KR102110435B1 - Waterproofing polyurea resin paints composition for protective explosion and earthquake-proof having flame retardant and preparation method thereof - Google Patents

Abstract

The present invention relates to an explosion-proof and earthquake-proof waterproof polyurea resin coating composition having flame retardancy and a method for manufacturing the same.
Explosion-proof and earthquake-proof waterproof polyurea resin coating compositions having flame retardancy of the present invention include 40 to 75 wt% of polyetherdiamine, 10 to 25 wt% of diethyltoluenediamine, 0.1 to 5 wt% of modified aminosilicon, and 0.1 to UV stabilizer. Curing agent consisting of 5 wt%, 0.1 to 10 wt% of pigment, 8 to 20 wt% of flame retardant additive, and 35 to 47 wt% of isocyanate prepolymer, 35 to 45 wt% of polyol, and 8 to 20 wt% of flame retardant additive It is characterized by consisting of;
According to the present invention, it is possible to flexibly change the shock and pressure of a structure by easily constructing it in a building, and not only protect the building due to its explosion-proof performance and shock-absorbing ability, but also exert its flame-retardant performance to its maximum, to provide explosion-proof and earthquake-resistant materials with flame-retardant properties that minimize human damage A waterproof polyurea resin coating composition and a method of manufacturing the same are provided.

Description

Waterproofing polyurea resin paints composition for protective explosion and earthquake-proof having flame retardant and preparation method thereof

The present invention relates to a polyurea resin coating composition for explosion-proof and earthquake-proof waterproofing materials having flame retardancy and a method for manufacturing the same, and more particularly, excellent flame retardancy and tack free time, hardness, tensile strength, elongation, tear strength It has excellent physical properties and high energy absorption rate for external or internal shock waves and explosive loads, so it is possible to prevent the effects of pressure loads caused by explosions and earthquakes on concrete structures or cement brick structures. Polyurea resin coating composition for explosion-proof and earthquake-proof waterproof materials having flame-retardant properties to minimize the amount thereof and a method for manufacturing the same.

In general, explosive explosive explosive energy transfers at a rapid rate, which is transmitted at a supersonic speed through the surrounding air as a shock wave.

In recent years, many human casualties have occurred due to fires and destruction of building structures due to bombs, such as the North Korean shelling of Yeonpyeong Island on November 23, 2010, as well as military and economic losses due to the destruction of major national facilities. have.

Therefore, it is urgently necessary to take measures to protect these major facilities and human life, and in particular, to understand the explosion load applied to the structure basically to prevent building collapse and human damage due to recent earthquakes in Japan and Korea. Is required, and since such an explosive load is a load that acts on a concrete structure in a very fast time, it is necessary to evaluate the dynamic response in consideration of strain, speed, and local damage to the structure. It is an urgent need.

Several studies related to this have been conducted as follows. As related arts, disclosed patents No. 10-2013-0074699 (Composition of silicone polyurea resin for protective explosion-proof and construction method thereof) and Patent No. 10-0976831 (Water-soluble polyurea resin coating composition for protecting concrete structures and coating composition for this) Construction method).

However, the above known technologies have only a protective effect on the concrete structure, and although there is a phosphorus-based flame retardant applied, it has a function of self-extinguishing, but has poor heat resistance, so that the flame retardancy is insufficient, thereby minimizing human damage caused by explosion fires. There are some shortcomings.

The present invention not only protects a building due to its explosion-proof performance and shock-absorbing ability by flexibly changing the impact and pressure of a structure by easily constructing it in a building, it also exerts its flame-retardant performance to the maximum, thereby providing explosion-proof and seismic-resistant waterproof material poly that minimizes human damage. The purpose is to provide a urea resin coating composition and a method for manufacturing the same.

Explosion-proof and earthquake-proof waterproofing polyurea resin coating composition having flame retardancy of the present invention for achieving the above object, 40 to 75 wt% of polyetherdiamine, 10 to 25 wt% of diethyltoluenediamine, and 0.1 to 5 wt% of modified aminosilicone Wow, 0.1 to 5 wt% of UV stabilizer, 0.1 to 10 wt% of pigment, 8 to 20 wt% of flame retardant additive, and 35 to 47 wt% of isocyanate prepolymer, 35 to 45 wt% of polyol, and flame retardant additive 8 It is characterized by consisting of; curing agent portion consisting of ~20wt%.

The polyurea resin coating composition is characterized in that the main portion and the curing agent portion is composed of a weight ratio of 1 to 4: 1.

The flame retardant synthetic additive is characterized by comprising a phosphoric acid-based flame retardant and a phosphorus-based flame retardant.

The method for manufacturing the flame retardant waterproofing and waterproofing polyurea resin coating composition of the present invention has 35 to 66 wt% of polyetherdiamine having a weight average molecular weight of 2000, 10 to 25 wt% of diethyl toluenediamine, based on the total weight of the main part. 5~9wt% of polyetherdiamine having a weight average molecular weight of 5000 is first placed in a container, mixed for 5-10 minutes at 500~1500 rpm, and then modified amino silicone 0.1~5wt%, UV stabilizer 0.1~5wt%, pigment 0.1~ Adding 10 wt%, 8-20 wt% of a flame retardant synthetic additive, and mixing for 20-30 minutes at 1000-1500 rpm to prepare a main part; After adding the isocyanate prepolymer 35-47 wt% and the polyol 35-45 wt% based on the total weight of the curing agent part in the reactor where the stirring speed of 30-150 rpm is maintained, the temperature of the reactor is raised to 70-80° C., 70 When the temperature is reached to ~80 ℃ to polymerize by reacting for 3 to 4 hours, and then lowering it to 50 ~ 60 ℃ 8 to 20 wt% of a flame retardant synthetic additive and mixed to prepare a curing agent portion, and the main part And mixing the curing agent portion in a weight ratio of 1 to 4: 1, wherein the equivalent ratio of the main portion and the curing agent portion is mixed within a range of 1.05 to 1.15 to prepare a polyurea resin coating composition.

The flame retardant synthetic additive of the main part is charged with a phosphate-based flame retardant butylphenyl diphenyl phosphate and a phosphate-based flame retardant phenyl dichlorophosphate in a container for 1 to 2 hours at 50 to 60°C. After the primary reaction, triphenyl phosphate, a phosphorus-based flame retardant, is added thereto, and is produced by secondary reaction at 50-60° C. for 1-2 hours.

The flame retardant synthetic additive of the curing agent is phosphate-based flame retardant butylphenyl diphenyl phosphate (butylphenyl diphenyl phosphate) in a primary reaction for 50 to 60 ℃ 1 to 2 hours, and then again the phosphoric acid flame retardant phosphoric acid flame retardant Phenyl dichlorophosphate was added and reacted for 2 hours at 50~60℃ for 1~2 hours, then phosphorus-based flame retardant Triphenyl phosphate was added and for 3~1 hours at 50~60℃ It is characterized by producing by reacting.

The method of coating and constructing the polyurea resin coating composition of the present invention is characterized by spraying the polyurea resin coating composition on the surface of a concrete structure or cement brick structure with a high-temperature, high-pressure spraying device.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems that are not mentioned can be clearly understood by a person having ordinary knowledge in the technical field to which the present invention belongs from the following description. There will be.

According to the present invention, a polyurea resin coating composition that is resistant to flame retardant performance and earthquake and explosion-proof resistance is provided, which has excellent physical properties and flame retardant performance of tack free time, hardness, tensile strength, elongation, and tear strength. As it appears, it can absorb and apply strong energy, prevent fire occurrence, prevent collapse of buildings, etc., and can be applied to the entire infrastructure of industries requiring construction wall seismic design, facility protection, and rapid construction as a super-curable polyurea resin coating composition. At the same time, construction is possible regardless of temperature changes.

1 is a view showing the structural formulas of polyetherdiamine and diethyltoluenediamine according to an embodiment.
2 is a view showing the structural formula of a phosphoric acid-based flame retardant and a phosphorus-based flame retardant constituting a flame retardant synthetic additive according to an embodiment.
3 is a view showing the explosion-proof performance after the flame-retardant and anti-seismic waterproofing polyurea resin coating composition having flame retardancy of the present invention.

Hereinafter, the present invention will be described in detail, and detailed descriptions of well-known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted.

The explosion-proof and earthquake-proof waterproof polyurea resin coating composition having the flame retardancy of the present invention is divided into two parts, the main part and the curing agent part, wherein the main part is polyetherdiamine, diethyltoluenediamine, modified amino silicone, ultraviolet stabilizer, pigment, flame retardant It is characterized by being made of a synthetic additive, and the curing agent is characterized by being composed of an isocyanate prepolymer, a polyol, and a flame retardant synthetic additive.

The polyurea resin coating composition of the present invention has excellent mechanical and chemical properties and can form a seamless continuous coating film and is an excellent elastic polymer composite material that can withstand a large impact from an explosion, and can suppress fire occurrence. It has the advantages of flame retardant performance and various color expressions, and can be easily applied to complex areas.

In addition, the polyurea resin coating composition of the present invention has a fast curing property compared to the conventional method or the floor coating system, so it can achieve the performance of the work, and it is possible to secure a predetermined film thickness continuously without flowing even in the vertical plane, and recently It is effective in immersion, drought, and earthquake caused by climate change and can be used for facility protection and seismic design to respond quickly when designing facilities.

In addition, the polyurea resin coating composition of the present invention has excellent elasticity due to resin characteristics, excellent mechanical strength such as tensile strength and elongation, and particularly excellent elongation, so it has excellent crack followability for the behavior of the lower limb and excellent chemical resistance. Since it does not contain non-reactive substances such as catalysts and plasticizers, it is not harmful to the human body after construction, so it can be used as a coating material for water purification plants and drinking water storage tanks.

Hereinafter, as one embodiment of the polyurea resin coating composition of the present invention, the components that may be included in the main part and the curing agent part and a method for manufacturing the same are as follows.

(Subject)

1.polyether diamine

Polyetherdiamine is a raw material that affects basic resin properties, and preferably has a weight average molecular weight of 1,000 to 5,000. In other words, when the weight average molecular weight of the polyetherdiamine is less than 1,000, physical properties such as elongation and tensile strength may be deteriorated. When the weight average molecular weight exceeds 5,000, the above physical properties are improved. A problem occurs that the tensile strength is lowered.

In addition, the content of the polyetherdiamine is preferably added at 40 to 75 wt% based on the main part weight. This may cause physical properties such as tensile strength and elongation to deteriorate when the content of the polyetherdiamine is less than 40 wt%, and when it exceeds 75 wt%, unreacted polyether by excessive mixing of polyetherdiamine Diamine may remain and the polyurea synthesis yield may decrease.

As an example of the polyetherdiamine used in the present invention, as shown in FIG. 1A, BASF Corporation D-2000 with a weight average molecular weight of 2000, D-2000 Corporation by Huntsman, and BASF Corporation with a weight average molecular weight of 5000 T-5000 It is preferred to use Huntsman's T-5000, and more preferably, a polyetherdiamine having a weight average molecular weight of 2000 and a polyetherdiamine having a weight average molecular weight of 5000 are mixed and used in a weight ratio of 8 to 10:1.

2. Di-ethyltoluene diamine

The curing rate of the polyurea resin coating composition of the present invention is usually adjusted by using di-ethyltoluene diamine.

In other words, di-ethyltoluene diamine is used as a chain extender and contributes to controlling the gel time of the polyurea paint. Adjusting the curing rate, the reaction rate becomes faster as the amount of wt% increases, and the reaction rate becomes slower when the amount of wt% decreases. When the tack free time is slowed down to 30 seconds or more, a problem occurs in that when the vertical surface or ceiling is sprayed, it is lumped into a liquid state. Specifically, the primary amine can shorten the gelation time of the polyurea paint, and the secondary amine can extend the gelation time of the polyurea paint.

Thus, for example, diethyl toluenediamine used in the present invention can be used as a diamine toluenediamine as a primary amine in order to shorten the gelation time of the paint, and more preferably, as shown in FIG. 1B. , It is preferable to use the diethyltoluenediamine (DETDA) of Albermal, the primary amine having a weight average molecular weight of 178.3.

The amount of the diethyl toluene diamine added is preferably 10 to 25 wt% based on the main part weight. It is difficult to expect improvement of mechanical properties because the effect of the crosslinking agent is insignificant when the diethyltoluenediamine is added at less than 10 wt%, and when it exceeds 25 wt%, the curing rate is generated too quickly and the appearance is reduced. The problem is that the spray jet nozzle is clogged and easily breaks even under weak impact.

3. Modified amino silicone

Modified aminosilicon is used to act as a shock absorber for explosion-proof performance, and the modified aminosilicone has a structure in which the structure of -Si-O-Si- forms a central skeleton, and various organic groups are bonded thereto. In the modified aminosilicon according to the present invention, the organic group may be at least one selected from the group consisting of an epoxy group, an alkyd group, and a urethane group. More preferably, the organic group is an epoxy group. Such modified aminosilicon can be prepared by copolymerizing silicone and epoxy resin, alkyd resin, or urethane resin.

The amount of the modified amino silicone is preferably added in an amount of 0.1 to 5 wt% based on the main part weight. This is because when the modified amino silicone is added in an amount of less than 0.1 wt%, the elastic effect of absorbing the impact is weak, and when it exceeds 5 wt%, the curing rate occurs too quickly, and rather, it easily breaks even with a weak impact.

4. UV stabilizer

The ultraviolet stabilizer is for preventing yellowing caused by ultraviolet rays, and its addition amount is preferably added in an amount of 0.1 to 5 wt% based on the weight of the main part. That is, when the addition amount of the UV stabilizer is less than 0.1 wt%, the effect of preventing yellowing caused by ultraviolet light is lowered, and when it exceeds 5 wt%, the effect of preventing yellowing caused by ultraviolet light is no longer improved, but rather There is a concern that other physical properties of the coating composition may be deteriorated.

5. Pigment

The pigment is for imparting the color of the polyurea resin coating composition, and its addition amount is preferably added in an amount of 0.1 to 10 wt% based on the weight of the main part, but is not necessarily limited to the above range according to the needs of the consumer or the needs of the manufacturer. No, it can be adjusted accordingly.

6. Flame retardant additive

The flame retardant synthetic additive is a material that is added to be resistant to flame retardant performance and earthquake and explosion proof, and provides the self-extinguishing function of the polyurea resin coating composition of the present invention to prevent the transition to flame, which is a disadvantage of the organic paint. When it stops, the fire immediately disappears. At this time, the flame retardant synthetic additive is characterized in that it is composed of a phosphoric acid-based flame retardant and a phosphorus-based flame retardant, more preferably, a phosphoric acid-based flame retardant and a phosphorus-based flame retardant are preferably composed by mixing in a 1 to 2: 1 weight ratio.

Here, as the phosphoric acid-based flame retardant, butylphenyl diphenyl phosphate and phenyl dichloro phosphate are used alone or in combination of two or more, and phosphorus-based flame retardants include triphenyl phosphate, tris(2,3-dichloropropyl)phosphate, It is preferable to use any one of ammonium polyphosphate, phosphoric acid ester, tricresyl phosphate, and trichloroethyl phosphate, and the phosphoric acid and phosphorus systems are preferably mixed in a weight ratio of 1 to 2:1.

As a manufacturing method according to an embodiment of the flame retardant synthetic additive added to the main part, the reactor is first heated up to a temperature of 50 to 60° C. while maintaining stirring at a rate of 30 to 150 rpm in a reactor within 65% of humidity, and then FIG. 2A. Phosphate-based flame retardant butylphenyl diphenyl phosphate (butylphenyl diphenyl phosphate) and phosphoric acid-based flame retardant phenyl dichloro phosphate (Phenyl dichlorophosphate) in a 1:1 ratio, and the primary for 1 to 2 hours at 50 ~ 60 ℃ After reacting, the phosphorus-based flame retardant triphenyl phosphate shown in FIG. 2B is added in the same amount as the phosphate-based flame retardant butylphenyl diphenyl phosphate, and then at 50-60° C. for 1-2 hours. It is preferable to prepare a flame retardant synthetic additive by completing a condensation polymerization by secondary reaction.

The flame retardant synthetic additive prepared in this way is characterized in that it is added in an amount of 8 to 20 wt% based on the total weight of the main part, and when the added amount of the flame retardant synthetic additive exceeds 8 wt% outside the weight, the function of self-extinguishing is lost. In addition, physical properties such as tensile strength and elongation decrease, and when it exceeds 20 wt%, the increased flame retardant performance is not only difficult to expect, but rather, the carbonized layer becomes too hard, and the carbonized layer is easily broken, making it impossible to exhibit flame retardant performance. .

(Manufacturing method of subject)

As a manufacturing method according to one embodiment of the subject part of the present invention, a polyethyleneamine having a weight average molecular weight of 2000 is first introduced into a container at 35 to 66 wt% based on the weight of the subject part, and then diethyl toluenediamine After adding 10 to 25 wt% based on the weight of the part, again, 5 to 9 wt% of polyethyleneamine having a weight average molecular weight of 5000 is added based on the weight of the main part, and then mixed for 5 to 10 minutes at 500 to 1500 rpm. After adding modified amino silicone 0.1 to 5 wt%, UV stabilizer 0.1 to 5 wt%, pigment 0.1 to 10 wt%, and flame retardant synthetic additive 8 to 20 wt% based on the weight of the main part, 1000 to 1500 rpm It is characterized by producing by mixing for 20 to 30 minutes.

(Ministry of Curing)

In the polyurea resin coating composition according to an embodiment of the present invention, the curing agent portion includes the above-described flame retardant synthetic additive and the following components that can usually constitute the curing agent portion of the polyurea resin coating composition.

1. Isocyanate prepolymer

The curing agent isocyanate prepolymer is characterized by exhibiting mechanical strength, tensile strength, elasticity, impact resistance, and low temperature stability by forming a hard segment in the coating film, preferably methylene diphenyl diisocyanate (MDI) ; methylene diphenyl diisocyanate), which is classified as Polymeric MDI, Monomeric MDI, Modified MDI. In particular, it is preferable that the weight average molecular weight of the MDI is 250 to 300. In other words, when the weight-average molecular weight of MDI is less than 250, there is a fear that the above properties may be deteriorated, and when it exceeds 300, it is difficult to expect further physical properties to be increased.

As an example of the isocyanate used in the present invention, it is preferable to use those manufactured and sold, such as Kumho Mitsui, Dow Corning, Aekyung Chemical, BASF, etc. In particular, MDI is the weight average molecular weight of BASF Co., Ltd. It is preferable to mainly use Modified MDI of 250.3, Lupranate MI, and Monomeric MDI, Cosmonate LL having a weight average molecular weight of 285 by Kumho Mitsui Co., Ltd.

2. Polyether Polyol

Polyol is a material that is commonly used to improve the curing ability of the isocyanate prepolymer, and mainly uses polyols manufactured and sold by BASF, KPX, etc. for non-foaming, and more preferably, the weight average molecular weight. Polyether polyols of 2000-3000 are used. At this time, if the weight average molecular weight is less than 2000, the absorption rate of the cured coating film tends to increase, and if it exceeds 3000, the surface hardness decreases and the stain resistance also tends to deteriorate.

More preferably, KPX Co., Ltd. uses polyether polyol PP-2000, and has a weight average molecular weight of 2000. There are many other types of polyols, but in the present invention, there are several companies that mainly use PP-2000 polyols and manufacture and sell components such as PP-2000. The product ingredients are similar, but the product names are all sold differently.

(Manufacturing method of hardener part)

The manufacturing method of the curing agent portion of the present invention is prepared by dividing into three types of methods as follows according to the classified MDI of the isocyanate prepolymer.

1. Manufacturing method of hardener part according to Monomeric MDI

The composition of the curing agent part is composed of 35 to 47 wt% of Monomeric MDI, 35 to 45 wt% of polyol, and 8 to 20 wt% of a flame retardant additive based on the total weight of the curing agent.

The manufacturing method of the present curing agent part according to an embodiment, first, while maintaining the reactor within a humidity of 65% at a rate of 30 to 150 rpm, after introducing Monomeric MDI at 35 to 47 wt% based on the weight of the curing agent part, polyether After the polyol is added at 35 to 45 wt% based on the weight of the curing agent, the temperature of the reactor is raised to 70 to 80°C, and when the temperature reaches 70 to 80°C, it is reacted for 3 to 4 hours to polymerize, then 50 to It lowered again to 60°C.

Then, the flame retardant synthetic additive is mixed to include 8 to 20 wt% based on the total weight of the curing agent portion to prepare a curing agent portion used in the present invention.

At this time, the flame retardant synthetic additive is phosphate-based flame retardant butylphenyl diphenyl phosphate (butylphenyl diphenyl phosphate), phenyl dichloro phosphate (Phenyl dichlorophosphate) and phosphorus-based flame retardant triphenyl phosphate (Triphenyl phosphate) is preferably used. Specifically, the flame retardant synthetic additive is preferably prepared through a third condensation polymerization reaction, and first, phosphate-based flame retardant butylphenyl diphenyl phosphate (butylphenyl diphenyl phosphate) is 50 to 60 ℃ for 1 to 2 hours After the first reaction, phenyl dichlorophosphate (Phenyl dichlorophosphate), a phosphoric acid-based flame retardant, was added, followed by a second reaction at 50-60°C for 1 to 2 hours, and then triphenyl phosphate, a phosphorus-based flame retardant, ) And is produced by condensation polymerization by reacting for 3 hours at 50~60℃ for 1~2 hours, wherein the phosphoric acid-based flame retardant and phosphorus-based flame retardant are the most flame-retardant to achieve a weight ratio of 1-2:1. Excellent performance.

The flame retardant synthetic additive is characterized in that it is added in an amount of 8 to 20 wt% based on the total weight of the curing agent portion, when the amount of the flame retardant synthetic additive is less than 8 wt% outside the weight, the flame retardant performance is low, the desired effect It is difficult to obtain, and when the amount exceeds 20 wt%, the increased flame retardant performance is not only difficult to expect, but rather adversely affects the curing ability of the isocyanate prepolymer, so that there is a fear that the tack free time is lowered.

2. Manufacturing method of hardener part according to Modified MDI

Prepared in the same manner as in the manufacturing method of 1, but by applying a Modified MDI instead of Monomeric MDI to prepare a curing agent portion used in the present invention.

3. Manufacturing Method of Hardener Part by Mixing Monomeric MDI and Modified MDI

Prepared in the same manner as in the manufacturing method of 1, but instead of the Monomeric MDI, the MDI mixed with the Monomeric MDI and the Modified MDI in a 1:1 weight ratio is applied to prepare a curing agent portion used in the present invention.

At this time, the content (%) of the NCO group of the MDI classified in the curing agent part is preferably contained in 10 to 20% by weight based on the total weight of the MDI, which increases as the NCO group content (%) increases. The hardening rate appears quickly and the hardness is high, whereas, as the NCO group content (%) decreases, the hardness decreases.

The explosion-proof and earthquake-proof waterproof polyurea resin coating composition of the present invention constituted in this way is completed by mixing the main part and the curing agent part, and gelled according to the type and composition of materials in the main part and the material and composition of the material in the curing agent part. The time is changed and the performance is changed, so that the form of the polyurea resin paint is distinguished.

The polyurea resin coating composition for explosion-proof and earthquake-proof waterproof materials having flame retardancy of the present invention has excellent physical properties and can be used for various purposes such as concrete structures or cement brick structures, and is constructed using high-temperature, high-pressure spray equipment. do.

In general, polyurea is difficult to form a coating film of 500 µm or more in a single spray because pressure is generated at a pressure of 1500 psi or more and excessive discharge is generated. The curing time of polyurea is as fast as 10 seconds to 10 minutes, but when the curing speed is high, self-leveling of the coating surface is insufficient when spraying, and a rough surface is formed and dust is blown to emboss pattern on the coating surface.

According to another embodiment of the present invention, removing the foreign material on the surface of the concrete or cement brick structure; As a construction method using a polyurea resin coating composition comprising the step of spraying the coating composition after applying the normal primer after removing the foreign material, the liquid temperature during the mixing is set to 60 to 80°C, and the spray injector pressure is applied. It provides a construction method using the polyurea resin coating composition to 2000 to 3500 psi. At this time, when the pressure of the spray injector is lower than 2000 psi, there is a problem of deterioration in physical properties due to uncuring due to poor mixing, and when the pressure is higher than 3,500 psi, a smooth coating surface cannot be obtained.

On the other hand, it is preferable to maintain the temperature of the main part and the curing agent part at the time of the mixing collision at 60 to 80°C. When the temperature is 600° C. or less, a problem of mixing failure occurs, and when the temperature is 80° C. or more, the reaction speed of the main part and the curing agent part is increased, so that a smooth coating surface cannot be obtained, which is not preferable.

The polyurea resin coating composition of the present invention configured as described above is formed of a reactive thermosetting resin by mixing the main part and the curing agent part in a mixing ratio of 1 to 4: 1 by weight ratio, and the equivalent ratio of the main part and the curing agent part is within the range of 1.05 to 1.15. It is characterized by being adjusted in.

In other words, in the polyurea resin coating composition of the present invention, the mixing ratio of the main part and the curing agent part is formed in a weight ratio of 1 to 4:1, but physical properties vary greatly depending on the difference in mixing ratio. In other words, when the equivalent ratio of the main part and the curing agent part is either high or low, a problem occurs in that the coating properties of the polyurea are uncured or foamed. Accordingly, as a problem occurs in polyurea, preferably, the volume ratio equivalent ratio of the main portion and the curing agent portion is adjusted to 1.05 to 1.15 and applied.

The polyurea resin coating composition of the present invention constituted in this way is excellent in flame retardant performance to prevent the effect of pressure loads due to explosions and earthquakes on concrete structures or cement brick structures, and is resistant to earthquake and explosion resistance, elongation and tensile strength. It has excellent physical properties and has high energy absorption against external or internal shock waves and explosion loads, and serves to reduce damage to earthquake-resistant facilities and human lives and facilities.

In particular, the energy of the shock wave according to the friction performance is reflected and dispersed in close relationship with the frictional force, and the residual energy is absorbed by the polyurea, thereby preventing the energy of the shock wave with high elasticity, thereby exhibiting explosion-proof performance.

In addition, it is a coating material of high-retardant polyurea resin composition that is highly resistant to flame retardant performance and earthquake and explosion-proof, made of high crosslinking degree, and has high durability, impact resistance, scratch resistance, and excellent flame retardant performance compared to conventional polyurea and tensile strength. , Excellent elongation properties, improved explosion-proof performance, and excellent elasticity and crack followability.

Hereinafter, examples and experimental examples will be described in more detail with respect to the present invention, but these examples and experimental examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.

<Examples 1 to 5> Preparation of polyurea resin coating composition of the present invention

In order to manufacture the main part, foreign substances such as moisture, water, and dust must not be contained in the container, and BASF Corporation D-2000 having a polyetherdiamine molecular weight of 2000 is first introduced into the container within a humidity of 65%, and the primary amine is DETDA of Albermal's diethyltoluenediamine molecular weight of 178.3 was added, followed by addition of BASF's T-5000 of polyethyleneamine molecular weight of 5000, followed by mixing at 1000 rpm for 10 minutes, followed by pigment (Samyoung) and UV stabilizer (Zico), modified amino silicone (Dow Corning), and a flame retardant synthetic additive (DeChem) were added and then mixed at 1000 rpm for 30 minutes to prepare a main part to be used in the present invention.

Here, the flame retardant synthetic additive should not contain foreign substances such as moisture, water, dust, etc. in the reactor, and the reactor is stirred and maintained at a rate of 100 rpm within 65% of humidity, after heating up to a temperature of 50° C., butyl phosphate flame retardant Condensation polymerization by adding phenyl diphenyl phosphate and phenyl dichloro phosphate to each for 1 hour at 50°C for 1 hour and then adding phosphorus-based flame retardant triphenyl phosphate to it for 2 hours at 50°C for 2 hours. It was used to complete.

Next, in order to manufacture a curing agent portion, foreign substances such as moisture, water, and dust should not be included in the reactor, and within 65% of the humidity, the reactor is kept stirred at a rate of 100 rpm, while monomeric MDI (Kumho Mitsui Cosmonate LL) or After adding Modified MDI (Lupranate MI from BASF) or a mixture thereof, and adding PP-2000 polyether polyol from KPX, the temperature of the reactor was raised to 70°C, and then reacted for 3 hours when the temperature reached 70°C. After polymerization, the mixture was lowered to 50° C., and then the flame retardant synthetic additive was added and reacted at 50° C. for 1 to 3 hours. First, butylphenyl diphenyl phosphate, a phosphoric acid flame retardant, which is a part of the flame retardant synthetic additive, was introduced, followed by 50. After the primary reaction for 1 hour at ℃ ℃, phosphate dichlorophosphate, a phosphoric acid-based flame retardant, was added thereto, followed by a secondary reaction at 50°C for 1 hour, followed by the addition of triphenyl phosphate, a phosphorus-based flame retardant, at 50°C. A third curing reaction was performed for 1 hour to prepare a curing agent part to be used in the present invention.

The main part and the curing agent part prepared as described above were mixed in a 1:1 weight ratio, and the equivalent ratio was set to 1.05 to prepare the polyurea resin coating compositions of the present invention.

At this time, the mixing ratio of the components constituting the composition was applied as described in Table 1 below.

division ingredient
Mixing ratio (wt%) Subject Poly
Etherdiamine Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Molecular weight 2000 59.8 62.8 65.8 68.8 71.8 59.8 59.8 Molecular weight 5000 7 7 7 7 7 7 7 Diethyltoluenediamine
(Primary amine)
13 13 13 13 13 13 13 Modified amino silicone
0.2 0.2 0.2 0.2 0.2 0.2 0.2 UV stabilizer
One One One One One One One Pigment
4 4 4 4 4 4 4 Flame Retardant
synthesis
additive Butylphenyl diphenyl phosphate
(Phosphoric acid) 5 4 3 2 One 5 - Phenyl dichloro phosphate
(Phosphoric acid) 5 4 3 2 One 5 - Triphenyl phosphate
(taking over) 5 4 3 2 One 5 15 Hardener

Isocyanate prepolymer Monomeric MDI 42 - - 48 50 42 42 Modified
MDI - 44 - - - - - Monomeric MDI +
Modified
MDI (1:1 mix) - - 46 - - - - Polyether polyol
43 44 45 46 47 43 43 Flame Retardant
synthesis
additive Butylphenyl diphenyl phosphate
(Phosphoric acid) 5 4 3 2 One - 5 Phenyl dichloro phosphate
(Phosphoric acid) 5 4 3 2 One - 5 Triphenyl phosphate
(taking over) 5 4 3 2 One 15 5

<Comparative Example 1> Preparation of polyurea resin coating composition

Prepared in the same manner as in Example 1, was prepared by applying a different weight ratio of the flame retardant additive. The contents are shown in Table 1 above.

<Comparative Example 2> Preparation of polyurea resin coating composition

Prepared in the same manner as in Example 1, was prepared by applying a different weight ratio of the flame retardant additive. The contents are shown in Table 1 above.

<Comparative Example 3> Preparation of polyurea resin coating composition

Prepared in the same manner as in Example 1, the coating composition was prepared by applying 100% of phosphorus-based flame retardant instead of the flame retardant synthetic additive in the main part.

<Comparative Example 4> Preparation of polyurea resin coating composition

Prepared in the same manner as in Example 1, the coating composition was prepared by applying 100% of the phosphorus flame retardant instead of the flame retardant synthetic additive in the curing agent.

<Experimental Example 1> Physical properties confirmation

1. Experimental method

By spraying the polyurea resin coating composition consisting of the mixing ratios according to Examples 1 to 5 of Table 1 with a dedicated coating equipment, 10 specimens were prepared with a thickness of 300mm x 300mm and a film thickness of 2000㎛. KS M6518 Tensile strength (N/mm ² ), elongation (%), and tear strength (N/mm) were measured by the test method of (Shore A), KS F 4922, and the hardness test of KS M 6518. Hardness test method Shore A test was conducted.

2. Experimental results

As a result of the experiment, it was shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Tack Free Time
(Sec) 16 17 18 18 18 14 15 Hardness
(Shore A) 89 92 93 93 93 86 86 The tensile strength
(N/mm ² ) 19.5 20 21 21 21 19 18 Elongation
(%) 410 430 450 340 320 380 370 Tear strength
(N/mm) 75 77 78 65 66 68 67

As shown in Table 2, it was confirmed that the curing power (Trac Free Time), hardness, tensile strength, elongation, and tear strength were all higher than Comparative Examples 1 to 4 in the compositions of Examples 1 to 3.

<Experiment 2> Flame retardant test grade check

1. Experimental method

Several classes of flame retardants were tested in the present invention. In the test of expanded expandable graphite, there was a high heat resistance and self-extinguishing function, but the viscosity of the main part and the curing agent part increased so that when using the coating equipment for exclusive use of polyurea, there was a problem that spraying was not possible due to the effect of viscosity, and the amount of expanded expandable graphite added When was decreased, the flame retardant effect was extremely small.

In particular, triphenyl phosphate, a commonly used phosphorus flame retardant of the conventional polyurea, has a function of self-extinguishing, but is not only inferior to the flame retardant due to its poor heat resistance, and the conventional polyurea is based on petrochemicals and based on isocyanate prepolymers. Since it is composed of polyamine resin, the heat-resistant part is inferior to epoxy or ceramic.

Thus, although not shown in the present invention, in the flame retardant performance test, when applying various flame retardant additives such as melamine, halogen, phosphorus, graphite, the flame retardant performance was confirmed to be limited. As a test method of flame retardant performance, the test of UL-94V (DIN IEC 60695-11-10) was conducted. As a result, when using a flame retardant synthetic additive made of a phosphorus-based or phosphoric acid-based as in the present invention, it was confirmed that the flame retardant performance is the best. The result of this flame retardant performance is as follows.

2. Experimental results

As a result of the experiment, it was shown in Table 3 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Flame retardant test grade
UL-94V V-0 V-1 V-2 FAIL FAIL FAIL FAIL

As shown in Table 3 above, the result of the test is that V-O represents the highest grade. In other words, the flame retardant synthetic additive applied to the present invention is added to the curing agent portion and the main portion of the isocyanate prepolymer as phosphate-based butylphenyl diphenyl phosphate, phenyl dichloro phosphate, phosphorus-based triphenyl phosphate at 8 to 20 wt%, respectively. When used, it was confirmed that the flame retardant grade was superior to Comparative Examples 1 and 2 using only phosphorus-based flame retardants. This is preferably a number of excellent and innumerable flame retardants of the present invention, in order to maintain the flame retardant performance and the natural properties of polyurea, phosphorus-based or phosphoric-based flame retardants are prepared by the method of condensation polymerization, but flame retardant mixed in an appropriate ratio It has been confirmed that the use of synthetic additives allows the intrinsic physical properties to be retained and thus to have excellent flame retardant performance.

<Experimental Example 3> Explosion-proof performance confirmation

1. Experimental method

The polyurea resin coating composition for explosion-proof of Example 1 was applied to the surface of a concrete brick structure to a thickness of 6 mm to perform explosion-proof construction and confirm the practical effectiveness of its function. This was conducted at the Army Engineer School test site, and after the 1st bombing 155mm high-bomb (bullet) blasting test, the 2nd bombing test TNT 120kg was continuously blasted, the explosion-proof construction condition was confirmed, and the separation distance between explosives and structures was 6.5. m.

2. Experimental results

As a result, as shown in FIG. 3, in the case of the wall constructed with the polyurea resin coating composition for explosion-proof of Example 1, it was confirmed that the structure retains its original state such as the structure support state or the resin property state even after the explosion, and thus has explosion-proof effect. Was confirmed.

The present invention has been described with reference to preferred embodiments, and those of ordinary skill in the art to which the present invention pertains may implement embodiments in different forms from the detailed description of the present invention within the essential technical scope of the present invention. Will be able to. Here, the essential technical scope of the present invention is indicated in the claims, and all differences within the equivalent range should be interpreted as being included in the present invention.

Claims (7)

40 to 75 wt% of polyetherdiamine, 10 to 25 wt% of diethyltoluenediamine, 0.1 to 5 wt% of modified aminosilicon, 0.1 to 5 wt% of UV stabilizer, 0.1 to 10 wt% of pigment, and 8 to 20 wt% of flame retardant additive Subject part consisting of,
It consists of a curing agent portion consisting of 35 to 47 wt% of isocyanate prepolymer, 35 to 45 wt% of polyol, and 8 to 20 wt% of a flame retardant synthetic additive;
The flame retardant synthetic additive is characterized by consisting of a phosphoric acid-based flame retardant and a phosphorus-based flame retardant,
Polyurea resin paint composition with flame retardant, explosion-proof and earthquake-proof waterproofing material.
According to claim 1,
The polyurea resin coating composition is characterized in that the main portion and the curing agent portion is composed of a weight ratio of 1 to 4: 1 ratio,
Polyurea resin paint composition with flame retardant, explosion-proof and earthquake-proof waterproofing material.
delete Based on the total weight of the main part, 35~66wt% of polyetherdiamine having a weight average molecular weight of 2000, 10~25wt% of diethyltoluenediamine, and 5~9wt% of polyethyleneamine having a weight average molecular weight of 5000 are put in a container first and then at 500~1500 rpm. After mixing for 5 to 10 minutes, add denatured amino silicone 0.1 to 5 wt%, UV stabilizer 0.1 to 5 wt%, pigment 0.1 to 10 wt%, flame retardant synthetic additive 8 to 20 wt% and mix for 20 to 30 minutes at 1000 to 1500 rpm. Manufacturing the subject by;
After adding the isocyanate prepolymer 35-47 wt% and the polyol 35-45 wt% based on the total weight of the curing agent part in the reactor where the stirring speed of 30-150 rpm is maintained, the temperature of the reactor is raised to 70-80° C., 70 When the temperature is reached to ~80 ℃ to polymerize by reacting for 3 to 4 hours, and then lowering it to 50 ~ 60 ℃ 8 to 20 wt% of the flame retardant synthetic additives and mixed to prepare a curing agent portion, and
It comprises mixing the main part and the curing agent part in a weight ratio of 1 to 4: 1, and the equivalent ratio of the main part and the curing agent part is mixed within a range of 1.05 to 1.15 to prepare a polyurea resin coating composition.
A method of manufacturing a polyurea resin coating composition having a flame retardant, explosion-proof and earthquake-proof waterproof material.
The method of claim 4,
The flame retardant synthetic additive of the main part is charged with a phosphate-based flame retardant butylphenyl diphenyl phosphate and a phosphate-based flame retardant phenyl dichlorophosphate in a container for 1 to 2 hours at 50 to 60°C. After the primary reaction, a phosphorus-based flame retardant, triphenyl phosphate, is added thereto, and is produced by performing a secondary reaction at 50-60° C. for 1 to 2 hours.
A method of manufacturing a polyurea resin coating composition having a flame retardant, explosion-proof and earthquake-proof waterproof material.
The method of claim 4,
The flame retardant synthetic additive of the curing agent is phosphate-based flame retardant butylphenyl diphenyl phosphate (butylphenyl diphenyl phosphate) in a primary reaction for 50 to 60 ℃ 1 to 2 hours, and then again the phosphoric acid flame retardant phosphoric acid flame retardant Phenyl dichlorophosphate was added and reacted for 2 hours at 50~60℃ for 1~2 hours, then phosphorus-based flame retardant Triphenyl phosphate was added and for 3~1 hours at 50~60℃ Characterized by being produced by reaction,
A method of manufacturing a polyurea resin coating composition having a flame retardant, explosion-proof and earthquake-proof waterproof material.
A method of coating and coating a polyurea resin coating composition on the surface of a concrete structure or cement brick structure by spraying the polyurea resin coating composition of any one of claims 1, 2, and 4 with a high-temperature, high-pressure spray device.

Images