KR102562932B1 - Eco-Friendly Complex Water Proofing Process Using Hand-workable Polyurethane-Polyurea Two Liquid Composition - Google Patents

Abstract

In the present invention, (step 1) applying a primer to the entire surface of the concrete base; (Step 2) Placing waterproof sheets on the primer at intervals of 5 to 10 mm; (Step 3) reinforcing the gap between the waterproof sheets by using a two-component polyurethane-urea resin composition for fixing the waterproof sheets; (Step 4) forming a waterproof sheet layer by connecting the waterproof sheets with an adhesive reinforcing tape; And (Step 5) applying an eco-friendly polyurethane composition on the reinforced waterproof sheet layer to form a waterproof coating layer; a composite waterproof method including an eco-friendly polyurethane waterproof coating film and a waterproof sheet is provided.
The composite waterproofing method according to the present invention can form a composite waterproofing membrane having excellent workability, mechanical properties and eco-friendliness by applying both the coating waterproofing method and the sheet waterproofing method.

Description

Eco-Friendly Complex Water Proofing Process Using Hand-workable Polyurethane-Polyurea Two Liquid Composition}

The present invention relates to an eco-friendly composite waterproofing method using a polyurethane-urea resin two-component composition for fixing a waterproof sheet that can be manually worked.

In general, inorganic materials such as concrete or mortar that form buildings may crack due to heat of hydration or various vibrations caused by the hydration reaction of cement. There is a structural problem that further weakens the durability of the building and accelerates aging. In order to prevent or repair cracks that occur in such concrete buildings, waterproofing methods are implemented.

Polyurethane is widely used in coating waterproofing methods due to its dense structure and excellent waterproofing properties. The polyurethane coating waterproofing method arranges the floor to be installed, applies a primer to it, sufficiently penetrates the floor and dries it, then applies liquid polyurethane resin to the floor surface, dries and hardens it to form a polyurethane coating film of a certain thickness. It is a method of forming and waterproofing through it. This polyurethane coating waterproofing method has excellent elasticity, so it can maintain a certain degree of waterproof performance even against cracks in the lower extremities, and it is relatively easy to construct in narrow or complex areas, and it is possible to perform seamless construction and repair is relatively easy. There is one advantage.

However, since the polyurethane coating waterproofing method is an adhesion method that adheres to the substrate surface such as concrete, it is difficult to fundamentally solve cracks in the substrate, and the polyurethane coating film applied when cracks occur or decrease in adhesive performance according to the moisture content of the substrate surface. There are structural problems that weaken the durability of the structure due to water leakage due to damage or lifting, deterioration in adhesive performance according to the water content of the base surface, formation of an uneven waterproof layer, and failure to comply with construction standards.

In order to solve this problem, various composite waterproofing construction methods are applied in which a polyurethane coating waterproofing method is applied together with a sheet waterproofing method using a waterproof sheet. However, a satisfactory eco-friendly polyurethane composition having workability, physical properties and eco-friendliness suitable for use in such a composite waterproofing construction method has not yet been known.

The inventors of the present invention calculated the problems that occur frequently in the composite waterproofing method developed so far through prior research, that is, the problem that the adhesive performance or adhesive performance is lowered according to the characteristics of heterogeneous materials between the coating waterproof layer and the sheet waterproof layer, and the construction period It is difficult to adjust or adjust it flexibly, the problem of low reliability in waterproofness, and the problem of unsatisfactory eco-friendliness have been proposed.

On the other hand, the sheet waterproofing method basically fills the gaps between the waterproof sheets with polyurethane or polyurea and connects them with reinforcing tape, thereby fixing the waterproof sheets or preventing movement, securing waterproofness between the waterproof sheets, and applying polyurethane waterproof coating on the upper part. Adhesion is guaranteed.

In this situation, in the composite waterproofing method using the waterproof sheet and the eco-friendly polyurethane waterproofing film together, the fixation of the waterproof sheet, the waterproofness between the waterproof sheets, and the adhesion between the waterproof sheet and the waterproof coating film without compromising workability. It is required to develop a new waterproof sheet fixing agent or fixing method that can improve.

In particular, the adhesiveness of the coating waterproof layer with the waterproof sheet due to the solvent is lowered, and the waterproof performance is reduced by penetrating the joint and swelling the waterproof sheet.

Therefore, the present applicant has completed the present invention by using a solvent-free composition, using a polyurea fixative that can be manually worked, shortening the air, and improving the deterioration in waterproof performance.

An object of the present invention is to solve the above problems, and to improve the fixability of the waterproof sheet, the waterproofness between the waterproof sheets, and the adhesiveness between the waterproof sheet and the waterproof coating film without compromising workability. to develop fixation methods.

Another object of the present invention is to develop an eco-friendly composite waterproofing method using the above-described new waterproof sheet fixing agent or fixing method.

The problem to be solved by the present invention is not limited to the above-mentioned problem (s), and another problem (s) not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above object, the present invention

In order to solve the above object, the present invention provides a composite waterproof method comprising an eco-friendly polyurethane waterproof coating film and a waterproof sheet comprising the following steps:

(Step 1) Applying a primer to the entire surface of the concrete base;

(Step 2) Placing waterproof sheets on the primer at intervals of 5 to 10 mm;

(Step 3) reinforcing the gap between the waterproof sheets by using a two-component polyurethane-urea resin composition for fixing the waterproof sheets;

(Step 4) forming a waterproof sheet layer by connecting the waterproof sheets with an adhesive reinforcing tape; and

(Step 5) Forming a waterproof coating layer by applying an eco-friendly polyurethane composition on the waterproof sheet layer.

According to one embodiment of the present invention, step 2 may include the following steps:

(Step 2-1) Forming a first waterproof coating film with an eco-friendly polyurethane composition on the primer; and

(Step 2-2) Placing waterproof sheets on the first waterproof coating at intervals of 5 to 10 mm.

According to one embodiment of the present invention, in step 2-1, the first waterproof coating may be installed up to the corner where the wall and the slab meet.

According to one embodiment of the present invention, the waterproof sheet may be one or more selected from the group consisting of modified asphalt, synthetic rubber, modified rubber, vinyl chloride (PVC), and thermoplastic polyolefin (TPO).

According to one embodiment of the present invention, the polyurethane-urea resin two-part composition for fixing the waterproof sheet may include the following (a) and (b):

(a) a main part comprising a urethane-based prepolymer obtained by reacting a polyisocyanate and a polyol and having a free isocyanate group; and

(b) a curing agent portion comprising a polyamine.

According to one embodiment of the present invention, the urethane-based prepolymer may have a free isocyanate (Free NCO) content of 3 to 15% by weight.

According to one embodiment of the present invention, the urethane-based prepolymer has a free isocyanate content of 3 to 15% by weight, (i) a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500 and (ii) a weight A polyisocyanate compound is added in an equivalent ratio of 1:1.0 to 2 to a polyol in which a high-molecular weight polypropylene glycol triol having an average molecular weight (Mw) of 3,500 to 5,000 is mixed, and the reaction is performed at 80 ° C. It may be prepared by carrying out until it becomes.

According to one embodiment of the present invention, the polyamine may be selected from the group consisting of a polyamine of Formula 1, a polyether polyamine of Formula 2, and a polyaspartate polyamine of Formula 3 below:

[Formula 1]

R-(-NH ₂ ) _n

(In Formula 1, R has a functionality of n and represents an aliphatic, alicyclic or aromatic hydrocarbon group,

n is 2 to 4, preferably 2 or 3, more preferably 2.)

[Formula 2]

X ₁ -(-NH) _n

(In Formula 2 above,

X ₁ represents a residue obtained by removing an amino group from a polyetherpolyamine having a functionality of n and having a number average molecular weight of less than 600, preferably less than 300, wherein the amino group is bonded to a primary carbon atom and the ether group is 2 separated by one or more carbon atoms,

n is 2 to 4, preferably 2 or 3, more preferably 2.)

[Formula 3]

(In Formula 3,

X ₁ and n represent the same meaning as above,

R- ₁ and _R2 are the same or different and are an organic group, preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl or butyl group), and

R ₃ and R ₄ may be the same or different and represent hydrogen or an organic group which is inactive towards isocyanate groups at temperatures below 100° C. or hydrogen, preferably hydrogen)

According to one embodiment of the present invention, the polyamine may be polyaspartate polyamine of Chemical Formula 3.

According to one embodiment of the present invention, the eco-friendly polyurethane composition (A) 20 to 40 parts by weight of a polyol having a functional group of 2 to 3, 1 to 3 parts by weight of polyaldimine as a chain extender, and 1 to 3 parts by weight of a nonphthalate-based plasticizer 3 parts by weight, 0.1 to 0.4 parts by weight of a dispersant, 0.1 to 0.4 parts by weight of an antifoaming agent, 1 to 3 parts by weight of a coloring pigment, 50 to 70 parts by weight of an extender pigment as an inorganic filler, and 0.4 to 1.0 parts by weight of a bismuth compound as a curing accelerator. subject section; And (B) a curing part containing a prepolymer having a free isocyanate (Free NCO) content of 3 to 15% by weight;

The (A) main part and (B) curing part may be included in a weight ratio of 3 to 4: 1,

The bismuth compound may be at least one selected from bismuth octoate, bismuth naphthenate, bismuth propionate, bismuth maleinate, bismuth neothecanoid and bismuth neopentanoid,

The nonphthalate-based plasticizer is at least one selected from the group consisting of DOTP (dioctyl terephthalate), ESO (epoxidized soybean oil), DINCH (dinonylcyclohexanedicarboxylate), and AMG (acetylated monoglyceride) can

According to one embodiment of the present invention, in the main part (A), the polyol is (i) 70 to 85% by weight of a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500 and (ii) a weight average 15 to 30% by weight of a polymeric polypropylene glycol triol having a molecular weight (Mw) of 3,500 to 5,000 may be included.

According to one embodiment of the present invention, in the subject part (A), the polyaldimine may be selected from compounds represented by Formula 4 below:

[Formula 4]

In the formula, n is 2 to 4, preferably 2 or 3, more preferably 2,

Z is an aryl radical substituted by an alkyl group and/or an alkoxy group and having a total of 12 to 26 carbon atoms;

A is an n-valent having a molecular weight in the range of 42 to 6,000 g/mol, optionally containing an ether oxygen and/or containing a bicyclic or tricyclic ring system, bonded through at least one tertiary or quaternary carbon atom. It is an aliphatic, cycloaliphatic or aromatic hydrocarbyl radical.

According to one embodiment of the present invention, the polyaldimine may have an aldimine equivalent of 100 g/eq to 140 g/eq, preferably 110 g/eq to 130 g/eq. This may mean that 0 to 50%, preferably 10 to 40%, and more preferably 20 to 30% of the total number of aldimine groups in the polyaldimine of Chemical Formula 4 exist in the form of an amine.

According to one embodiment of the present invention, in the (B) curing part, the prepolymer has a free isocyanate content of 3 to 15% by weight, and (i) a low molecular weight polypropylene glycol having a weight average molecular weight (Mw) of 2,000 to 3,500 A polyisocyanate compound is added in an equivalent ratio of 1: 1.0 to 2 to a polyol in which a diol and (ii) a polymeric polypropylene glycol triol having a weight average molecular weight (Mw) of 3,500 to 5,000 are mixed, and the reaction is performed at 80 ° C. It may be prepared by performing until the free isocyanate content reaches the above range, wherein the polyisocyanate compound is aromatic polyisocyanate, toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI) , from the group consisting of xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate, modified MDI of the carbodiimide or urethane type, or hexamethylene diisocyanate (HDI) as aliphatic polyisocyanates. There may be one or more selected.

The polyurethane-urea resin two-component composition for fixing a waterproof sheet without using a solvent according to the present invention is a composite waterproofing method using a waterproof sheet and an eco-friendly polyurethane waterproof coating film together, without impairing workability, Fixation, waterproofness between waterproof sheets, and adhesion between waterproof sheets and waterproof coating films can be improved.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.

Hereinafter, various preferred embodiments of the present invention will be described with reference to the accompanying drawings.

Before describing the present invention in detail, the terms or words used in this specification should not be construed unconditionally in a conventional or dictionary sense, and in order for the inventor of the present invention to explain his/her invention in the best way It should be noted that concepts of various terms may be appropriately defined and used, and furthermore, these terms or words should be interpreted as meanings and concepts corresponding to the technical idea of the present invention.

That is, the terms used in this specification are only used to describe preferred embodiments of the present invention, and are not intended to specifically limit the contents of the present invention, and these terms represent various possibilities of the present invention. It should be noted that it is a defined term.

In addition, in this specification, it should be noted that singular expressions may include plural expressions unless the context clearly indicates otherwise, and similarly, even if they are expressed in plural numbers, they may include singular meanings. do.

Throughout this specification, when a component is described as "including" another component, it does not exclude any other component, but further includes any other component, unless otherwise stated. It can mean you can do it.

In addition, in this specification, in specifying the reference numerals for each component of each drawing, for the same component, even if the component is displayed in different drawings, it has the same reference numeral, that is, the same reference throughout the specification. Symbols indicate identical components.

In the drawings accompanying this specification, the size, position, coupling relationship, etc. of each component constituting the present invention is partially exaggerated, reduced, or omitted in order to sufficiently clearly convey the spirit of the present invention or for convenience of explanation. may be described, and therefore the proportions or scale may not be exact.

In addition, in the following description of the present invention, a detailed description of a configuration that is determined to unnecessarily obscure the subject matter of the present invention, for example, the known technology including the prior art, may be omitted.

An object of the present invention is to provide a composite waterproofing method comprising an eco-friendly polyurethane waterproofing coating and a waterproofing sheet comprising the following steps:

(Step 1) Applying a primer to the entire surface of the concrete base;

(Step 2) Placing waterproof sheets on the primer at intervals of 5 to 10 mm;

(Step 3) reinforcing the gap between the waterproof sheets by using a two-component polyurethane-urea resin composition for fixing the waterproof sheets;

(Step 4) forming a waterproof sheet layer by connecting the waterproof sheets with an adhesive reinforcing tape; and

(Step 5) Forming a waterproof coating layer by applying an eco-friendly polyurethane composition on the reinforced waterproof sheet layer.

In the present invention, step 2 may further include the following steps:

(Step 2-1) Forming a first waterproof coating film with an eco-friendly polyurethane composition on the primer; and

(Step 2-2) Arranging waterproof sheets at intervals of 5 to 10 mm on the first waterproof coating film.

In the present invention, in step 2-1, the first waterproof coating may be installed up to the corner where the wall and the slab meet. Preferably, in step 5, the eco-friendly polyurethane composition is applied to the corner where the wall and the slab meet.

In the present invention, in step 2 or step 2-2, the waterproof sheet may be arranged so that the corners are in contact without gaps or the corners are overlapped. In this case, the waterproof sheets may be reinforced with an adhesive made of the polyurethane-urea composition for fixing the waterproof sheet in step 3, and fixed with a reinforcing tape for fixing the waterproof sheet in step 4.

In the present invention, the waterproof sheet may be one or more selected from the group consisting of modified asphalt, synthetic rubber, modified rubber, vinyl chloride (PVC), and thermoplastic polyolefin (TPO), and in some cases, the waterproof sheet may be fibrous. there is.

In the present invention, the waterproof sheet may have a polyester long fiber non-woven fabric, a polypropylene non-woven fabric, silica sand and sand, a high-density polyethylene film, or the like formed or attached thereto. In addition, a long fiber nonwoven fabric, a polypropylene nonwoven fabric, silica sand and sand may be formed or attached to the lower portion of the waterproof sheet, for example, instead of a release film.

In the present invention, the polyurethane-urea resin two-part composition for fixing a waterproof sheet used in step 3 includes (a) a main part comprising a urethane-based prepolymer obtained by reacting polyisocyanate and a polyol and having a free isocyanate group; and (b) a curing agent part containing polyamine.

The present invention provides a polyurea paint characterized in that the molar ratio between the isocyanate group of the urethane prepolymer, the amine group of the polyaspartate, and the hydroxyl group of the polyol is 1:0.8 to 1.2.

Here, when the curing agent is used in excess of the above range in the production of the polyurethane-urea resin, curing may be delayed and the dry film tends to be too soft, and when the curing agent is used less than the above range, the dry film tends to be too hard.

In the present invention, the urethane-based prepolymer may have a free isocyanate (Free NCO) content of 3 to 15% by weight.

In the present invention, the urethane-based prepolymer has a free isocyanate content of 3 to 15% by weight, (i) a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500 and (ii) a weight average molecular weight (Mw) ) The polyisocyanate compound is added at an equivalent ratio of 1: 1.0 to 2 with respect to the polyol in which the high molecular weight polypropylene glycol triol having 3,500 to 5,000 is mixed, and the free isocyanate content (wt%) is in the above range at about 80 ° C. It may be prepared by reacting as much as possible.

In the present invention, the polyamine may be selected from the group consisting of a polyamine of Formula 1, a polyether polyamine of Formula 2, and a polyaspartate polyamine of Formula 3 below:

[Formula 1]

R-(-NH ₂ ) _n

(In Formula 1, R has a functionality of n and represents an aliphatic, alicyclic or aromatic hydrocarbon group,

n is 2 to 4, preferably 2 or 3, more preferably 2.)

[Formula 2]

X ₁ -(-NH) _n

(In Formula 2, X ₁ represents a residue obtained by removing an amino group from a polyether polyamine having a functionality of n and having a number average molecular weight of less than 600, preferably less than 300, wherein the amino group is bonded to a primary carbon atom, and the ether groups are separated by at least two carbon atoms,

n is 2 to 4, preferably 2 or 3, more preferably 2.)

[Formula 3]

(In Formula 3, X ₁ and n represent the same meaning as above,

R- ₁ and _R2 are the same or different and are organic groups, preferably alkyl groups of 1 to 9 carbon atoms, more preferably alkyl groups of 1 to 4 carbon atoms (e.g., methyl, ethyl or butyl group), and

R ₃ and R ₄ are the same or different and represent hydrogen or an organic group that is inert to an isocyanate group at a temperature of 100° C. or lower, preferably represents hydrogen.)

In the present invention, the compound of Formula 3 may be prepared by reacting a polyamine of Formula 1 or a polyether polyamine of Formula 2 with maleic acid ester or fumaric acid ester.

Specifically, the compound of Chemical Formula 3 is prepared by converting polyamine to maleic acid ester at a temperature of 0 to 100° C. using a starting material at a ratio in which one or more, preferably one unsaturated group is present for each primary amino group. Alternatively, it can be obtained by reacting with a fumaric acid ester. The reaction can be carried out without solvent or in the presence of suitable solvents such as methanol, ethanol, propanol, dioxane, aromatic solvents such as toluene and mixtures of these solvents. Preferably, the reaction is conducted without solvent. The reaction is generally complete within 2 weeks of cooling the reaction mixture to room temperature. In order to be able to control the exothermic reaction, it is preferred to add the amine to the flask followed by the addition of the maleic acid or fumaric acid ester. However, it is also possible to add the maleic or fumaric acid ester to the flask and then slowly add the amine to this mixture. A catalyst may be added to increase the reaction rate, but it is also possible to use no catalyst. Excess starting materials and solvents, especially isocyanate-reactive solvents, can be removed by distillation after the reaction.

In the present invention, the polyamine may be polyaspartate polyamine of Chemical Formula 3.

In the present invention, if the eco-friendly polyurethane composition does not use MOCA, which is harmful to the human body, as a chain extender, does not contain the four major heavy metals (lead, chromium, mercury, cadmium), and does not use a phthalate-based plasticizer, , may not be particularly limited.

According to the present invention, the above-described eco-friendly polyurethane composition may use a two-component composite waterproofing eco-friendly polyurethane composition comprising the following (A) main part and (B) curing part:

(A) 20 to 40 parts by weight of a polyol having 2 to 3 functional groups, 1 to 3 parts by weight of polyaldimine as a chain extender, 1 to 3 parts by weight of a nonphthalate plasticizer, 0.1 to 0.4 parts by weight of a dispersing agent, and 0.1 to 0.4 parts by weight of an antifoaming agent a main part containing 1 to 3 parts by weight of a color pigment, 50 to 70% by weight of an extender pigment as an inorganic filler, and 0.4 to 1.0 parts by weight of a bismuth compound as a curing accelerator; and

(B) A curing part containing a prepolymer having a free isocyanate (Free NCO) content of 3 to 15% by weight.

In the two-component composite waterproofing eco-friendly polyurethane composition, the main part and the curing part may be included in a weight ratio of 3 to 4: 1.

In addition, the polyol used in the main part (A) is (i) 70 to 85% by weight of a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500, and (ii) a weight average molecular weight (Mw) of 3,500 15 to 30% by weight of a high molecular weight polypropylene glycol triol having ~5,000, preferably, each having a unimodal molecular weight distribution.

In general, MOCA [4,4'-Methylene bis (ortho-chloroaniline)], which is mainly used as a chain extender or epoxy curing agent in the production of polyurethane or polyurea, improves the hardness of waterproof and moisture-proof urethane paints and mixes hardeners It has been used for a long time because it enables stable painting work by securing an appropriate painting time after painting, but it has been identified as a carcinogenic substance that is harmful to the human body and causes cancer to humans (Carcinogenicity of Some Aromatic Amines, Organic Dyes, and Related Exposures, See The Lancet Oncology, Volume 9, Issue 4, Pages 322 - 323, April 2008). For this reason, MOCA has been designated as a substance subject to ban on manufacturing, importing, and selling for products containing 0.1% or more after September 2020 in Korea.

In order to solve this problem, Registration Patent No. 10-1777432 (Title of Invention: Paint Composition) used a mixture of a number of primary and secondary bis-aromatic diamines, but since the diamines used are expensive, the replacement effect of MOCA is It is not meeting expectations.

Alternatively, it has been proposed to use a compound having an aldimine group, a ketimine group or an oxazolidine group, called a latent curing agent, which releases amino groups in contact with moisture and rapidly crosslinks with isocyanate groups without formation of carbon dioxide.

However, these latent curing agents can trigger a premature crosslinking reaction, thereby reducing the storage stability of the composition, and/or accelerating curing to such an extent that it results in too short an open time and too short a working time, making it difficult to operate smoothly. known to be unfavorable.

In addition, many known latent curing agents, upon curing, result in the release of a nuisance malodor caused by volatile aldehydes or ketones generated through hydrolysis, although the latent curing agent acts as a barrier agent.

In the present invention, in order to solve the problems associated with conventional chain extenders and substitutes thereof, a polyaldimine compound represented by Formula 4 is used:

[Formula 4]

In formula (4), n is 2 to 4, preferably 2 or 3, more preferably 2;

Z is an aryl radical substituted by an alkyl group and/or an alkoxy group and having a total of 12 to 26 carbon atoms;

A is an n-valent having a molecular weight in the range of 42 to 6,000 g/mol, optionally containing an ether oxygen and/or containing a bicyclic or tricyclic ring system, bonded through at least one tertiary or quaternary carbon atom. It is an aliphatic, cycloaliphatic or aromatic hydrocarbyl radical.

The polyaldimine compound of Formula 4 is odorless, pH-neutral, liquid or has a low-melting point and relatively low viscosity at room temperature, has low sensitivity to heat and moisture, and can be stored, transported, weighed and processed in a simple manner, , can be used as polyurethane for composite waterproofing.

The polyaldimine compound of Chemical Formula 4 is inactive even at elevated temperatures with aromatic isocyanates (eg, MDI) that are sterically unhindered and highly reactive, and thus can provide a composition with high storage stability, even in the presence of moisture, even in the presence of moisture. Although the reaction rate is slow, it reacts completely and flawlessly with isocyanates. However, since the reaction can be accelerated by an appropriate catalyst (curing accelerator), the reaction time can be appropriately controlled. In addition, the aldehyde released upon hydrolysis is non-volatile, odorless and colorless, and does not cause any odor or discoloration.

Since the polyaldimine compound of Formula 4 has excellent compatibility in polyurethane, it does not require additional addition of a plasticizer and does not cause migration of the plasticizer.

According to one embodiment of the present invention, in Chemical Formula 4, A is 1,2-propylene, 1,3-pentylene, 2-methyl-1,5-pentylene, 2,2(4),4-trimethyl -1,6-hexamethylene, 1,2-cyclohexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3,4(2)-methyl-1,3-cyclo Hexylene, methylenebicyclohexan-4-yl, methylenebis(2-methylcyclohexan-4-yl), (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)dimethylene, (tricyclo[5.2.1.0 ^2,6 ]decane-3(4),8(9)-diyl)dimethylene, α,ω-polyoxypropylene having an average molecular weight ranging from 170 to 5,000 g/mol and 330 to 6,000 g/mol of trimethylolpropane- or glycerol-initiated tris(ω-polyoxypropylene).

Accordingly, as diamines containing A, the following can be exemplified: 1,2-propanediamine, 1,3-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2,2(4 ), 4-trimethyl-1,6-hexanediamine (TMD), 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3 ,5,5-trimethylcyclohexane (isophoronediamine or IPDA), 4(2)-methyl-1,3-cyclohexanediamine, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methyl Cyclohexyl)methane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (norbornandiamine or NBDA), 3(4),8(9)-bis(aminomethyl) Tricyclo[5.2.1.0 ^2,6 ]decane (TCD diamine), an α,ω-polyoxypropylenediamine having an average molecular weight in the range of 200 to 4,000 g/mol, especially Jeffamine® products D-230, D-400; XTJ-582, D-2000, XTJ-578 and D-4000 (all from Huntsman), and trimethylolpropane- or glycerol-initiated tris(ω) having an average molecular weight ranging from 380 to 6,000 g/mol -polyoxypropyleneamines), particularly Jeffamine® products T-403, T-3000 and T-5000 (all from Huntsman).

In the present invention, as specific examples of the polyaldimine compound of Formula 4, it can be prepared from the following polyamines: N,N'-bis(4-alkylbenzylidene)-1,2-cyclohexanediamine, N,N '-bis(4-alkylbenzylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine, N,N'-bis(4-alkylbenzylidene)-4(2)-methyl-1, 3-cyclohexanediamine, N,N'-bis(4-alkylbenzylidene)-bis(4-aminocyclohexyl)methane, N,N'-bis(4-alkylbenzylidene)-2,5(2, 6)-bis(aminomethyl)bicyclo[2.2.1]heptane, N,N'-bis(4-alkylbenzylidene)-3(4),8(9)-bis(aminomethyl)tricyclo[5.2 .1.0 ^2,6 ]decane, N,N'-bis(4-alkylbenzylidene)polyoxypropylenediamine having an average molecular weight of 650-1050 g/mol. As another example of a polyamine that can be used, mention can be made of N,N',N''-tris(4-alkylbenzylidene)polyoxypropylenetriamine having an average molecular weight of 1050 to 1350 g/mol, wherein in each case Alkyl is a linear or especially branched decyl, undecyl, dodecyl, tridecyl or tetradecyl radical.

The polyaldimine compound of Formula 4 is an advantageous property for use in a polyurethane composition for composite waterproofing, and exhibits excellent miscibility and low separation tendency in the composition, and reacts with an isocyanate group in the absence of water or moisture (eg, cross-linking). ), and therefore the obtained polyurethane composition can have very good storage stability.

Finally, the aldehyde released upon curing is non-volatile and hydrolysis-stable, does not cause any odor sensation, has good compatibility with the cured polymer, and causes little bleeding or migration into the substrate.

In the present invention, the polyaldimine compound of Chemical Formula 4 can be prepared using the following aromatic diamines: 1,4-diaminobenzene, 2,4- and/or 2,6-diaminotoluene, 2,4'- and/or 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl-methane, 3,3'-dichloro-4,4' -Diaminodiphenylmethane (MOCA), 1-methyl-3,5-bis(methylthio)-2,4- and/or -2,6-diaminobenzene, 1,3,5-triethyl-2 ,4-diamino-benzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4- and/or -2,6-dia minobenzene (also known as 3,5-diethyl-2,4- and/or -2,6-toluenediamine, or DETDA), 3,5-dithiomethyl-2,4-diamino toluene ( i.e., ETHACURE 300), 4,6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3',5'-tetraethyl-4,4-diaminodiphenylmethane, 3,5 ,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane, 2,4,6-triethyl-m-phenylenediamine (TEMPDA), 3,5-diisopropyl-2,4-diaminotoluene, 3,5-di-sec-butyl-2,6-diamino Toluene, 3-ethyl-5-isopropyl-2,4-diaminotoluene, 4,6-diisopropyl-m-phenylenediamine, 4,6-di-tert-butyl-m-phenylenediamine, 4 ,6-diethyl-m-phenylenediamine, 3-isopropyl-2,6-diaminotoluene, 5-isopropyl-2,4-diaminotoluene, 4-isopropyl-6-methyl-m-phenyl Rendiamine, 4-isopropyl-6-tert-butyl-m-phenylenediamine, 4-ethyl-6-isopropyl-m-phenylenediamine, 4-methyl-6-tert-butyl-m-phenylenediamine , 4,6-di-sec-butyl-m-phenylenediamine, 4-ethyl-6-tertbutyl-m-phenylenediamine, 4-ethyl-6-sec-butyl-m-phenylenediamine, 4- Ethyl-6-isobutyl-m-phenylenediamine, 4-isopropyl-6-isobutyl-m-phenylenediamine, 4-isopropyl-6-sec-butyl-m-phenylenediamine, 4-tert- Butyl-6-isobutyl-m-phenylenediamine, 4-cyclopentyl-6-ethyl-m-phenylenediamine, 4-cyclohexyl-6-isopropyl-m-phenylenediamine, 4,6-dicyclo Pentyl-m-phenylenediamine, 2,2',6,6'-tetraethyl-4,4'-methylenebisaniline, 2,2',6,6'-tetraisopropyl-4,4'-methylene Bisaniline (methylenebisdiisopropylaniline), 2,2',6,6'-tetra-sec-butyl-4,4'-methylenebisaniline, 2,2'-dimethyl-6,6'-di- tert-butyl-4,4'-methylenebisaniline, 2,2'-di-tert-butyl-4,4'-methylenebisaniline, 2-isopropyl-2',6'-diethyl-4,4 '-Methylenebisaniline and mixtures thereof.

Among the above aromatic diamine compounds, aromatic diamine compounds containing two primary amine groups, such as diethyltoluenediamine (i.e., DETDA) isomers and mixtures thereof, diethyltoluenamine isomers and mixtures thereof, di-(methylthio) Toluenediamine (ie, ETHACURE 300) isomers and mixtures thereof, or di-(methylthio)toluene-diamine isomers and mixtures thereof can be particularly preferably used.

According to one embodiment of the present invention, the polyaldimine compound is diethyltoluenediamine (ie, DETDA) isomers and mixtures thereof, diethyltoluenamine isomers, di-(methylthio) toluenediamine (ie, ETHACURE 300) isomers and mixtures thereof, and at least one aromatic diamine compound selected from the group consisting of di-(methylthio)toluene-diamine isomers and mixtures thereof, or mixtures thereof.

According to one embodiment of the present invention, the polyaldimine may have an equivalent weight of 100 g/eq to 140 g/eq, preferably 110 g/eq to 130 g/eq. The higher the aldimine equivalent, the longer the gelation time and the improved workability, but on the other hand, physical properties such as curability, tensile strength, tear strength, elongation and hardness tend to decrease. That is, when the aldimine equivalent of polyaldimine is lower than the above range, workability is deteriorated, and when it is higher than the above range, physical properties may be deteriorated. Therefore, in the present invention, the aldimine equivalent of polyaldimine is preferably selected within a range of 100 g/eq to 140 g/eq, which is a range in which workability and physical properties of the resulting polyurethane can be balanced.

In the present invention, the fact that the aldimine equivalent of the polyaldimine is present in the above range means that a part of all amine groups in the polyamine may exist in the form of amines without being converted to aldimine. Specifically, all amine groups 1 to 50%, preferably 10 to 40%, more preferably 20 to 30% of may be present in the form of amines.

In the present invention, rather than adjusting the molecular weight of the amine compound, it is preferable to adjust the aldimine equivalent by adjusting the ratio of aldimine groups and amine groups (amine groups that are not changed to aldimine groups). That is, a molar ratio of polyamine and aldehyde (or ketone) of 1:0.5 to 2 (corresponding to an equivalent ratio of 1:0.25 to 1), preferably a molar ratio of 1:0.8 to 1.6 (equivalent ratio of 0.4 to 0.8), more preferably is reacted at a molar ratio of 1:1 to 1.4 (equivalent ratio of 0.5 to 0.7), and then, it is preferable to adjust the amount of polyamine and/or aldehyde to obtain an aldimine equivalent of 100 g/eq to 140 g/eq.

In the present invention, the bismuth compound has a group 13 non-metal-based characteristic, and thus has the advantage of accelerating product curing while being environmentally friendly. In some cases, when only a bismuth compound is used as a curing accelerator for a polyol curing agent, there may be a problem of deterioration in workability due to a decrease in mechanical strength and shortened pot life. It is possible to obtain the effect of improving mechanical strength and improving workability by adjusting the curing reaction time by the action of accelerating the crosslinking reaction.

According to one embodiment of the present invention, the bismuth compound may be selected from bismuth octoate, bismuth naphthenate, bismuth propionate, bismuth maleinate, bismuth neothecanoid and bismuth neopentanoid.

The bismuth compound may be included in the above-mentioned content, alternatively, in the main part in an amount of 0.01 to 5% by weight, preferably 0.4 to 1% by weight. When the content of the polyol is within the above range, an effect of securing workability, increasing elasticity, and increasing mechanical strength according to reaction rate control can be expected.

According to one embodiment of the present invention, a zinc compound or a mixture with a zinc compound may be used instead of the bismuth compound as the curing accelerator.

Therefore, the zinc compound is 0.01 to 5% by weight in the main part. Preferably it may be included in 0.4 to 1% by weight. When the content of the zinc compound is within the above range, there is an effect of increasing mechanical strength and reducing tackiness by accelerating the crosslinking reaction.

The zinc compound may include one selected from zinc octoate, zinc naphthenate, zinc propionate, zinc maleinate, zinc neothecanoid and zinc neopentanoid, and zinc carboxylate. no.

The polyol curing agent preferably includes a bismuth compound to a zinc compound in a weight ratio of 1:0.1 to 10. When the weight ratio of the bismuth compound to the zinc compound is within the above range, there is an effect of improving mechanical strength and adjusting the curing reaction time by accelerating the crosslinking reaction during the curing reaction.

According to one embodiment of the present invention, in addition to the bismuth compound and/or the zinc compound, a tertiary amine compound may be further contained as the curing accelerator.

The tertiary amine compound serves as a catalyst for the reaction of isocyanate-hydroxyl (a reaction in which a polymer gel is formed due to the growth of a polymer chain) and isocyanate-water (a reaction in which CO ₂ gas is produced through a foaming reaction). It serves as a catalyst for trimerization of isocyanate, which is called the polyisocyanurate reaction (PIR), and at this time, the rate of generation of polymer and the rate of gas generation are balanced so that the gas has sufficient strength (destruction) of the cell wall composed of polymer gel. It is preferred that the final curing be surrounded by (without shrinkage or shrinkage).

In addition, the most suitable factors for the catalytic reactivity of tertiary amine compounds are the basicity and the steric hindrance of the nitrogen atom of the amino group. As the basicity increases and the steric hindrance decreases, the catalytic activity generally increases, and also the ability to form hydrogen bonds. The degree of spatial separation between the activation site and the activation site can affect the catalyst selectivity.

Tertiary amine compounds usable in the present invention include 1,4-diazabicyclo (2,2,2) octane (DABCO or triethylene diamine), 2,2'-bis-(dimethyl aminoethyl ether) (BDMAEE), and N-alkylmorpholine, substituted piperazine, and the like.

According to one embodiment of the present invention, the non-phthalate plasticizer is DOTP (dioctyl terephthalate), ESO (epoxidized soybean oil), DINCH (dinonylcyclohexanedicarboxylate), AMG (acetylated monoglyceride) ) may be one or more selected from the group consisting of. Their chemical structure, eco-friendly characteristics and plasticity are shown in Table 1 below.

plasticizer Features structure eco-friendliness plasticity DOP (dioctyl
phthalates) Phthalates doesn't exist Great DOTP (dioctyl
terephthalate) Non-phthalate type Great Great ESO (Epoxidized
Soybean Oil) Eco-friendly plasticizer
stabilizator very good error DINCH (1,2-cyclohexane dicarboxylic acid diisononyl ester) Eco-friendly plasticizer Great Great AMG (Acetylated
Monoglycerides) Eco-friendly plasticizer very good Great

According to one embodiment of the present invention, the eco-friendly polyurethane composition for two-component composite waterproofing may be applied to one or more waterproof sheets selected from the group consisting of modified asphalt, synthetic rubber, modified rubber, vinyl chloride (PVC), and TPO.

According to one embodiment of the present invention, the prepolymer of the curing part has a free isocyanate content of 3 to 15% by weight, (i) a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500, and (ii) The free isocyanate content (wt%) at about 80 ° C. It may be prepared by reacting to be within the above range.

In the present invention, usable polyisocyanates may be specially selected from commercially available polyisocyanates, for example, the following may be mentioned.

Aromatic di- or triisocyanate, preferably diphenylmethane 4,4'- or 2,4'- or 2,2'-diisocyanate (MDI) or any mixture of these isomers, tolylene 2,4- or 2,6-diisocyanate (TDI) or any mixture of these isomers, MDI and mixtures of MDI homologs (polymeric MDI or PMDI), phenylene 1,3- or 1,4-diisocyanate, 2,3,5 ,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), dianisi din diisocyanate (DADI), tris(4-isocyanatophenyl)methane or tris(4-isocyanatophenyl) thiophosphate; preferably MDI or TDI;

aliphatic, cycloaliphatic or aromatic diisocyanates or triisocyanates, preferably tetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 2, 2,4- and/or 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), decamethylene 1,10-diisocyanate, dodecamethylene 1,12-diisocyanate, lysine diisocyanate or lysine Ester diisocyanate, cyclohexane 1,3- or 1,4-diisocyanate, 1-methyl-2,4- and/or -2,6-diisocyanatocyclohexane (H6TDI), 1-isocyanato -3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate (H12MDI), 1, 3- or 1,4-bis-(isocyanatomethyl)cyclohexane, m- or p-xylylene diisocyanate, tetramethylxylylene 1,3- or 1,4-diisocyanate, 1,3,5 -tris(isocyanatomethyl)benzene, bis(1-isocyanato-1-methylethyl)naphthalene, dimer or trimer fatty acid isocyanates such as, in particular, 3,6-bis(9-isocyanate) tononyl)-4,5-di-(1-heptenyl)cyclohexene (dimeryl diisocyanate); preferably H12MDI or HDI or IPDI; and

oligomers or derivatives of the mentioned di- or triisocyanates derived from HDI, IPDI, MDI or TDI, in particular oligomers containing uretdione or isocyanate or iminooxadiazinedione groups or various groups among them; or di- or polyfunctional derivatives containing an ester or urea or urethane or biuret or allophanate or carbodiimide or uretonimine or oxadiazinetrione group or various groups thereof. In practice, polyisocyanates of this kind are typically mixtures of substances having different degrees of oligomerization and/or chemical structures. They especially have an average NCO functionality of 2.1 to 4.0.

Particularly preferred polyisocyanates may be in the form of HDI, IPDI, H12MDI, TDI, MDI or MDI that is liquid at room temperature.

According to one embodiment of the present invention, the polyisocyanate compound is an aromatic polyisocyanate, toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), xylene diisocyanate (XDI), isophorone It may be at least one selected from the group consisting of diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate, carbodiimide or urethane-type modified MDI, or hexamethylene diisocyanate (HDI) as an aliphatic polyisocyanate.

According to one embodiment of the present invention, the polyisocyanate compound may be toluene diisocyanate (TDI).

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention.

Example

Preparation Example 1: Preparation of urethane-based prepolymer using isophorone diisocyanate (IPDI)

(A) 100 parts by weight of low molecular weight polypropylene glycol diol (Mw = 2,000), 35 parts by weight of high molecular weight polypropylene glycol triol (Mw = 3,000), 5 parts by weight of 1,3-butylene glycol, as a non-phthalate plasticizer 3 parts by weight of NEO-T (manufacturer: Aekyung Petrochemical), 15 parts by weight of isophorone diisocyanate (IPDI), and 5 parts by weight of xylene were mixed.

In the above mixture, the equivalent ratio of the isocyanate (NCO) groups of the tolylene diisocyanate compound to the hydroxyl (OH) groups of the polyol was approximately 1:1.2.

The obtained mixture was heated to 80° C. and reacted until the free isocyanate (%) content was 5.5±0.2% to obtain a polyisocyanate prepolymer.

Preparation Example 2: Preparation of urethane-based prepolymer using tolylene diisocyanate (TDI)

(A) 100 parts by weight of low molecular weight polypropylene glycol diol (Mw = 2,000), 35 parts by weight of high molecular weight polypropylene glycol triol (Mw = 3,000), 5 parts by weight of 1,3-butylene glycol, as a non-phthalate plasticizer 3 parts by weight of NEO-T (manufacturer: Aekyung Petrochemical), 15 parts by weight of tolylene diisocyanate (TDI), and 5 parts by weight of xylene were mixed.

In the above mixture, the equivalent ratio of the isocyanate (NCO) groups of the tolylene diisocyanate compound to the hydroxyl (OH) groups of the polyol was approximately 1:1.2.

The obtained mixture was heated to 80° C. and reacted until the free isocyanate (%) content was 5.5±0.2% to obtain a polyisocyanate prepolymer.

Preparation Example 3: Preparation of polyaspartic ester amine

As described in Example 1 of Korean Patent Publication No. 10-2004-0027397, a stirrer, a heating mantle, a nitrogen inlet, a thermocouple, and an addition funnel were equipped in a round bottom flask. 74.1 g (1 eq.) of 2-[2-(2-aminoethoxy)ethoxy]ethylamine (Jeffamine XTJ-504 available from Huntsman) was charged to the flask at room temperature. 172 g (1 eq) of diethyl maleate was added over 60 minutes through an addition funnel. The temperature of the flask was fixed at 35°C. The reaction mixture was heated to 60 °C, held at this temperature for 12 hours and then cooled to room temperature. As a result of iodine titration, the reaction was more than 98% complete after 1 day at room temperature and 100% complete within 2 weeks. The clear, colorless final product had an amine value of 227.93 (theoretical amine number: 227.03).

Preparation Example 4: Preparation of polyaspartic ester amine

As described in Example 2 of Korean Patent Publication No. 10-2004-0027397, a stirrer, a heating mantle, a nitrogen inlet, a thermocouple, and an addition funnel were equipped in a round bottom flask. To the flask was charged 110.15 g (1 equivalent) of 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (BASF TTD available from BASF) at room temperature. 172 g (1 equivalent) of diethyl maleate was added over 60 minutes through an addition funnel. The temperature of the flask was fixed at 35°C. The reaction mixture was heated to 60 °C, held at this temperature for 12 hours and then cooled to room temperature. As a result of iodometric titration, the reaction was more than 98% complete after 1 day at room temperature and 100% complete within 2 weeks. The clear, colorless final product had an amine number of 196.7 (theoretical amine number: 198.8).

Example 1: Composite waterproofing method using a polyurethane-urea resin composition:

(1) Preparation of polyurethane-urea resin composition:

A polyurethane-urea resin composition was prepared by mixing 100 parts by weight of the urethane-based prepolymer obtained in Preparation Example 1 as the main part and 30 parts by weight of the polyaspartic ester amine obtained in Preparation Example 3 as the curing agent part.

(2) Preparation of environmentally friendly polyurethane resin composition:

(A) Manufacture of subject part

Low molecular weight polypropylene glycol diol (Mw = 3,000) 238 parts by weight, high molecular weight polypropylene glycol triol (Mw = 4,000) 80 parts by weight, DETDA aldimine (118 g / eq) 18.5 parts by weight, NEO as a non-phthalate plasticizer -T (manufacturer: Aekyung Petrochemical) 10 parts by weight, bismuth compound (manufacturer: Jinyang Chemical Co., Ltd.) 5 parts by weight, PE-wax 6 parts by weight, defoamer 1 part by weight, TiO ₂ 20 parts by weight and calcium carbonate as an inorganic filler 619 parts by weight were mixed to obtain 997.5 parts by weight of the main part.

(B) Preparation of hardened part

The polyisocyanate prepolymer (Free NCO 5.5% by weight) obtained in Preparation Example 1 was used as a curing part.

(3) Complex waterproofing method

(Step 1) The base concrete surface (support layer) was thoroughly cleaned and a primer was applied.

(Step 2) On the formed primer, glass fiber waterproof sheets impregnated with asphalt were placed at intervals of 5 to 10 mm.

(Step 3) The polyurethane-urea resin composition prepared in Example 1 was manually applied to the gap between the waterproof sheets to reinforce them.

(Step 4) A waterproof sheet layer was formed by connecting the polyurethane-urea resin composition reinforcing layer reinforced in the gap between the waterproof sheets and the adhesive reinforcing tape having an area capable of covering both sides of the waterproof sheets. The reinforcing tape reinforces a joint between sheets and is a fiber tape coated with an adhesive on one side. In some cases, a mesh type fiber tape having excellent tensile and tear strength may be used.

(Step 5) A waterproof coating layer was formed by applying the eco-friendly polyurethane resin composition prepared in (2) above to the waterproof sheet layer adhered and connected with adhesive reinforcing tape.

Finally, the composite waterproof layer composed of the waterproof sheet layer and the waterproof coating layer was dried.

Comparative Example 1

A polyurea waterproof paint was prepared by mixing a main part composed of methylenedipheryl diisocyanate prepolymer and a curing agent part containing polyetheramine, diethyltoluenediamine, pigment and additives in a volume ratio of about 1:1.

The composite waterproof method was performed in the same manner as in Example 1, but in step 3, the gap between the waterproof sheets was reinforced with the polyurea waterproof paint obtained above.

Comparative Example 2

A main part composed of toluene diisocyanate prepolymer (TDI) obtained in Preparation Example 2 and 20 to 30 parts by weight of polyol, 1 to 2 parts by weight of polyaldimine, 50 to 60 parts by weight of calcium carbonate and other additives (foaming agent, dispersant, Toner, etc.) were mixed in a weight ratio of approximately 4:1 to prepare a polyurethane waterproof paint.

The composite waterproofing method was performed in the same manner as in Example 1, but in step 3, the gap between the waterproof sheets was reinforced with the polyurethane waterproofing material paint obtained above.

Experimental Example 1

The physical properties of the waterproof sheet reinforcement layer and the resulting composite waterproof layer prepared according to the composite waterproofing method performed in Example 1 and Comparative Examples 1 and 2 were measured and summarized in Table 2 below.

The following coating film strength, tensile strength, tear strength, elongation, touch drying, curing drying, pot life, weather resistance, and adhesion are the physical properties of the paint.

Among them, the tensile strength, tear strength and elongation test methods were tested according to the KSF3211 and KSM6518 test methods for waterproofing materials for construction coatings.

physical properties Example 1 Comparative Example 1 Comparative Example 2 coating hardness 90(Shore A)45(Shore A) 90 (Shore A)
45 (Shore A) 90 (Shore A)
45 (Shore A) Tensile strength (N/㎟) 9.0 18 3.0 Tear strength (N/mm) 45 100 19.3 Elongation (%) 500 350 850 dry to the touch 1 hour 30 minutes within 10 seconds 5 hours cure drying 8 hours - 72 hours pot life 30 - 80 Weatherability ( within 2.0 over 10 over 10 adhesion 600 200 150

As can be seen in Table 2, when the composite waterproof method is performed using the polyurethane-urea fiber sheet reinforcing material according to the present invention (Example 1), the coating waterproofing in the case of using the existing polyurea reinforcing material (Comparative Example 1) Compared to the case of using the same environmentally friendly polyurethane as used in the law (Comparative Example 2), the following advantages are obtained:

First, the tensile strength, tear strength and elongation are intermediate between the polyurea coating film and the polyurethane coating film, so the overall balance of physical properties is excellent.

Second, the touch drying time and the curing drying time are appropriately balanced so that the composite waterproofing method can be performed without compromising workability.

Third, while the polyurea resin (Comparative Example 2) has a very short pot life, manual work is impossible and only mechanical application is possible, whereas the polyurethane-urea according to the present invention has a significantly increased pot life, allowing manual work.

Fourth, adhesion and weather resistance are excellent.

So far, specific embodiments of the composite waterproofing method including the eco-friendly polyurethane waterproofing coating film and the waterproofing sheet according to the present invention have been described, but various modifications are possible within the scope of the present invention. It is obvious.

Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.

That is, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims and All changes or modified forms derived from the equivalent concept should be construed as being included in the scope of the present invention.

Claims (13)

(Step 1) Applying a primer to the entire surface of the concrete base;
(Step 2) Placing waterproof sheets on the primer at intervals of 5 to 10 mm;
(Step 3) reinforcing the gap between the waterproof sheets by using a two-component polyurethane-urea resin composition for fixing the waterproof sheets;
(Step 4) forming a waterproof sheet layer by connecting the waterproof sheets with an adhesive reinforcing tape; and
(Step 5) forming a waterproof coating layer by applying an eco-friendly polyurethane composition on the reinforced waterproof sheet layer;
The eco-friendly polyurethane composition includes (A) 20 to 40 parts by weight of a polyol having 2 to 3 functional groups, 1 to 3 parts by weight of polyaldimine as a chain extender, 1 to 3 parts by weight of a nonphthalate plasticizer, and 0.1 to 0.4 parts by weight of a dispersant. a main component containing 0.1 to 0.4 parts by weight of an antifoaming agent, 1 to 3 parts by weight of a color pigment, 50 to 70 parts by weight of an extender pigment as an inorganic filler, and 0.4 to 1.0 parts by weight of a bismuth compound as a curing accelerator; And (B) a curing part containing a prepolymer having a free isocyanate (Free NCO) content of 3 to 15% by weight;
The (A) main part and (B) curing part are included in a weight ratio of 3 to 4: 1,
the bismuth compound is at least one selected from bismuth octoate, bismuth naphthenate, bismuth propionate, bismuth maleinate, bismuth neothecanoid and bismuth neopentanoid;
The non-phthalate plasticizer is one selected from the group consisting of DOTP (dioctyl terephthalate), ESO (epoxidized soybean oil), DINCH (dinonylcyclohexanedicarboxylate), and AMG (acetylated monoglyceride) Characterized in that more than
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 1,
In step 2,
(Step 2-1) Forming a first waterproof coating film with an eco-friendly polyurethane composition on the primer; and
(Step 2-2) arranging waterproof sheets at intervals of 5 to 10 mm on the first waterproof coating film; characterized in that it further comprises,
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 2,
In step 2-1 above,
Characterized in that the first waterproofing film is installed to the corner where the wall and the slab meet,
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 1,
Characterized in that the waterproof sheet is at least one selected from the group consisting of modified asphalt, synthetic rubber, modified rubber, vinyl chloride (PVC), and thermoplastic polyolefin (TPO),
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 1,
The polyurethane-urea resin two-part composition for fixing the waterproof sheet,
(a) a main part comprising a urethane-based prepolymer obtained by reacting a polyisocyanate and a polyol and having a free isocyanate group; and
(b) a curing agent part containing polyamine; characterized in that it is a two-component composition comprising
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 5,
The urethane-based prepolymer is characterized in that the free isocyanate (Free NCO) content is 3 to 15% by weight,
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 5,
The urethane-based prepolymer has a free isocyanate content of 3 to 15% by weight, (i) a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500, and (ii) a weight average molecular weight (Mw) of 3,500 to 5,000 A polyisocyanate compound is added at an equivalent ratio of 1: 1.0 to 2 to a polyol mixed with a polymeric polypropylene glycol triol having a reaction at 80 ° C. characterized in that,
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 5,
Characterized in that the polyamine is one selected from the group consisting of a polyamine of Formula 1 below, a polyether polyamine of Formula 2 below, and a polyaspartate polyamine of Formula 3 below.
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
[Formula 1]
R-(-NH ₂ ) _n
(In Formula 1, R has a functionality of n and represents an aliphatic, alicyclic or aromatic hydrocarbon group,
n is 2 to 4, preferably 2 or 3, more preferably 2.)

[Formula 2]
X ₁ -(-NH) _n
(In Formula 2 above,
X ₁ represents a residue obtained by removing an amino group from a polyetherpolyamine having a functionality of n and having a number average molecular weight of less than 600, preferably less than 300, wherein the amino group is bonded to a primary carbon atom and the ether group is 2 separated by one or more carbon atoms,
n is 2 to 4, preferably 2 or 3, more preferably 2.)

[Formula 3]

(In Formula 3,
X ₁ and n represent the same meaning as above,
R- ₁ and _R2 are the same or different, and are organic groups that are inactive to isocyanate groups at a temperature of 100° C. or lower, preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms (e.g., methyl , an ethyl or butyl group), and
R ₃ and R ₄ may be the same or different and represent hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100° C. or lower, and is preferably hydrogen.)
delete According to claim 1,
In the subject part (A),
The polyol is (i) 70 to 85% by weight of a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500 and (ii) a high molecular weight polypropylene glycol triol having a weight average molecular weight (Mw) of 3,500 to 5,000 Characterized in that it comprises 15 to 30% by weight,
Composite waterproofing method including eco-friendly polyurethane waterproof coating and waterproof sheet.
According to claim 1,
In the subject part of (A) above,
The polyaldimine is a composite waterproof method comprising an eco-friendly polyurethane waterproof coating film and a waterproof sheet, characterized in that it is selected from the compounds of Formula 4 below:
[Formula 4]

In Formula 4,
n is 2 to 4;
Z is an aryl radical substituted by an alkyl group and/or an alkoxy group and having a total of 12 to 26 carbon atoms;
A is an n-valent aliphatic having a molecular weight in the range of 42 to 6,000 g/mol, optionally containing an ether oxygen and/or containing a bicyclic or tricyclic ring system, bonded through at least one tertiary or quaternary carbon atom; It is an alicyclic or aromatic hydrocarbyl radical.
According to claim 1,
Characterized in that the polyaldimine has an aldimine equivalent of 100 g / eq to 140 g / eq,
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According to claim 1,
In the (B) curing part,
The prepolymer has a free isocyanate content of 3 to 15% by weight, (i) a low molecular weight polypropylene glycol diol having a weight average molecular weight (Mw) of 2,000 to 3,500 and (ii) a weight average molecular weight (Mw) of 3,500 to 5,000 It is prepared by adding a polyisocyanate compound in an equivalent ratio of 1: 1.0 to 2 to the polyol in which the polymeric polypropylene glycol triol is mixed, and performing the reaction at 80 ° C. until the free isocyanate content reaches the above range,
The polyisocyanate compound is an aromatic polyisocyanate, such as toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), polymethylene poly Characterized in that at least one selected from the group consisting of phenyl polyisocyanate, carbodiimide or urethane-type modified MDI, or hexamethylene diisocyanate (HDI) as aliphatic polyisocyanate,
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