KR101680539B1

KR101680539B1 - Low Scattering Polyurea-Polyurethan Composition For Underground Conduit Rehabilitation And Constructing Method Using The Same

Info

Publication number: KR101680539B1
Application number: KR1020160021832A
Authority: KR
Inventors: 임세준; 문병하
Original assignee: 삼화페인트공업주식회사
Priority date: 2016-02-24
Filing date: 2016-02-24
Publication date: 2016-12-12

Abstract

The present invention relates to a low scattering polyurea-polyurethane composition for rehabilitation of an underground conduit and a construction method, more specifically, to a low scattering polyurea-polyurethane composition which can be applied to a trenchless rehabilitation method for repairing a conduit without ground demolition, especially is optimized for a closed underground conduit environment, thereby minimizing dust scattering.

Description

TECHNICAL FIELD The present invention relates to a low-acid polyurea-polyurethane composition for underground pipe rehabilitation, and a low-acid polyurea-

The present invention relates to a low-acid polyurea-polyurethane composition for regenerating underground pipes and a method of construction. More specifically, the present invention can be applied to a non-excavated rehabilitation method for repairing a pipeline without dismantling the ground, and more particularly, to a low-scattering polyurea-polyurethane composition capable of minimizing scattered dust optimized for a closed underground pipe environment It is about.

In order to repair the pipeline buried in the basement, a new pipe replacement method is used in which the ground is excavated and replaced with a new pipe. However, there are various problems caused by ground excavation. Therefore, in order to overcome such problems as causing traffic congestion, unreachable construction methods for repairing the pipeline without dismantling the ground are attracting attention. In the above-mentioned unguarded method, there is a PE lining reversing method in which a polyethylene liner of a water supply pipe is inverted after being subjected to a pretreatment process for removing corrosive substances and scales in an aged pipe, and the polyethylene liner is expanded and adhered to a hot steam and compressed air. A method in which a lining coating is applied using an inorganic material, an epoxy, and a polyurethane-polyurea is used in the pipe.

The cement-mortar lining, which has been applied to the existing old-age pipe rehabilitation coating material described in Related Technology 1 (Korean Patent Publication No. 1996-0004271), has been widely used for over 70 years in North America.

According to the related art 2 (Korean Unexamined Patent Application Publication No. 2005-0118430), the amine-epoxy type system has good chemical resistance and good characteristics, and it is possible to prevent the occurrence of defects caused by the manual work of the constructor, A method is known that can eliminate factors.

According to the related art 3 (Korean Patent Laid-Open Publication No. 2013-0028708), the polyurea product is excellent in abrasion resistance performance and elasticity, and also suppresses scattering of resin. Moreover, the spray gun, spraying apparatus, It is known to provide a construction method.

However, the related art 1 has a drawback that the softening of the steel pipe can be accelerated by deterioration of mortar lining due to softening, corrosion, water quality, and fatigue phenomenon at a high flow rate. In the related art 2, there is a restriction due to inferior bendability and abrasion resistance, a slow curing rate at room temperature, and a delay in curing at low temperature. Above all, it contains bisphenol, which affects the human body. In the related art 3, the airtightness (adherence performance) of the substrate is lowered due to the rapid curing speed, and when the coating film is broken, the spreading speed of the gelling agent is very fast. Above all, arsenic dust is inevitably generated at high temperature and high pressure, which is disadvantageous in terms of worker safety when working underground pipelines, and the scattered dust generated in the closed field condition remains on the surface of the coating, There is a disadvantage that the coating surface is implemented and the flow velocity coefficient is adversely affected as a result.

The object of the present invention to solve the above problems is to provide a polyurethane resin composition which is excellent in water resistance, corrosion resistance, flexural resistance, abrasion resistance, durability and adhesion, has both advantages of polyurethane and polyurea, And a polyurethane-polyurea coating for internal coating in accordance with the present invention.

Another object of the present invention is to provide a polyurethane-polyurea coating material for interior coating, which can realize a beautiful surface, and can realize a beautiful surface because the scattered dust generated during piping maintenance work is much smaller than general polyurea, And a method for producing the same.

It is still another object of the present invention to provide a coating film on the inner surface of a conduit buried underground using the above-mentioned polyurea-polyurethane paint for intra-conduit coating, thereby contributing to the extension of the life of the old conduit, It has its purpose.

The present invention relates to an oil-modified polyol, a polyamine compound, a polyether polyol, a first filler, a first moisture absorber, and a pigment; A curing agent part containing a urethane prepolymer, an isocyanate monomer, a second filler, a second moisture absorber, and a foaming agent; Wherein the mixing ratio of the main portion and the curing agent is 1: 0.9 to 1: 1.1 in volume ratio, and more particularly, to a low-acid polyurea-polyurethane composition for regenerating the underground pipe.

Another embodiment of the present invention relates to a low-acid polyurea-polyurethane composition for regenerating a subterranean conduit, wherein the oil-modified polyol is 40 to 60 wt% and the polyether polyol is 10 to 30 wt%.

In another embodiment of the present invention, the oil-modified polyol is obtained by reacting a natural oil obtained from a castor oil or a sunflower seed oil with an alcohol compound, or by subjecting it to epoxidation, ring opening reaction, ester exchange reaction, ethoxylation or propoxylation Polyurea-polyurethane composition for regenerating underground pipes.

In another embodiment of the present invention, the urethane prepolymer may be obtained through the reaction of an aromatic diisocyanate, a polyoxyalkylene glycol and 1,3-butylene glycol, and has an isocyanate group at the terminal. Regenerated low-acid polyurea-polyurethane composition.

In another embodiment of the present invention, the urethane polymer is obtained by reacting 40 to 50 parts by weight of methylene diphenyl diisocyanate, 5 to 10 parts by weight of polyoxyalkylene glycol, and 0.1 to 5 parts by weight of 1,3-butylene glycol To a low-acid polyurea-polyurethane composition for regenerating an underground pipe.

In another embodiment of the present invention, the isocyanate monomer is an aliphatic diisocyanate or an aromatic isocyanate, and more particularly, to a low-acid polyurea-polyurethane composition for underground pipe regeneration.

In another embodiment of the present invention, the aliphatic diisocyanate is 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and the aromatic isocyanate methylenediphenyl diisocyanate. The low-acid polyurea-poly Urethane compositions.

Another embodiment of the present invention relates to a method of applying a coating film using a low-acid polyurea-polyurethane composition for underground pipe regeneration at a low temperature of 40 to 50 DEG C and a low pressure of 100 to 300 psi.

Another embodiment of the present invention is a method of manufacturing a semiconductor device, comprising: partially cutting an old channel; Removing the rust generated in the old duct by a scraper or the like; Performing water spraying at a high pressure and a high speed; Removing the water using a contact type sponge or a non-contact type nitrogen spraying method; Mixing the low-acid polyurea-polyurethane composition for regenerating the underground pipe with a screw mixer using a static mixer; And spraying the mixture at a low temperature and a low pressure on the inner surface of the pipe by a moving injection method.

The low-boiling polyurea-polyurethane product according to the present invention has an advantage that it has a high physical stiffness higher than that of polyurea, an initial curability is slow and an excellent surface, and an excellent airtightness with a substrate, If the paint film breaks down, the spreading of the film is slow. Above all, since it is painted at low temperature and low pressure, it is suitable for sealing environment, especially underground pipe rehabilitation, because scattering dust is much smaller.

Hereinafter, preferred embodiments of the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments described herein are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be substituted for them at the time of application of the present invention.

Hereinafter, the present invention will be described in more detail.

As described above, in order to attain the object, in order to develop a normal polyurea-polyurethane reaction under conditions having a low-temperature and low-pressure static mixer of various diameters (a device that is mounted on a device and mixes the liquid) A paint composition comprising a main part containing natural oil, more specifically 40 to 60% by weight of an oil-modified polyol and 5 to 25% by weight of polyamine and other additives, and a hardener part containing isocyanate mixed with the main part in a ratio of 1: 1 .

The polyurea-polyurethane coatings usable at low temperature and low pressure according to the present invention include a main part and a hardener part. Here, the polyurea-polyurethane coating material according to the present invention can be used at a low temperature of 40 to 50 DEG C and a low pressure of 100 to 300 psi.

In general polyurea paints, it is difficult to expect normal physical properties because mixing efficiency of the base and curing agent is less than 40 ℃ and 100 psi. If it exceeds 50 ℃ and 300 psi, scattered dust is generated and does not fit the purpose of this product .

The above conditions can be achieved by the following physical conditions.

An oil-modified polyol, a polyether polyol, a filler, and a moisture absorbent; A urethane prepolymer, an isocyanate monomer, a filler, a moisture absorbent and an additive.

(Subject section)

The oil-modified polyol is preferably 40 to 60% by weight. More preferably 45 to 55% by weight. If the amount is less than 40% by weight, the curing rate is accelerated to cause a problem of clogging inside the mixer, and if it is more than 60% by weight, the physical properties of the coating film (coating film hardness) become poor.

The oil-modified polyol can be obtained by reacting a natural oil obtained from a flower or seed, such as castor oil or sunflower oil, with an alcohol compound. Alternatively, it is preferable to minimize the influence on the human body by using a plant raw material obtained by modifying by epoxidation, ring-opening reaction, transesterification, ethoxylation, propoxylation and the like.

Here, when castor oil is used, it is most preferable because it has high viscosity and specific gravity as a fat oil and also has high fluidity at low temperatures.

The polyether polyol is preferably 10 to 30% by weight. More preferably from 15 to 25% by weight. If the amount is less than 10% by weight, the curing rate is accelerated, which causes a problem of clogging in the mixer. If the amount is more than 25% by weight, physical properties (film hardness)

As the polyamine compound, it is preferable that the amine group is located at the secondary carbon atom at the end of the aliphatic polyether chain. As an example of the polyamine compound, a compound represented by the following formula (1) can be used.

(Formula 1)

(N in the formula (1) represents a range of 30 to 40)

The use of 5 to 25% by mass of the polyamine compound represented by the above formula (1) has the advantage that the viscosity can be lowered due to low vapor pressure.

In addition, 1,4-butanediol may preferably be contained in an amount of 2 to 7% by mass as the diol compound.

As the other first additives, a first filler, a first moisture absorber, a pigment, a first thickener, and the like may be further mixed and used.

As the first filler, calcium carbonate, barium sulfate, talc, silicon oxide, magnesium oxide, calcium oxide and the like may be used, and these may be used alone or in combination and 15 to 25 mass%.

As the first moisture absorbent, calcium oxide, zeolite, dolomite and the like may be used, and these may be used individually or in a mixture of 5 to 15 mass%.

As the pigment, titanium dioxide, carbon black, iron oxide, or the like can be used, and these pigments can be used individually or in combination in an amount of 0.1 to 5 mass%.

(Hardener part)

Urethane prepolymer, which can be obtained through the reaction of an aromatic diisocyanate, a polyoxyalkylene glycol and 1,3-butylene glycol, and preferably has an isocyanate group at the terminal.

The urethane polymer is preferably obtained by reacting 40 to 50 parts by weight of methylene diphenyl diisocyanate, 5 to 10 parts by weight of polyoxyalkylene glycol, and 0.1 to 5 parts by weight of 1,3-butylene glycol.

The reaction for obtaining the urethane prepolymer is preferably carried out at 40 ° C to 60 ° C, and the residual isocyanate of the urethane prepolymer is preferably 15 to 30%. The weight average molecular weight of the urethane prepolymer is preferably from about 2,000 to about 4,000.

The isocyanate monomer is preferably an aliphatic diisocyanate. The aliphatic diisocyanate may be 1,6-hexamethylene diisocyanate or isophorone diisocyanate.

When an aromatic isocyanate is used, it may include, for example, methylene diphenyl isocyanate and the like.

The urethane prepolymer is preferably 40 to 50% by weight. If the amount is less than 40% by weight, the curing rate is accelerated, thereby causing a problem of clogging in the mixer, which is undesirable. If it exceeds 50% by weight, physical properties of the coating film (coating film hardness) are not preferable.

The content of the isocyanate monomer is preferably 20 to 40% by weight. If it is less than 20% by weight, physical properties of the coating film (coating film hardness) are lowered, and if it is more than 40% by weight, the coating film crosslinking density becomes high.

As an additive, it may include a second filler, may include a second moisture absorbent, and may include 0.1 to 1 wt% of a dispersant.

The compound represented by the general formula (2) can further contain an antifoaming agent capable of reacting with the isocyanate of the curing agent part to inhibit the generation of carbon dioxide and has an effect of increasing the hardness. In order to react with the isocyanate of the curing agent part, it is preferable to use 0.5 to 3 mass%.

(2)

(Wherein R1, R2, and R3 each independently represent an alkyl group having 1 to 5 carbon atoms)

As the other second additives, a second filler, a second moisture absorbent, a second thickening agent, a dispersant, and the like may be further mixed and used.

As the second filler, calcium carbonate, barium sulfate, talc, silicon oxide, magnesium oxide, calcium oxide and the like may be used. These may be used alone or in combination, and 15 to 25 mass% may be used.

As the second moisture absorbent, calcium oxide, zeolite, dolomite and the like may be used, and they may be used individually or in combination at 5 to 15 mass%.

The dispersant may be used in an amount of 0.1 to 3 mass%.

(Mixing of the main part and the hardener part)

The mixing ratio of the main portion and the curing agent is preferably 1: 0.9 to 1: 1.1 in terms of volume ratio, and more preferably, the mixing ratio of the main portion and the curing agent is 1: 1 by volume.

The molar ratio of the hydroxyl group of the subject polyol to the isocyanate group of the curing agent part is preferably from 1: 1.1 to 1: 1.2. If the ratio is less than 1.1, the curing rate is accelerated, thereby causing a problem of clogging in the mixer, which is undesirable. When the ratio is more than 1: 1.2, the physical properties of the coating film (coating film hardness) deteriorate. Therefore, in order to use the low-acid polyurea-polyurethane composition for regenerating the underground pipe at a low temperature of 40 to 50 DEG C and a low pressure of 100 to 300 psi, it is necessary to satisfy the above condition.

(Construction method of coating film)

Partially cutting the old channel; Removing the rust generated in the old duct by a scraper or the like; Performing water spraying at a high pressure and a high speed; Removing the water using a contact type sponge or a non-contact type nitrogen spraying method; Mixing the low-acid polyurea-polyurethane composition for regenerating the underground pipe with a screw mixer using a static mixer; And spraying the mixture on the inner surface of the pipe by a moving spraying method.

It is possible to increase the convenience of construction at the time of scraping by partially cutting the scraper to cut the scraper of the old duct to construct a coating film. After removing the rust, the step of spraying at a high pressure and at a high speed can easily purify the surface for coating the coating film by adjusting the flow rate from 400 Bar to 500 Bar and 10 Litter / min to 20 Litter / min. Drying after natural spraying can take a long time, so it is possible to remove water using a sponge. Also, the nitrogen injection method is useful when it is not easy to remove water from the outside in a contact manner. In order to use the low-acid polyurea-polyurethane composition for regenerating the underground pipe at a low temperature of 40 to 50 DEG C and a low pressure of 100 to 300 psi, the dispenser of the static mixer is preferably 150 mm to 180 mm in length and 4 mm to 5 mm in inner diameter. The diameter of the skew flow provided inside the dispenser is preferably 0.05 mm to 0.1 mm smaller than the diameter of the dispenser.

By satisfying the length and the inner diameter of the dispenser of the static mixer and the diameter of the skew of the inside of the dispenser, the low-acid polyurea-polyurethane composition for regenerating the underground pipe of the present invention can be manufactured at low temperature, It is preferable to use at a low pressure of 300 psi.

(Example)

Example 1 and Comparative Examples 2 to 4 were prepared according to the composition of Table 1 below. In the following Table 1, GP-280 is a polyether polyol, HS 3G-100M is an oil-modified polyol, EFKA 5065 is a dispersant, Sylosiv A4 POWDER is a hygroscopic agent, OMYACARB 100 is calcium carbonate, BAYFERROX 303T is a black pigment, Represents a thickener.

Topic section Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 GP-280
(Korea, KPX) 13 53 25 15 1,4 Buthane diol
(BASF, Germany) 5 5 10 - HS 3G-100M
(Japan, Hokoku corporation) 45.0 - 20 30 The polyamine compound represented by the formula (1)
(n is about 33) 9.5 9.5 9.5 9.5 EFKA-5065
(Germany, EFKA) 0.5 0.5 0.5 0.5 OMYACARB 100
(Korea, OMYA) 20 20 33 43 Sylosiv A4
(Grace, Korea) 10 10 - - KONASIL K-200
(Korea, OCI) One One One One BAYFERROX 303T
(Korea, LANXESS KOREA) One One One One

In Table 1, the unit represents a mass part.

Example 1 and Comparative Examples 2 to 4 of a curing agent part were prepared according to the composition shown in Table 2 below. In the following [Table 2], the isocyanate monomer is MDI and the KONASIL K-200 is a thickener.

Hardener part Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Urethane prepolymer 40 57.5 67.5 - Isocyanate monomer 27.5 10 - 67.5 EFKA-5065
(Germany, EFKA) 0.5 0.5 0.5 0.5 OMYACARB 100
(Korea, OMYA) 20 20 20 20 Sylosiv A4
(Grace, Korea) 10 10 10 10 KONASIL K-200
(Korea, Dongyang Steel Chemical) One One One One (R1 is an ethyl group, R2 and R3 are butyl groups) represented by the general formula (2) One One One One

In Table 2, the unit represents a mass part.

In the above Examples and Comparative Examples, the mixing ratio of the base and the curing agent was 1: 1.

The tensile strength, elongation, adhesive strength, flexural resistance and test of the coating film samples obtained from the compositions of Example 1 and Comparative Examples 2 to 4 were tested and the results are shown in Table 3 below. The tensile strength and elongation of each coating film were measured by the ASTM test method at room temperature for about 7 days, and then the tensile strength and elongation were measured. The adhesion strength was measured by ASTM D-4541, flexural strength ASTM D-522 .

Referring to [Table 3], it was found that cracks were generated in flexing resistance results by using only isocyanate monomer of Comparative Example 4, and Comparative Examples 2 and 3 had insufficient tensile strength or hardness.

Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Remarks The tensile strength ○ △ × ○ ASTM D638 Phosphorus strength ○ ○ ○ ○ ASTM D624 Elongation rate ○ ○ ○ ○ ASTM D638 Hardness ○ △ × △ ASTM D2240 Flexibility ○ ○ ○ × ASTM D522

* Tensile strength test

○: 30 N / ㎟ or more

?: 25 N / mm 2 to 30 N / mm 2

×: less than 25 N / mm 2

* Tear strength test

○ 90 N / ㎟ or more

× 90 N / ㎟ or less

* Extension rate test

○ 10% or more

× 10% or less

* Hardness test (SHORE D)

○: 80 or more

?: 75 or more and less than 80

×: less than 75

* Flexibility

○: 6 mm or more

×: less than 6 mm

This product is suitable for rehabilitation of irrigation pipelines, which is more economical than the excavation method in which the ground is dismantled and replaced with a new pipe. By minimizing scattered dust, it is advantageous in terms of worker safety and minimizes traffic congestion during construction. So that economic value can be secured. In addition, the physical properties such as tensile strength, film hardness, water resistance, corrosion resistance, and adhesive force of the coating film are superior to those of conventional polyurea, so that the waterproof performance of the pipe can be maintained for a long time.

Claims

An oil-modified polyol, a polyamine compound, a polyether polyol, a first filler, a first moisture absorbent, and a pigment;
A curing agent part containing a urethane prepolymer, an isocyanate monomer, a second filler, a second moisture absorbent, and an antifoaming agent;
/ RTI >
Wherein the oil-modified polyol is 40 to 60 wt%, the polyether polyol is 10 to 30 wt%, the polyamine is 5 to 25 wt%
The polyamine compound is a compound represented by the following formula (1)
(Formula 1)

(N in the formula (1) represents a range of 30 to 40)
The oil-modified polyol is obtained by reacting castor oil or a natural oil obtained from a sunflower seed oil with an alcohol compound, or by modifying by epoxidation, ring-opening reaction, ester exchange reaction, ethoxylation, or propoxylation,
Wherein the urethane prepolymer is 40 to 50 wt%, the isocyanate monomer is 20 to 40 wt%, the foam inhibitor is 0.5 to 3 wt%
The antifoaming agent is a compound represented by the general formula (2)
(2)

(Wherein R1, R2, and R3 each independently represent an alkyl group having 1 to 5 carbon atoms)
The isocyanate monomer is an aliphatic diisocyanate or an aromatic isocyanate,
Wherein the mixing ratio of the main portion to the curing agent is 1: 0.9 to 1: 1.1 in volume ratio.

delete

The method according to claim 1,
The urethane prepolymer may be obtained through the reaction of an aromatic diisocyanate, a polyoxyalkylene glycol, and 1,3-butylene glycol, and has an isocyanate group at the terminal. The low-acid polyurea- Polyurethane composition.

5. The method of claim 4,
Wherein the urethane prepolymer is obtained by reacting 40 to 50 parts by weight of methylene diphenyl diisocyanate, 5 to 10 parts by weight of polyoxyalkylene glycol, and 0.1 to 5 parts by weight of 1,3-butylene glycol. A non-acidic polyurea-polyurethane composition.

delete

The method according to claim 1,
The aliphatic diisocyanate is 1,6-hexamethylene diisocyanate or isophorone diisocyanate,
Wherein the aromatic isocyanate is methylenediphenyl diisocyanate. &Lt; RTI ID = 0.0 > 21. < / RTI >

Characterized in that the low-acid polyurea-polyurethane composition for regenerating the underground pipe according to any one of claims 1, 4, 5 and 7 is used at a low temperature of 40 to 50 DEG C and a low pressure of 100 to 300 psi By weight.

Partially cutting the old channel;
Removing the rust generated in the old channel with a scraper;
Spraying at a high pressure of 400 Bar to 500 Bar and at a high rate of 10 Litter / minute to 20 Litter / minute;
Removing the water using a contact type sponge or a non-contact type nitrogen spraying method;
Mixing the low-acid polyurea-polyurethane composition for underground pipe regeneration according to any one of claims 1, 4, 5, and 7 with a screw mixer using a static mixer;
Spraying the mixture at low temperature of 40 to 50 DEG C and low pressure of 100 to 300 psi on the inner surface of the conduit by the moving injection method;
Wherein the coating layer is formed on the surface of the substrate.

10. The method of claim 9,
The dispenser of the static mixer has a length of 150 mm to 180 mm and an inner diameter of 4 mm to 5 mm,
Wherein the diameter of the skew flow provided inside the dispenser is 0.05 mm to 0.1 mm smaller than the diameter of the dispenser.