KR101110575B1 - Environment friendly polyurea paint composition having superior toughness and method using the same - Google Patents

Abstract

PURPOSE: A polyurea paint composition is provided to give strength and tenacity inside molecular structure, thereby using for various usage like waterproofing, floor material, etc, and to increase the construction efficiency due to short hardening time. CONSTITUTION: A polyurea paint composition comprises: a resin mixture containing 20-40 weight% epoxy prepolymer, 20-40 weight% polyoxypropylene amine, 15-25 weight% cross-linking agent, 2-8 weight% pigment, and 2-8weight% additive; and a hardener, which is obtained by mixing 70-130 parts by weight polypropylene glycol, or polyoxypropylene diamine into 100.0 parts by weight isophorone diisocyanate or methylene diphenol diisocyanate. The volume ratio of the resin mixture and the hardener is 1:1. The polyoxypropylene amine comprises 16-33 weight% polyoxypropylenediamin, and 4-7 weight% polyoxypropylene triamine.

Description

ENVIRONMENT FRIENDLY POLYUREA PAINT COMPOSITION HAVING SUPERIOR TOUGHNESS AND METHOD USING THE SAME}

The present invention relates to an environmentally friendly polyurea paint composition having excellent toughness and a construction method thereof, and more particularly, to a two-component polyurea paint composition which can be used in various applications such as waterproofing, anticorrosion, and flooring due to its excellent physical properties and wear resistance. And it relates to a construction method using the composition.

Polyurea molecules are usually composed of evenly distributed elements that increase flexibility and those that increase hardness.

It is generally known that the element having high flexibility has a low glass transition temperature (Tg), and the molecular weight is 400- such as polyether, polyester, polyalkyldiol, etc. Flexibility is increased between 5000 and high hardness to increase hardness. The semi-crystalline aromatic diisocyanate binds to a low molecular weight chain extender to increase hardness.

In general, polyurea is synthesized with diamines having chain extension and low molecular weight to form urea units. Therefore, polyurea is widely changed in its properties by various materials such as selected material, molecular weight, or reaction rate. In other words, it is possible to change the material from a brittle material to a hard material or a soft material, or even a material having a certain viscosity. Particularly in the case of polyurea, since the amide ester bonds of fatty acids have mixed bonds, the properties at high temperatures have intermediate properties between these polyester and polyamide systems.

The synthesis of polyurea can be divided into two large domains: addition and condensation. The addition reaction occurs when the unsaturated monomer reacts in the reaction initiation stage, propagation stage, and termination stage. Normally, monomers are simple molecules with double bonds. At the start, one of the two double bonds is broken and reacts rapidly.

In most cases, the addition reaction proceeds without producing byproducts. Condensation or step growth reactions occur when monomers react with molecules with double functional groups at the stages made to form the polymer's chains. This is similar to the condensation reaction between molecules of small molecular weight. At this time, small molecules such as water and carbon dioxide may be removed. The addition reaction can be classified into homogeneous polymers or copolymers. The fine form of the copolymer can be divided into random, cross, and lump forms, but this varies according to reaction conditions, concentrations, and monomer reactivity ratios. Furthermore, controlling the molecular weight or distribution of molecular weight after the reaction of the polymers as the final reaction product is more difficult than the condensation reaction controlled by using a reagent that changes the chain shape. The control of reactivity can be controlled by anionic polymerisation and in some cases the synthesis of nearly single chain distributions is also possible. Condensation reactions are also used to make copolymerized polymers.

Bifunctional monomers are used to make a chain polymer, and having three or more functional groups may constitute a cross-linked polymer network in a three-dimensional space.

Polyurea is an elastomeric material formed by the reaction of polyoxyether polyamine mixture with isocyanate prepolymer and isocyanate prepolymer, and it can't generally be mixed at room temperature due to rapid reactivity of amine and isocyanate. Proceed.

In other words, the two-component high-temperature high-pressure spray device is passed through the mixing collision-type device without a mixing process, and the two solutions are combined to cure within a few seconds or minutes after spraying to form a solid and thick coating film.

However, in general, polyurea has the same elastomeric properties as synthetic rubber and thus has good properties such as flexibility and elongation.However, it is difficult to characterize strength and toughness due to the repetitive structure of the oxyether in the molecule and the limitation of the currently available raw materials. There is a problem.

In order to solve the above problems, the present invention

The purpose is to introduce epoxy prepolymers into the polymer molecule to improve the strength and toughness of the finally completed polyurea to provide differentiation and optimization of physical properties.

In addition, to solve the above problems, the present invention

It is an object of the present invention to provide a construction method using a two-component polyurea coating composition that shortens the curing time within a few minutes and improves the construction efficiency, including shortening the air and reducing labor costs.

In order to achieve the above object, the present invention

A resin mixture consisting of 20 to 40% by weight epoxy prepolymer, 20 to 40% by weight polyoxypropylene amine, 15 to 25% by weight crosslinking agent, 2 to 8% by weight pigment, 2 to 8% by weight additive,

A two-component polyurea coating composition comprising a curing agent obtained by mixing 70 to 130 parts by weight of polypropylene glycol or polyoxypropylene diamine with 100 parts by weight of isophorone diisocyanate (IPDI) or methylene diphenol diisocyanate (MDI),

The volume ratio of the resin mixture and the curing agent is 1: 1,

The polyoxypropylene amine provides a polyurea coating composition, characterized in that formed by mixing 16 to 33% by weight of polyoxypropylene diamine and 4 to 7% by weight of polyoxypropylene triamine.

The epoxy prepolymer is preferably prepared by holding a bifunctional epoxy resin with an end group formed of an amine and a amine having a molecular weight of 50 to 250 and two functional groups at 60 to 80 ° C. for 2 hours.

The polyoxypropylene amine preferably has a weight average molecular weight of 1,000 to 6,000.

The crosslinking agent is preferably at least one selected from diethyltoluenediamine and polyetheramine.

In order to achieve the above another object, the present invention

Removing foreign matter on the concrete or steel surface;

Applying a primer; And

As a construction method using a polyurea paint composition comprising the step of mixing and spraying a resin mixture and a curing agent in the composition,

It provides a construction method using a polyurea paint composition characterized in that the liquid temperature at the time of mixing 50 to 80 ℃, spray injector pressure 1500 to 2500 psi.

Polyurea coating composition according to the present invention is given strength and toughness in the molecular structure and can be used for various uses such as waterproofing, anticorrosion, flooring, etc., the curing time is short within a few minutes to improve the construction efficiency, such as shortening the air of work and reducing labor costs In addition to higher mechanical properties and wear resistance than conventional paints.

Hereinafter, the present invention will be described in detail.

The present invention is a resin mixture consisting of 20 to 40% by weight epoxy prepolymer, 20 to 40% by weight polyoxypropylene amine, 15 to 25% by weight crosslinking agent, 2 to 8% by weight pigment, 2 to 8% by weight additive, and isophorone A two-component polyurea coating composition comprising a curing agent obtained by mixing 70 to 130 parts by weight of polypropylene glycol or polyoxypropylene diamine with 100 parts by weight of diisocyanate (IPDI) or methylene diphenol diisocyanate (MDI), the resin mixture And a volume ratio of the curing agent is 1: 1, and the polyoxypropylene amine is formed by mixing 16 to 33% by weight of polyoxypropylene diamine and 4 to 7% by weight of polyoxypropylene triamine. do.

Polyurea of the present invention is a resin having excellent mechanical properties such as water resistance, chemical resistance, salt water resistance, and mechanical properties such as abrasion resistance and impact resistance, and is water-soluble and has eco-friendly properties that are harmless to the human body.

In the present invention, the epoxy prepolymer is introduced into the polyurea molecular structure as a method of imparting the toughness of the polymer, thereby improving the strength and toughness of the finally completed polymer, thereby making it possible to expect differentiation and optimization of physical properties according to the use.

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The epoxy prepolymer according to the present invention may be prepared by maintaining a terminal group formed of an amine group, maintaining a bifunctional epoxy resin with an amine having a molecular weight of 50 to 250 and two functional groups at 60 to 80 ° C. for 2 hours.

Epoxy prepolymers in which the terminal group is an amine are main polymers that impart the toughness of the composition, and provide main functions such as adhesion to paint surfaces, durability, weather resistance, and crack resistance. The content of the epoxy prepolymer in the present invention is preferably 20 to 40% by weight. When the content of the epoxy prepolymer is less than 20% by weight, the effect of toughness of the composition is insignificant, and when the content of the epoxy prepolymer is more than 40% by weight, the viscosity of the epoxy prepolymer is increased and the content of the other composition is relatively small. It is not desirable because it can not make urea paint.

Polyoxypropylene amines may be used polyoxypropylene diamine and / or polyoxypropylene triamine. In the present invention, the content of polyoxypropylene amine is preferably 20 to 40% by weight. When the content of polyoxypropylene is less than 20% by weight, the elongation of the paint is lowered. When the content of polyoxypropylene is greater than 40% by weight, the tensile strength is increased, but it is not preferable because the wear resistance is lowered and the durability is lowered. Also preferably, the weight average molecular weight is 1,000 to 6,000.

The cross-linking agent may be an aromatic or alicyclic amine compound used as a chain extender. Among them, one or more selected from diethyltoluenediamine and polyetheramine is preferable. The crosslinking agent contributes to controlling the gel time of the polyurea paint. Specifically, the primary amine can shorten the gelling time of the polyurea paint, and the secondary amine can extend the gelling time of the polyurea paint. In the present invention, the content of the crosslinking agent is preferably 15 to 25% by weight. If the content of the crosslinking agent is less than 15% by weight, it is not preferable because the effect as a chain extender is insignificant, and it is difficult to expect the improvement of the mechanical properties. Because it is not desirable.

The pigment imparts the color of the polyurea paint. In the present invention, the pigment is used to impart the color of the polyurea coating composition, and it is preferable to use 2 to 8% by weight, but it is not necessarily limited to the above range according to the needs of the consumer or the needs of the manufacturer, and may be appropriately adjusted. .

The additive is usually used alone or mixed within the range of 2 to 8% by weight of UV-stabilizers, adhesion promoters and the like used in the composition of the paint for painting.

In the present invention, the UV stabilizer prevents premature degradation due to ultraviolet rays, and it is preferable to add 1 to 4% by weight. When the amount of UV stabilizer added is less than 1% by weight, the effect of preventing premature degradation due to ultraviolet rays is lowered. When the amount of added UV stabilizer is more than 4% by weight, the effect of preventing early degradation by UV rays is no longer improved. On the other hand, there is a risk of lowering other physical properties of the coating composition. As an example of the UV stabilizer, it is preferable to use Tinuvin 571 (Tibavin 571, Ciba) which can be used in water systems.

In the present invention, the adhesion promoter plays a role of reinforcing the adhesion to the material and the strength of the paint composition through a chemical action on the binder and the composition, it is preferred to add 1 to 4% by weight. If the addition amount of the adhesion promoter is less than 1% by weight, the adhesion between the coating composition and the concrete surface may be lowered. If the addition amount of the adhesion promoter is more than 4% by weight, the adhesion between the coating composition and the concrete surface is no longer present. It is not preferable because there is a possibility that the other physical properties of the coating composition may be lowered without remarkably improving. It is preferable to use the silane compound of Dow Corning Corporation specifically, as an example of an adhesion promoter.

The epoxy prepolymer prepared above is obtained with a one-component resin mixture in which polyoxypropylene amine, a crosslinking agent, a pigment, and an additive are premixed as a polymer. Next, an isocyanate prepolymer is used as a hardening agent, and the polyurea coating composition to a waterproof floor is constructed, and it is constructed using a two-component high temperature, high pressure spray device.

Isocyanate prepolymers as curing agents include Hexamethylene Diisocyanate (HDI), Isophorone Diisocyanate (IPDI), Cyclohexylmethane diisocyanate (H ₁₂ MDI), Methylene Diphenyl Diisocyanate , MDI), 70 to 130 parts by weight of one or more selected from polypropylene glycol or polyoxypropylene diamine are mixed with respect to 100 parts by weight of an isocyanate mixture containing one or more selected from toluene diisocyanate (TDI). The NCO content is maintained at a temperature of 60 to 120 ° C. for 3 to 5 hours and the NCO content is 10 to 20% by weight, and the viscosity is preferably 200 to 2,000 cps / 25 ° C.

The two-component polyurea coating composition of the present invention having excellent toughness is completed by mixing the resin mixture and the curing agent, and the gelation time varies according to the type of polymer, crosslinking agent, and curing agent in the resin mixture and the form of the polyurea coating. Are separated.

The environmentally friendly polyurea paint composition having excellent toughness of the present invention can be used in various applications such as waterproofing, anticorrosion, and flooring because of excellent physical properties and wear resistance.

According to another aspect of the invention, the step of removing the foreign matter on the surface of the concrete or steel surface; Applying a primer; And a polyurea paint composition comprising the steps of mixing and spraying a resin mixture and a curing agent in the coating composition, wherein the mixing liquid temperature is 50 to 80 ° C., and the spray injector pressure is 1500 to 2500 psi. It provides a construction method using a polyurea paint composition characterized in that.

Looking specifically at the work process, the concrete floor removes the latency layer and other contaminants from the concrete surface. Next, the part with the pore area is filled with a sealing agent, applied with a primer, and then sprayed with the polyurea paint. In the case of the steel surface, the rust surface treatment of the steel surface removes rust and foreign substances, and the antirust primer is applied. Next, it is completed by spraying the polyurea paint.

In the construction according to the present invention conditions of the two-component high temperature and high pressure spray device are as follows. It is preferable to maintain the pressure of the spray injector at the time of mixing collision of a resin mixture and a hardening | curing agent. When the pressure is lower than 1500 psi, there is a problem of deterioration of physical properties due to unhardening due to poor mixing, and when the pressure is higher than 2,500 psi, a smooth coating surface cannot be obtained.

On the other hand, it is preferable to maintain the temperature of resin and hardening | curing agent at the time of mixing collision at 50-80 degreeC. When the temperature is 50 ° C. or lower, a problem of poor mixing occurs, and when the temperature is 80 ° C. or higher, the reaction rate between the main body and the curing agent is increased, which is not preferable because a smooth coating surface cannot be obtained.

Ordinary urethane and epoxy paints are two-component products that must be properly mixed with the main agent and hardener, and fail to comply with them or in particular cause deterioration of physical properties due to uncuring depending on the working conditions. Although there is a disadvantage in that it takes more than 24 hours, the polyurea paint of the present invention has a hardening time of less than a few minutes, thereby improving construction efficiency by shortening the air and reducing labor costs, and also excellent mechanical properties and wear resistance than conventional paints.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not necessarily limited to the following Examples.

Example

Example 1

First, to prepare a curing agent, 46.5% by weight of isophorone diisocyanate (IPDI) and 53.5% by weight of polyoxypropylene diamine D-2000 were mixed and maintained at a reaction temperature of 100 to 120 ° C for 5 hours to prepare a curing agent having an NCO content of 15.3% by weight. Prepared.

Next, a resin mixture is prepared. 35 weight% of amine terminal epoxy prepolymer resins produced by maintaining a bifunctional epoxy resin with an amine having a molecular weight of 50 to 250 and two functional groups at 60 to 80 ° C. for 2 hours were used. 35 weight% of a polyoxypropylene mixture containing 29 weight% polyoxypropylene diamine D-2000 and 6 weight% polyoxypropylene triamine T-5000 was obtained. In addition, 20 wt% of a crosslinking agent including 17 wt% of diethyltoluenediamine and 3 wt% of polyetheramine D-400 was prepared and mixed. 5% by weight of pigment TiO _2, 3% by weight of UV Absorber (Tinuvin 571 from Ciba) and 2% by weight of adhesion promoter (silane compound from Dow Corning) were used.

Example 2

First, in order to prepare a curing agent, 50.5% by weight of methylene diphenol diisocyanate (MDI) and 49.5% by weight of polypropylene glycol PP-4000 were mixed and maintained at a reaction temperature of 80 to 90 ° C. for 3 hours to prepare a curing agent having an NCO content of 15.4% by weight. Prepared.

Next, a resin mixture is prepared. 25 weight% of amine terminal epoxy prepolymer resins produced by maintaining a bifunctional epoxy resin with an amine having a molecular weight of 50 to 250 and two functional groups at 60 to 80 ° C. for 2 hours were used. 40 wt% of a polyoxypropylene mixture containing 33 wt% of polyoxypropylene diamine D-2000 and 7 wt% of polyoxypropylene triamine T-5000 was obtained. In addition, 25 wt% of a crosslinking agent including 22 wt% of diethyltoluenediamine and 3 wt% of polyetheramine D-400 was prepared and mixed. 5% by weight of pigment TiO _2, 3% by weight of UV Absorber (Tinuvin 571 from Ciba) and 2% by weight of adhesion promoter (silane compound from Dow Corning) were used.

Example 3

First, to prepare a curing agent, 52.9% by weight of methylene diphenol diisocyanate (MDI) and 47.1% by weight of polypropylene glycol PP-2000 and PP-3000 were added at a 1: 1 mixing ratio and maintained at a reaction temperature of 80 to 90 ° C for 3 hours. To prepare a curing agent having an NCO content of 15.4% by weight.

Next, a resin mixture is prepared. 38 weight% of amine terminal epoxy prepolymer resins produced by maintaining a bifunctional epoxy resin with an amine having a molecular weight of 50 to 250 and two functional groups at 60 to 80 ° C. for 2 hours were used. 30 weight% of a polyoxypropylene mixture containing 26 weight% polyoxypropylene diamine D-2000 and 4 weight% polyoxypropylene triamine T-5000 was obtained. In addition, 22% by weight of diethyltoluenediamine was prepared as a crosslinking agent and mixed. 5% by weight of pigment TiO _2, 3% by weight of an additive (Tinuvin 571 from UV Absorber Ciba) and 2% by weight of an adhesion enhancer (silane compound of Dow Corning) were added to enhance adhesion to the material.

Comparative Example 1

First, 46.5 wt% of isophorone diisocyanate (IPDI) and 53.5 wt% of polyoxypropylene diamine D-2000 were mixed and maintained at a reaction temperature of 100 to 120 ° C. for 5 hours to prepare a curing agent having an NCO content of 15.3 wt%.

10 weight% of the amine terminal epoxy prepolymer resin produced by carrying out the bifunctional epoxy resin and the amine which has a molecular weight of 50-250 and two functional groups at 60-80 degreeC for 2 hours was hold | maintained. 54 wt% of polyoxypropylene diamine D-2000 and 60 wt% of polyoxypropylene including 6 wt% of polyoxypropylene triamine T-5000 were mixed, and 10 wt% of diethyltoluene diamine and polyetheramine D-400 as crosslinking agents. 10 wt% was used. 5 wt% of pigment TiO ₂ was added thereto, and 3 wt% of UV Absorber (Tinuvin 571 from Ciba) and 2 wt% of adhesion promoter (silane compound of Dow Corning) were mixed as additives.

Comparative Example 2

First, 50.5% by weight of methylene diphenyl diisocyanate (MDI) and 49.5% by weight of Polypropylene Glycol PP-4000 were mixed and maintained at a reaction temperature of 80 to 90 ° C for 3 hours to prepare a curing agent having an NCO content of 15.4% by weight. .

62 weight% of the amine terminal epoxy prepolymer resin produced by carrying out the bifunctional epoxy resin and the amine which has a molecular weight of 50-250 and two functional groups at 60-80 degreeC for 2 hours was hold | maintained. 14% by weight of polyoxypropylene diamine D-2000, 8% by weight of diethyltoluene diamine and 6% by weight of polyetheramine D-400 as crosslinking agent, 5% by weight of pigment TiO ₂ , UV Absorber (Tinuvin 571 from Ciba) 3% by weight) and 2% by weight of an adhesion promoter (silane compound of Dow Corning).

Detailed contents of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1 below.

division
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hardener
Isocyanate 46.5 50.5 52.9 46.5 50.5 Polyol
(Polyamine) 53.5 49.5 47.1 53.5 49.5 Resin mixture



Amine-terminated epoxy prepolymer 35 25 38 10 62 Polyoxypropylene amine 35 40 30 60 14 Crosslinking agent 20 25 22 20 14 Pigment 5 5 5 5 5 additive 5 5 5 5 5

Physical property test of paint composition

In order to measure the physical properties of the compositions of the polyurea paints prepared in Examples 1 to 3 and Comparative Examples 1 and 2, the physical properties of the polyurea paints were easily sprayed under the following conditions and measured according to the ASTM test method.

<Spray coating condition>

□ Painting machine: Gusmer's exclusive coating machine for polyurea

□ Spray liquid temperature: 65 ℃

□ Pressure when spraying: 2000 psi

<Test method>

□ Tear Strength and Elongation

A 6 mm wide dumbbell-shaped specimen is prepared by the tensile property test method of plastic, and the tensile strength and elongation at break of the material are measured by applying an external force to the specimen produced in the tensile tester (ASTM D 638).

□ tear strength

Measured by Tear and T-Peel Test Method of Vulcanized Rubber and Thermoplastic Elastomer (ASTM D 624).

□ hardness

It is measured using a rubber hardness tester (ASKER), a hardness measuring device for rubber and plastic (ASTM D 2240).

□ Wear test

It is a test method that wears the wear ring which rotates freely on the sample after fixing the specimen to the rotating plate disc by pressing a certain load (ASTM D 4060).

<H-18: Type of wear ring, 1Kg: Weight of wear ring, 1000 times: Revolutions>

Experiment result and analysis

Table 2 summarizes the test results for hardness, tensile strength, tear strength, elongation, and wear resistance of the compositions of the polyurea paints prepared in Examples 1 to 3 and Comparative Examples 1 and 2.

Test Items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Test Methods Hardness
(Scale) A 92 95 93 82 99 ASTM D 2240 D 40 48 45 33 67 The tensile strength
(Mpa) 20.9 24.9 23.0 16.4 25.2 ASTM D 638 Phosphorus strength
(N / cm) 798 1151 849 628 790 ASTM D 624 Elongation
(%) 480 352 348 388 48 ASTM D 638 Wear resistance? Taber
(mg loss) 67.2 99.0 83.9 142.3 350 ASTM D 4060
(H-18, 1Kg,
1000 times)

Referring to Table 2, Examples 1 to 3 show better results than Comparative Example 1 in terms of hardness, tensile strength, and tear strength, and abrasion resistance is shown to be superior to Comparative Examples 1 and 2. Examples 1 to 3 show excellent results compared to Comparative Example 2 in terms of elongation and wear resistance.

Therefore, it can be confirmed from the above test results that the coating composition according to the present invention is a polyurethane coating having excellent toughness in various physical properties including hardness and tensile strength.

Claims (5)

A resin mixture consisting of 20 to 40% by weight epoxy prepolymer, 20 to 40% by weight polyoxypropylene amine, 15 to 25% by weight crosslinking agent, 2 to 8% by weight pigment, 2 to 8% by weight additive,
A two-component polyurea coating composition comprising a curing agent obtained by mixing 70 to 130 parts by weight of polypropylene glycol or polyoxypropylene diamine with 100 parts by weight of isophorone diisocyanate (IPDI) or methylene diphenol diisocyanate (MDI),
The volume ratio of the resin mixture and the curing agent is 1: 1,
The polyoxypropylene amine is a polyurea coating composition, characterized in that formed by mixing 16 to 33% by weight of polyoxypropylene diamine and 4 to 7% by weight of polyoxypropylene triamine.
The method of claim 1,
The epoxy prepolymer is a polyurea coating composition, characterized in that the terminal group is formed of an amine group, a bifunctional epoxy resin and a molecular weight of 50 to 250 and an amine having two functional groups at 60 to 80 ℃.
The method of claim 1,
The polyoxypropylene amine is a polyurea coating composition, characterized in that the weight average molecular weight of 1,000 to 6,000.
The method of claim 1,
The crosslinking agent is a polyurea coating composition, characterized in that using at least one selected from diethyltoluenediamine and polyetheramine.
Removing foreign matter on the concrete or steel surface;
Applying a primer; And
A construction method using a polyurea paint composition comprising the steps of mixing and spraying a resin mixture and a curing agent in the composition according to claim 1,
The mixing method using a polyurea paint composition, characterized in that the liquid temperature at 50 to 80 ℃, spray injector pressure 1500 to 2500 psi.