while maintaining the temperature of the mixture at 70 to 80 to form a waterproof film; And (D) cooling the formed waterproof film to room temperature, reheating it again to 50 to 60, and cooling to room temperature.

[Chemical Formula 1]

In the above formula (1)

X is alkyl, alkylene, aryl or arylene having a valence n,

R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each independently selected from hydrogen, C _1-20 alkyl and aryl, and adjacent R ₁ and R ₂ are bonded to each other to form a ring Can,

R ₃ is C _{1 - 20} alkyl or aryl group,

Wherein said aryl is phenyl or naphthyl,

n is an integer of 1 or more.

The waterproof coating formed only by the steps (A) to (C) by omitting the step (D) in the above steps (A) to (D) is superior in durability .

In addition, by regulating the temperature within the reheating temperature range and reheating the coating film, the flatness of the waterproof coating film can be ensured not only in a local range but also in a large area. However, when the temperature is out of the range, The above reheating temperature range is also a very important feature of the present invention in that it exhibits a very unusual effect of greatly reducing the flatness.

In the present invention, the C _{1 - 20} alkyl is a paraffinic hydrocarbon group derived from an alkane by removing one hydrogen, means that the number of carbon atoms is 1 to 20, and may be straight, branched or cyclic. According to the present invention, the number of carbon atoms is preferably 1 to 6, and specific examples thereof may be methyl, ethyl or butyl.

The aryl group is an unsaturated hydrocarbon group having aromatic ring structure characteristics such as benzene, naphthalene, etc., and is a condensed six-membered carbon ring of a six-membered carbon ring of benzene or other aromatic derivatives. It may be one substituted with a substituent selected from the group consisting of ₆ alkyloxy, hydroxy, nitro, amino, and _{halogen, wherein} the aryl is unsubstituted or substituted by C _{1 - 6} alkyl, C _1.

In the present invention, the alkylene means an organic radical formed by removing hydrogen from two or more carbon sites of an aliphatic hydrocarbon, and specific examples thereof include ethylene (-C ₂ H ₄ -).

The arylene group means a polyvalent radical formed by removing hydrogen from two or more carbon sites of an aromatic nucleus, and specific examples thereof include phenylene (-C ₆ H ₄ -).

In the present invention, n is an integer of 1 or more, preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and still more preferably an integer of 1 to 10.

First, an isocyanate compound; Silane-based compounds; An A agent containing a titania compound and an oxidizing agent is produced. At this time, relative to 100 parts by weight of the isocyanate compound, 1 to 10 parts by weight of the silane compound; 1 to 10 parts by weight of a titania compound; 5 to 20 parts by weight of an oxidizing agent; And 80 to 130 parts by weight of an amine compound.

The amine compound of the formula 1 according to the present invention can be produced by a Michael type reaction of a primary amine with various amide-esters. Michael acceptors useful as precursors include the addition products of an alcohol and isomaleimide. This reaction is shown below as providing a compound.

[Reaction Scheme 1]

By using an organotin salt as the catalyst, the desired product can be obtained in increased yield. The method of the invention by an alcohol, R ₃ OH reacted with the isopropyl maleimide in the presence of an organotin catalyst in the product (formula of the above reaction scheme, R ₂ is an alkyl or aryl group, R _3, R ₄ and R ₅ is Lt; / RTI > as hereinbefore defined).

The reaction of the isomaleimide with the alcohol can be carried out at about 0 to about 100 캜, preferably at ambient temperature, i.e. about 25 to about 70 캜. Examples of the organotin salts that can be used as the catalyst include dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dilaurate, octadecylstannane, bis (lauryldibutyltin) oxide, dibutyltin dimercaptide And dibutyltin dimercaptide. A preferred catalyst is dibutyltin diacetate. The amount of catalyst used may vary from about 0.1 to about 10 mole percent based on the amount of alcohol. The isomaleimide starting material can be prepared by known methods.

An alternative method of preparing amide ester precursors involves reacting maleic anhydride with an amine followed by conversion of the carboxylic acid group to the desired ester. This reaction is as follows.

[Reaction Scheme 2]

Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined above and Hal represents a halide ion, preferably iodide

The reaction of primary amines with amide-ester Michael acceptors is often spontaneous, fast, and almost quantitative. This addition reaction product can be simply synthesized by allowing a mixture of the primary amine and the Michael acceptor to remain at about 70 DEG C for about 96 hours in the presence of a catalyst. This reaction is as follows.

[Reaction Scheme 3]

Wherein X, n and R ₁ to R ₅ are as defined above.

Examples of amines useful for preparing the secondary amines of the present invention include ethylenediamine, 1,2-diaminopropane, 2,5-diamino-2,5-dimethylhexane, 1,11-diaminoundecane, 1,12-diaminododecane, 2,4'-diamino-dicyclohexylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- or 2,6- Diaminotoluene, 2,4'- or 4,4'-diaminodiphenylmethane, or mixtures thereof. Preferred amines for the production of secondary amines include 1,4-diaminobutane, 1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, , 5-trimethyl-5-aminomethyl-cyclohexane, 4,4'-diamino-dicyclohexylmethane, 3,3-dimethyl-4,4'-diamino-dicyclohexylmethane or mixtures thereof . Particularly preferred amines are 4,4'-methylene-bis (cyclohexylamine), 2-methyl-1,5-pentanediamine, 1,6-diaminohexane and mixtures thereof.

The reaction generally proceeds from 80% to 99% within 96 hours. Since the reaction is clear, purification of the reaction product is unnecessary.

These sterically hindered secondary amines react with better control of the nucleophile than the corresponding primary amine, and the hydrogen bonding in this addition reaction product is significantly reduced or eliminated. The secondary amine reacts with the isocyanate to form a urea-amide / ester bond. This reaction illustrates the formation of the following compounds.

[Reaction Scheme 4]

Wherein X, R ₁ , R ₂ and R ₃ are as defined above, and Y is X.

Unlike urea-diester bonds, urea-amide / ester bonds are stable. Amide-esters are not cyclized to hydantoins. The hydantoin causes contraction and is formed to have a urea-diester bond as described above.

The crosslinking taking place in the process of the invention is based on the addition reaction of a polyisocyanate component with an isocyanate-reactive component, in particular a secondary amine.

Examples of the isocyanate compound include isocyanate compounds such as toluene isocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl- Hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI ), 2,4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanatodicyclohexylmethane, 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato- Diisocyanatotoluene, N, N ', N' '- tris- (6-isocyanatohexyl) -Buret, N, N ', N "-tris- (6-isocyanatohexyl) -isocyanurate, mixtures thereof or And copolymers thereof. The term " polyisocyanate " refers to a compound having at least one isocyanate group, and includes known polyisocyanates of polyurethane chemistry.

Specific examples of suitable low molecular weight polyisocyanates having a molecular weight of 168 to 5,000 include hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene di Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'- and / or 4-isocyanatoethylcyclohexane , 4'-diisocyanatodicyclohexylmethane, 2,4'- and 4,4'-diisocyanato-diphenylmethane and their isomers and aniline / formaldehyde condensates, 2,4- and / or 2,6-diisocyanato toluene, and mixtures with higher homologues prepared by phosgenation of any mixture of these compounds.

However, it is preferable to use derivatives of these monomeric polyisocyanates. These derivatives include, for example, polyisocyanates containing buret (carbamylurea) groups as described in U.S. Patent Nos. 3,124,605, 3,201,372, and DE-OS 1,101,394; Polyisocyanates containing isocyanate groups as described, for example, in U.S. Patent Nos. 3,001,973, DE-PS 1,022,789, 1,333,067 and 1,027,394 and DE-OS 1,929,034 and 2,004,048; For example, DE-OS 953,012, BE-PS 752,261, and polyisocyanates containing urethane groups as described in U.S. Patent Nos. 3,394,164 and 3,644,457; For example, polyisocyanates containing carbodiimide groups as described in DE-OP 1,092,007, U.S. Pat. No. 3,152,162 and DE-OS 2,504,400, 2,537,685 and 2,552,350; And polyisocyanates containing allophanate groups as described, for example, in GB-PS 994,890, BE-PS 761,626 and NL-OS 7,102,524.

Modified polyisocyanates are particularly preferred. For example, a mixture of N, N ', N "-tris- (6-isocyanatohexyl) -buret and a higher homologue thereof and a mixture of N, N', N" -tris- (6-isocyanatohexyl) ) -Isocyanurate and mixtures thereof with higher homologues containing at least one isocyanurate ring.

The isocyanate group-containing prepolymer and semi-prepolymer mainly composed of monomeric simple polyisocyanates or modified polyisocyanates and organic polyhydroxyl compounds exemplified above are preferable for use as the polyisocyanate component. These prepolymers and semi-prepolymers generally have from about 140 to about 8,400 equivalents, preferably from about 210 to about 420 equivalents, and the above starting materials have an NCO / OH equivalent ratio of about 1.05: 1 to about 10: 1, preferably about 1.1: 1 to 3: 1, and optionally, distilling off any unreacted volatile starting polyisocyanate present.

The prepolymer and semi-prepolymer are low molecular weight polyhydroxyl compounds having a molecular weight of from 62 to 299, such as ethylene glycol, propylene glycol, trimethylol propane, 1,6-dihydroxyhexane; Low molecular weight hydroxyl containing esters of the following types of these polyols and dicarboxylic acids; Low molecular weight ethoxylated and / or propoxylated products of these polyols; And mixtures of these polyfunctional or unmodified alcohols.

However, prepolymers and semi-prepolymers are prepared from known relatively high molecular weight polyhydroxyl compounds of polyurethane chemistry having a molecular weight of from 300 to about 8,000, preferably from about 1,000 to 5,000, as measured by the functionality and OH number. These polyhydroxyl compounds have two or more hydroxyl groups per molecule, and generally have a hydroxyl group content of about 0.5 to 17% by weight.

Examples of suitable relatively high molecular weight polyhydroxyl compounds that can be used in the preparation of prepolymers and semi-prepolymers include the above-described low molecular weight monomeric alcohols and polybasic carboxylic acids (e.g., adipic acid, sebacic acid, phthalic acid, iso Phthalic acid, tetra-hydrophthalic acid, hexahydrophthalic acid, maleic acid), anhydrides of these acids, and mixtures of these acids and / or acid anhydrides. The hydroxyl group-containing polylactone, especially poly-e-caprolactone, is also suitable for the preparation of prepolymers and semi-prepolymers.

Polyether polyols prepared by known methods by alkoxylation of molecules of suitable starting materials are also suitable for the preparation of isocyanate group-containing prepolymers and semi-prepolymers. Examples of suitable starting molecules of polyether polyols are the aforementioned monomeric polyols, water, organic polyamines having two or more NH bonds, and any mixture of these starting molecules. Ethylene oxide and / or propylene oxide are alkylene oxides particularly suitable for alkoxylation reactions. These alkylene oxides may be introduced into the alkoxylation reaction in any order or in mixture.

Hydroxyl group-containing polycarbonates which can be prepared by the reaction of the above-mentioned monomeric diols with phosgene and diaryl carbonates (e.g., diphenyl carbonate) are also suitable for the preparation of prepolymers and semi-prepolymers.

The other optionally used isocyanate-reactive compound is preferably an organic polyhydroxyl compound known from polyurethane chemistry, and is preferably used in combination with the above-described low molecular weight polyhydroxyl compound for preparation of a prepolymer suitable for use as a polyisocyanate component and a semi-prepolymer, Both of the high molecular weight polyhydroxyl compounds can be mentioned.

The isocyanate-reactive compound that can be used as part of the polyisocyanate component is a hydroxy-functional polyacrylate known for use in polyurethane coatings. These compounds vapor pressure or membrane can be measured by the osmotic pressure measurement method average molecular weight (M _n) of about 800 to 50,000, preferably from about 1,000 to 20,000, more preferably about 5,000 to 10,000, a hydroxyl group content of from about 0.11 to Containing copolymer of olefinically unsaturated compounds having from 1 to 12% by weight, preferably from about 1 to 10% by weight, most preferably from about 2 to 6% by weight. This copolymer is composed mainly of an olefinic monomer containing a hydroxyl group and an olefinic monomer containing no hydroxyl group. Examples of suitable monomers include vinyl and vinylidene monomers such as styrene,? -Methylstyrene, o- and p-chlorostyrene, o-, m- and p-methylstyrene, p-tert- butylstyrene, Methyl acrylonitrile, acrylic acid and methacrylic acid esters of alcohols having 1 to 8 carbon atoms (e.g., ethyl acrylate, methyl acrylate, n- and isopropyl acrylate, n-butyl acrylate, Acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and iso-octyl methacrylate), fumaric acid having 4 to 8 carbon atoms in the alcohol component (Meth) acrylic acid amide, vinyl esters of alkane monocarboxylic acids having 2 to 5 carbon atoms (e.g., vinyl acetate or vinyl propionate And hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 4 carbon atoms in the hydroxyalkyl group (e.g., 2-hydroxyethyl-, 2-hydroxypropyl-, 4-hydroxybutyl-acrylate And methacrylate and trimethylolpropane-mono- or pentaerythritol mono-acrylate or methacrylate). In addition, mixtures of monomers as exemplified above can also be used in the preparation of hydroxy-functional polyacrylates. Mixtures of the polyhydroxy compounds described above may be used as part of the polyisocyanate component.

In the composition, the equivalent ratio of the functional group of the isocyanate to the reactive group of the isocyanate of the amine compound represented by the formula (1) is 0.8: 1 to 20: 1, preferably 0.8: 1 to 2: 1, 0.8: 1 to 1.2: 1, and most preferably 1: 1. Any polyhydroxyl compound may be present in an amount such that no more than 20 hydroxyl groups are present for each secondary amino, preferably an equivalent ratio of hydroxyl groups to secondary amino groups of from about 10: 1 to about 1:10 ≪ / RTI > in the amine component.

Examples of preferred solvents in the present invention include xylene, butyl acetate, methyl isobutyl ketone, methoxypropyl acetate, N-methylpyrrolidone, petroleum hydrocarbons, isobutanol, butyl glycol, butoxyethanol, Lt; / RTI > The above-mentioned alcoholic solvent may be used, but in this case, any polyhydroxyl compound is not used.

In the present invention, the amine represented by the formula (1) includes at least one amide-ester amine, which may be optionally blended with one or more amine functional co-reactants instead of one type of amide-ester amine. The amine functional co-reactant is preferably a polymeric polyamine, more preferably a substantially polymeric diamine. These amine functional co-reactants are selected to combine the properties of the coating during the curing process with the properties of the coating in its final form, thereby making it possible to produce waterproof polyureas of superior quality.

The silane-based and titania-based compounds play an important role in forming a polymer having improved water resistance and durability. When the content is less than the lower limit, the effect of improving the water resistance and durability can not be expected. If the content exceeds the upper limit, the durability of the applied polyurea coating may be lowered.

In the present invention, the silane-based compound may be at least one selected from the group consisting of gamma-methacryloylpropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, tetraethoxyorthosilicate, Propyltrimethoxysilane, and n-hexadecyltrimethoxysilane, and at least one member selected from the group consisting of

The titania-based compound may be at least one compound selected from the group consisting of isopropyltriisostearoyltateate, neopentyl (diallyl) oxytrienodecane oleate and neopentyl (diallyl) oxytri (dodecyl) benzene-sulfonyltitrate May be used alone or in combination.

The oxidant may be alone or in combination of two or more selected from the group consisting of hydrogen peroxide, t- butyl hydroperoxide (tert -butyl hydroperoxide), and t- ethyl hydroperoxide (tert -ethyl hydroperoxide). If the content of the oxidizing agent is less than the lower limit value, the polymerization yield may be decreased. If the content of the oxidizing agent is higher than the upper limit value, the characteristics of the polyurea may be changed.

According to the present invention, the agent A is a saccharide powder selected from glucose, sucrose, fructose and a mixture of two or more thereof as an additive; A water-soluble metal salt powder selected from sodium chloride, potassium chloride, sodium hydrogencarbonate or a mixture of two or more thereof; And water-soluble polymer powders selected from polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, and mixtures thereof.

If the content of the additive is less than the above-mentioned content, it is difficult to improve the durability, and if it exceeds the above-mentioned content, the water resistance is deteriorated. In the samples added in the above range, excellent waterproof effect and strong durability were confirmed.

The urea composition according to the present invention may further comprise an additive. These additives include weathering additives, antioxidants, dispersion aids, polishing aids, wetting agents, impact modifiers, defoamers, pigments, fillers, extenders, diluents, plasticizers, thickeners and surfactants.

Fillers and extenders can be used to modify the fluidity of the liquid coating and can contribute to the bulk volume of the final coating. Fillers can also be used to achieve specific volume ratios without significantly affecting the reaction chemistry. Pigments, fillers and extenders have a significant effect on uncured formulations and cured film density, film hardening profile and track free time, cured film modulus, coating adhesion to substrate, response to heat cycle, wear and coating durability .

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. In addition, it is apparent that, based on the teachings of the present invention including the following examples, those skilled in the art can easily carry out the present invention in which experimental results are not specifically shown.

Example

Comparative Example  One

As described in the example of WO 2000/01665, 100 g of diisocyanate and 100 g of each material of secondary amine were mixed to prepare a polyurea composition. Due to the fast cure rate, the secondary amine was first placed in the beaker and then the diisocyanate was added. Thereafter, the mixture was stirred vigorously for 15 to 30 seconds, then heated to 75 DEG C, and discharged at a discharge pressure of 1,700 psi while maintaining the temperature. The tensile strength of the polyurea cured product thus prepared was measured according to the KS F 4922 standard using a universal material testing machine.

Comparative Example  2

The procedure of Example 1 was repeated except that 1.5 g of glucose powder, 2.5 g of sodium chloride powder and 1.5 g of polyvinyl alcohol powder were further added based on 100 g of diisocyanate to prepare a composition liquid.

Comparative Example  3

The procedure of Example 1 was repeated except that 2.5 g of glucose powder, 1.5 g of sodium chloride powder and 2.5 g of polyvinyl alcohol powder were further added based on 100 g of diisocyanate to prepare a composition liquid.

Example  One

5 g of gamma-metaacryloylpropyltrimethoxysilane, 5 g of isopropyltriisostearoyltitrate, and 5 g of hydrogen peroxide were added to 100 g of isocyanate to prepare a polyurea cured product in the same manner as in Comparative Example 1.

Example 2

5 g of gamma-metaacryloylpropyltrimethoxysilane, 5 g of isopropyltriisostearoyltitrate, and 5 g of hydrogen peroxide were added to 100 g of isocyanate to prepare a polyurea cured product in the same manner as in Comparative Example 2.

Example 3

5 g of gamma-metaacryloylpropyltrimethoxysilane, 5 g of isopropyltriisostearoyltitrate and 5 g of hydrogen peroxide were added to 100 g of isocyanate to prepare a polyurea cured product in the same manner as in Comparative Example 3.

Test Example

The tensile strength and waterproofing effect of the polyurea cured products prepared in Comparative Examples 1 to 3 and Examples 1 to 3 were measured, and the results are shown in Table 1 below. (x: bad,?: normal,?: excellent,? excellent)

division durability Waterproof Comparative Example 1 Δ Δ Comparative Example 2 ○ ○ Comparative Example 3 ○ ○ Example 1 ○ ◎ Example 2 ◎ ◎ Example 3 ◎ ◎

Claims (12)

(A) an isocyanate compound; Silane-based compounds; Mixing an A agent comprising a titania compound and an oxidizing agent and a B agent comprising an amine compound represented by the following formula (1); And
(B) heating the mixture to 70 to 80 占 폚;
(C) spraying the mixture at a discharge pressure of 1,500 to 2,000 psi while maintaining the temperature of the mixture at 70 to 80 to form a waterproof film; And
(D) cooling the formed waterproof film to room temperature, reheating it again to 50 to 60, and cooling to room temperature.
[Chemical Formula 1]

In the above formula (1)
X is alkyl, alkylene, aryl or arylene having a valence n,
R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each independently selected from hydrogen and C _1-20 alkyl, and adjacent R ₁ and R ₂ may be bonded to each other to form a ring ,
R ₃ is C _1-20 alkyl,
Wherein said aryl is phenyl or naphthyl,
n is an integer of 1 or more.
n is an integer of 1 or more. The method according to claim 1,
Coatings for water-proofing method according to claim ₆ alkyloxy, hydroxy, nitro, amino, and that the halogen-substituted with a substituent selected from the group consisting of _wherein aryl is unsubstituted or substituted by C _{1 - 6} alkyl, C _1. The method according to claim 1,
Examples of the isocyanate compound include toluene isocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene Diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), diisocyanate diisocyanate, 4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanatodicyclohexylmethane, 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-diphenylmethane, Diisocyanatotoluene, 2,6-diisocyanatotoluene, N, N ', N "-tris- (6-isocyanatohexyl) -buret, N , N ', N "-tris- (6-isocyanatohexyl) -isocyanurate, mixtures thereof, or copolymers thereof. Alone or in combination of two water-proof coating characterized in that more than type of compound. The method according to claim 1,
The silane-based compound may be at least one selected from the group consisting of gamma-metaacrylooxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, tetraethoxyorthosilicate, 3- glycidoxypropyltrimethoxy Silane, and n-hexadecyltrimethoxysilane, and at least one member selected from the group consisting of
The titania-based compound may be at least one compound selected from the group consisting of isopropyltriisostearoyltateate, neopentyl (diallyl) oxytrienodecane oleate and neopentyl (diallyl) oxytri (dodecyl) benzene-sulfonyltitrate Wherein the water-repellent coating method is a coating method. The method according to claim 1,
Said oxidizing agent is water-proof coating characterized in that hydrogen peroxide, t- butyl hydroperoxide (tert -butyl hydroperoxide), and t- ethyl hydroperoxide (tert -ethyl hydroperoxide) at least one or two selected from the group consisting of. The method according to claim 1,
Glucose, sucrose, fructose, and a mixture of two or more thereof. The method according to claim 1,
Characterized by further comprising a water-soluble metal salt powder selected from the group consisting of sodium chloride, potassium chloride, sodium hydrogencarbonate or a mixture of two or more thereof The method according to claim 1,
A water-soluble polymer powder selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, and mixtures thereof. Isocyanate compounds; Silane-based compounds; Titania-based compounds; Oxidant; And an amine compound represented by the following formula (1).
[Chemical Formula 1]

In the above formula (1)
X is alkyl, alkylene, aryl or arylene having a valence n,
R ₁ , R ₂ , R ₄ and R ₅ are the same or different and each independently selected from hydrogen and C _1-20 alkyl, and adjacent R ₁ and R ₂ may be bonded to each other to form a ring ,
R ₃ is C _1-20 alkyl,
Wherein said aryl is phenyl or naphthyl,
n is an integer of 1 or more. 10. The method of claim 9,
Wherein the aryl is unsubstituted or substituted by C _{1 - 6} alkyl, C _{1 - 6} for waterproofing polyurea composition according to claim alkyloxy, hydroxy, nitro, amino, and that the halogen-substituted with a substituent selected from the group consisting of. 10. The method of claim 9, wherein the saccharide powder is selected from glucose, sucrose, fructose, and a mixture of two or more thereof; A water-soluble metal salt powder selected from sodium chloride, potassium chloride, sodium hydrogencarbonate or a mixture of two or more thereof; And a water-soluble polymer powder selected from polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, and mixtures thereof; Wherein the waterproof polyurea composition further comprises at least one member selected from the group consisting of water-soluble polyurea resins and water-soluble polyurea resins. 12. The method of claim 11,
Based on 100 parts by weight of the isocyanate compound, 1 to 10 parts by weight of the silane compound; 1 to 10 parts by weight of a titania compound; 5 to 20 parts by weight of an oxidizing agent; And 80 to 130 parts by weight of an amine compound; 1 to 2 parts by weight of saccharine powder; 2 to 3 parts by weight of a water-soluble metal salt powder; 1 to 2 parts by weight of a water-soluble polymer powder.