KR102031566B1 - Waterproofing composition and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a high functional polyurea-urethane hybrid waterproof material composition and a method for manufacturing the same. The high functional polyurea-urethane hybrid waterproof material composition has improved durability and flame retardancy by performing hybrid-combination on polyurea and a polyurethane resin, adding heat resistance to a waterproof material by containing a heat-shielding pigment and a hollow ceramic, and adding and polymerizing flame retardant polyol to use the same, thereby preventing discharge of black smoke during combustion, preventing a fire from occurring by self-extinguishing in seconds, and simultaneously having heat resistance. A polyurea-urethane hybrid waterproof material is formed of two-liquid type components consisting of a main material and a curing agent, wherein the main material includes an amine-terminated ether polyol, a flame retardant, a polyether-based polyol, a castor oil, a chain extender, a heat-shielding pigment, a hollow ceramic, and a silane coupling agent, and the curing agent includes an isocyanate-terminated prepolymer obtained by adding and polymerizing a hydroxyl-terminated phosphorus-based polyol to a carbodiimide modified diphenyl methane diisocyanate.

Description

Polyurea-urethane hybrid waterproofing composition having heat shielding and flame retardancy and its manufacturing method {Waterproofing composition and Manufacturing method

The present invention relates to a method for producing a waterproofing material composition, and more particularly, a polyurea and a polyurethane resin are combined in a hybrid, heat shielding pigments and hollow ceramics are added to add heat shielding properties to a waterproofing material, and a flame-retardant polyol is further polymerized by By using it to improve durability and flame retardancy, through which there is no discharge of black smoke during combustion, it is self-extinguishable within a few seconds without fire occurs at the same time high functional polyurea-urethane hybrid waterproofing material composition and its manufacturing method It is about.

In recent years, the temperature of the city center is a heat island phenomenon due to air pollution, artificial structures, vehicle exhaust gas. Tropical islands occur at night due to this heat island phenomenon. To solve this problem, developed countries such as Japan are conducting research and construction to reduce the temperature of the city by heat shielding the roads, and to solve the summer heat problem in Korea. Increasingly, policies and interests in reducing urban temperatures, such as the formation of green zones, have been increasing.

This increase in temperature is mainly caused by the near infrared rays of sunlight, and thus the need for a waterproofing material having a heat shielding effect is reconsidered by having a component or structure capable of reflecting without absorbing the near infrared rays.

In addition, the waterproofing material is preferably added to the flame retardancy, in order to add the flame retardant in the case of adding a flame retardant from the outside, or chemically used to react the flame retardant, when the external flame retardant is used as the flame retardant over time It is preferable to react the flame retardant chemically because there is a problem of bleeding or blooming to reduce the flame retardancy or the performance of the waterproofing material.

On the other hand, in the prior art of the waterproof material, Patent No. 10-1141511 is used to illustrate the explosion-proof, dust-proof, waterproof, anticorrosive flooring using a two-component polyurea coating composition based on the amine-terminated epoxy prepolymer. There is a problem.

In still another conventional technique, Patent No. 10-1595041 describes a flame retardant poly-based material using a mixture of various flame retardants, solvents, plasticizers, polyamines, polyether polyamines, and the like in a prepolymer produced by the reaction of an isocyanate with a polyol. Urea is exemplified, which has a disadvantage in that flame retardant durability is reduced compared to reactive flame retardants using only non-reactive flame retardants.

In addition, as another conventional technology, Korean Patent Laid-Open Publication No. 10-2009-0080371 exemplifies an eco-friendly, low-melting film waterproofing material that uses a modified asphalt to generate less harmful gas and prevents fire. Oxidation and aging may occur over time, resulting in leaks or defects in buildings. Hazardous substances in asphalt may also cause environmental problems.

Furthermore, in another conventional technique, Korean Patent No. 10-1406932 discloses a one-component urea bottom waterproofing coating composition having abrasion resistance, fouling resistance, weather resistance, and flame resistance mainly using polyols, fluoroalcohols, blocking agents, isocyanates, and amine monomers. As illustrated, when the terminal isocyanate group is blocked with a blocking agent, there is a problem in that a high temperature must be applied so that the blocking agent dissociates later.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a waterproof material having excellent durability and flame retardant properties by simultaneously using an external flame retardant and an internal flame retardant through chemical synthesis.

In addition, the waterproofing material is coated on the roof or the upper part to prevent heat as it gives heat shielding function by paying attention not only to the waterproof function but also to the heat generated by solar light, and is particularly suitable for rooftop waterproofing and is suitable for the polyurea-urethane hybrid combination. The purpose of the present invention is to provide a strong yet elastic waterproof material that ensures proper reactivity and does not tear even at low temperatures in winter.

The present invention for the purpose of solving the above problems is a polyurea-urethane hybrid waterproofing material composed of a two-component component consisting of a main agent and a curing agent, the main subject is an amine-terminated ether polyol, flame retardant, polyether polyol, castor oil, chain An extender, a heat shield pigment, a hollow ceramic, and a silane coupling agent, and the curing agent is characterized in that it comprises an isocyanate-terminated prepolymer obtained by addition polymerization of a hydroxyl-terminated phosphorus-based polyol to a carbodiimide-modified diphenyl methane diisocyanate.

In addition, the castor oil is characterized in that 5 to 10 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal may be included.

In addition, the heat shielding pigment contains titanium dioxide, 5 to 10 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal, 5 to 20 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal It may be included.

In addition, the curing agent is characterized in that the carbodiimide-modified diphenyl methane diisocyanate may include an isocyanate terminal prepolymer by addition polymerization of the hydroxyl terminal phosphorus polyol in a weight ratio of 9: 1 to 8: 2:

In addition, the silane coupling agent is characterized in that 0.2 to 1.0 parts by weight relative to 100 parts by weight of the ether polyol of the amine terminal may be included.

When the main body and the curing agent are mixed in a 1: 1 ratio and sprayed at a thickness of 1 to 3 mm, a polyurea-urethane hybrid waterproofing film having heat shielding and flame retardancy is formed.

The present invention having the above-described constitution and characteristics shows flame retardancy having self-extinguishability within a few seconds when heating the coating film formed by spray coating with a torch, and exhibiting heat shielding property indicating a temperature lower than 7 ° C. in comparison with the surroundings, and when used for roof waterproofing, etc. It shows excellent functionality. In addition, the polyurea / urethane hybrid combination provides a predetermined elasticity so that cracks do not occur due to temperature change, and has a high-performance waterproofing material by maintaining strength and toughness by polyurea.

1 is a view of an experiment comparing and measuring the temperature of the concrete surface and the surface of the waterproofing material.

Since the present invention may be modified in various ways and have various forms, embodiments (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments (suns, aspects, and embodiments) (or embodiments) only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms “comprises” or “consists” are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described on the specification, but one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

In the present specification, the first to second and the second to refer to different components are not limited to the order of manufacture, and their names are used in the detailed description and claims of the present invention. May not match.

Hereinafter will be described in detail the contents for implementing the present invention.

The waterproofing composition (hereinafter the present composition) according to the present invention is composed of a two-component component consisting of a main agent and a curing agent.

Specifically, the first topic is 100 parts by weight of ether polyol of the amine terminal, 10 to 20 parts by weight of flame retardant, 10 to 20 parts by weight of polyether-based polyol, 5 to 10 parts by weight of castor oil, 10 to 30 parts by weight of chain extender, 5 to 10 parts by weight of the heat shield pigment, 5 to 20 parts by weight of the hollow ceramic and 0.2 to 1.0 part by weight of the silane coupling agent.

For each composition, 100 parts by weight of the amine-terminated ether polyol, which is one component of the subject matter, may be based on 100 parts by weight of the ether polyol of the amine-terminated composition.

Polyols are polyfunctional alcohols having two or more hydroxyl groups (-OH) in the molecule and are essential raw materials with isocyanates in polyurethane production. Polyols are largely divided into ether polyols and ester polyols. In the present invention, amine-terminated ether polyols are employed.

In the above, it is preferable that the amine-terminated ether polyol has a molecular weight of 1000 to 3000. If the molecular weight is lower than 1000, brittleness is excessively lowered. If the molecular weight is higher than 3000, the urea function is lowered and the coating film is weakened. A problem arises.

Next, the flame retardant may include 10 to 20 parts by weight, wherein the flame retardant may be used alone or mixed, such as expanded graphite, polyphosphate, inorganic, etc., if less than 10 parts by weight, the flame retardancy is lower, than 20 parts by weight The higher the viscosity, the poor the waterproofing.

Next, the polyether polyol may include 10 to 20 parts by weight, the polyether polyol preferably has a functional group of 2 to 6, if the content is less than 10 parts by weight of the urethane function is lower than 20 parts by weight If it is high, the reactivity is slow.

Next, castor oil is an environmentally friendly natural polyol extracted from castor plants, but it is preferable to include 5 to 10 parts by weight due to poor compatibility with ether-based polyols, especially when less than 5 parts by weight, the modification effect is lower, more than 10 parts by weight There is a problem of poor storage stability.

Next, as the chain extender, ethylene glycol, diethylene glycol, propylene glycol, butanediol, glycerin, and the like, which are short alcohols of 2 to 5, can be used, and short amine-based ethylene diamine, isophorone diamine, triethylene pentaamine, triethylene Tetramin or the like can be used, but if the content is less than 10 parts by weight, the coating film becomes weak, and if it is more than 30 parts by weight, the elasticity is reduced.

Next, the heat shield may include a heat shield pigment and a hollow ceramic. In this regard, the heat shield pigment reflects the infrared rays in that 50% of the infrared rays are converted from sunlight to heat. Absorbs and prevents temperature rise of waterproofing material.

Titanium dioxide (TiO ₂ ) is a main component of such a heat shielding pigment, and its amount is preferably 5 to 20 parts by weight.

In addition, it is preferable to use a hollow ceramic having an average particle diameter of 10 to 70 µm, a color of white, an apparent density of 0.1 to 0.4 g / cm 3, and a melting point of 1000 to 1500 ° C. The hollow ceramic is an inorganic material including internal pores, and excellent inertness, acid resistance, alkali resistance, flame retardancy, etc., but if it is used in a large amount, the coating performance is degraded and the water resistance is lowered. The preferred amount of use is 5 to 20 parts by weight.

Next, although the coupling agent has a titanium system and a silane system, since a silane system is economical, it is preferable to use a silane system. The coupling agent improves adhesion at the interface between the organic binder, inorganic pigments, and ceramics, thereby improving water resistance and improving coating properties.

Such a coupling agent preferably has an amine group at one end and a silane group at another end, for example N-β (amino ethyl) γ-amino propyl methyl dimethoxy silane, N-β (amino ethyl) γ- Amino propyl trimethoxy silane, N-β (amino ethyl) γ-amino propyl triethoxy silane, γ-amino propyl trimethoxy silane, γ-amino propyl triethoxy silane, N-phenyl-γ-aminopropyl tri It may comprise at least one of methoxy silanes.

The coupling agent is preferably included 0.2 to 1 parts by weight, for example, less than 0.2 parts by weight, the adhesive effect is lowered, more than 1.0 parts by weight is economical and reactivity is too fast.

In addition, the composition may further include an amine catalyst or a metal catalyst in order to promote the urea / urethane reaction because the reactivity is low at low temperatures, such as in winter, for example, diethyl ethanol amine, At least one may be selected from triethylene diamine, pentamethylene diethyltetramine, and N-ethyl morphine, and at least one may be selected from octinate, dibutyltin, dilaurate, and lead octylate as the metal catalyst. have.

The amine catalyst or the metal catalyst may be included in any one of 0.1 to 1.0 parts by weight, or 0.1 to 1.0 parts by weight of one or more of the amine catalyst and the metal catalyst is preferably included. If the content of the catalyst is less than 0.1 part by weight, the reaction is slow. If the content of the catalyst is more than 1.0 part by weight, the reaction is too fast and discoloration occurs.

On the other hand, in the matter concerning the hardening agent which is another structure of this composition, the method of manufacturing a hardening | curing agent is as follows.

First, as a prepolymer, a hydroxyl-terminated phosphorus polyol is added to a diphenyl methane diisocyanate having a carbodiimide bond in a reactor in a weight ratio of 9: 1 to 8: 2, and the temperature is set at 70 to 90 ° C. under a nitrogen atmosphere, followed by stirring. When the polymerization reaches a theoretical NCO%, the reaction is terminated and cooled. Theoretical NCO% here is NCO% calculated after the hydroxyl terminal phosphorus polyol has reacted with diphenylmethane diisocyanate, where the NCO% value is 10-25%. If the NCO% content is 10% or less, the flame retardancy is good, but the viscosity is too high. If the NCO% is 25% or more, the viscosity is low, but the flame retardancy is poor.

In the present invention, a method of lowering the viscosity and further increasing the flame retardancy may include at least one of trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, diisobutyl phthalate, dinormal octyl phthalate, diethylhexyl phthalate, and diisodecyl phthalate. One or more may be selected and added.

The main material and the hardener thus prepared are mixed at a weight ratio of 1: 0.5 to 0.5: 1 to be applied to the coated surface, and then cured to form a polyurea / urethane hybrid waterproofing material.

The two-component waterproof material according to the present invention can form a reactive coating having heat shielding properties and flame retardancy at the same time. The coating film formed according to the present invention was shown to be self-extinguishing in the butane gas torch, the heat shielding was also confirmed that the temperature is reduced by more than 7 ℃ compared to concrete or asphalt concrete is not coated.

Hereinafter, the present invention will be described in detail by way of examples, which are merely illustrative and the scope of the present invention is not limited thereto.

[Production Example 1]

To prepare a curing agent 1 to 5 according to the composition ratio of Table 1. When carbodiimide-modified diphenyl diisocyanate and hydroxyl-terminated phosphorus polyol were reacted at 80 ° C. for 3 to 5 hours under nitrogen atmosphere, the remaining isocyanate content was measured by dibutylamine reverse titration, and the reaction resulted in an isocyanate content of 10 to 25%. Terminated.

Hardener One 2 3 4 5 Carbodiimide Modified Diphenyl Methane Diisocyanate 100 100 100 100 100 Hydroxyl terminated phosphorus flame retardant 0 5 10 15 20

(Unit: parts by weight)

[Production Example 2]

According to the composition of Table 2, the stirring was performed at a high speed of stirring for 2000 minutes and a stirring time of 30 minutes to prepare a subject.

subject One 2 3 4 5 6 7 Amine-terminated ether polyols 100 100 100 100 100 130 130 Castor Oil 10 10 10 10 0 0 10 Polyether polyols 20 20 20 20 0 0 20 Chain extender 10 10 10 10 40 10 10 Polyphosphate Flame Retardant 0 0 10 10 10 10 0 Inorganic flame retardants 0 0 10 10 10 10 0 Heat shield pigment 0 10 0 10 10 10 0 Hollow Ceramic 0 5 0 5 5 5 0 Coupling agent 0 0 0 0.8 0.8 0.8 0 catalyst 0 0.3 0 0.3 0.3 0.3 0

(Unit: parts by weight)

[Examples 1 to 6]

The main ingredients and the curing agent were blended as shown in Table 3 below to spray the liquid ratio of the main agent and the curing agent to 1: 1 to obtain a coating film thickness of 1 to 3 mm.

Example subject Hardener One 4 5 2 5 4 3 4 3 4 6 5 5 5 2 6 6 3

[Comparative Examples 1 to 4]

The subjects and the curing agent were formulated as shown in Table 4 below, and the spray ratio was sprayed to 1-3 mm with a liquid ratio of 1: 1.

Comparative example subject Hardener One One One 2 7 One 3 2 One 4 3 One

In the above, the obtained polyurea / urethane hybrid coating film properties evaluation tables are shown in Table 5 and Table 6.

Example The tensile strength
(MPa) Elongation at Break
(%) Hardness Breathable
(g / m ² .24h) Water absorption
(%) Flame retardant Heat shield
(△ ℃) One 7.5 71 45 0.4 4.7 OK 7 2 7.9 68 51 0.3 4.2 OK 6 3 8.2 65 54 0.2 3.5 OK 5 4 8.4 62 56 0.2 3.1 OK 7 5 9.0 52 62 0.1 2.5 OK 6 6 8.6 56 58 0.2 2.8 OK 7

Comparative example The tensile strength
(MPa) Elongation at Break
(%) Hardness Breathable
(g / m ² .24h) Water absorption
(%) Flame retardant Heat shield
(△ ℃) One 6.3 66 50 0.6 5.4 NG 2 2 7.6 53 58 0.6 6.2 NG 4 3 7.0 73 54 0.5 5.5 NG 2 4 7.3 70 53 0.5 5.7 NG 2

Physical property measurement method in the experiment is as follows.

[Measurement Method]

-Tensile strength: measured according to ISO 527-1 test standard

Elongation at break: measured according to ISO 527 test standard

Hardness: measured according to ASTM D 2240 test standard (Shore D)

-Moisture permeability: measured according to ISO 12572 test standard

-Water absorption: measured according to DIN EN 12087 test standard

-Flame retardant: measured according to DIN 4102 (part 1, B2) test standard

-Thermal insulation: Temperature difference with concrete surface (Concrete surface temperature-Surface temperature of coated surface)

As can be seen from the above experimental results, when the heat shield pigment and the hollow ceramics included, the concrete surface and the waterproofing material surface showed a difference of 7 ℃, but did not include a difference of 2 ℃. When the reactive phosphorus-based flame retardant polyol was introduced by addition polymerization, the flame retardancy was excellent. However, when the flame retardant was added to the subject, the flame retardancy was excellent enough to have self-extinguishing within a few seconds.

In addition, the invention has excellent moisture permeability, moisture absorption, tensile strength, elongation at break, etc. so that the overall coating film properties are suitable for the waterproofing material. In addition, in Figure 1 it can be confirmed the results of measuring the surface of the concrete surface and the waterproof material.

Claims (5)

In the polyurea-urethane hybrid waterproofing material consisting of a two-component component consisting of a main body and a curing agent,
The subject matter includes amine-terminated ether polyols, flame retardants, polyether polyols, castor oil, chain extenders, heat shield pigments, hollow ceramics, silane coupling agents,
The hardener is a polyurea-urethane hybrid waterproofing material comprising an isocyanate-terminated prepolymer obtained by addition polymerization of a hydroxyl-terminated phosphorus-based polyol to carbodiimide-modified diphenyl methane diisocyanate.
The method according to claim 1,
The castor oil is a polyurea-urethane hybrid waterproofing material, characterized in that 5 to 10 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal.
The method according to claim 1,
The heat shield pigment includes titanium dioxide, 5 to 10 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal,
The hollow ceramic is a polyurea-urethane hybrid waterproofing material, characterized in that 5 to 20 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal.
The method according to claim 1,
The curing agent is a polyurea-urethane hybrid, characterized in that the carbodiimide-modified diphenyl methane diisocyanate is an isocyanate terminal prepolymer obtained by addition polymerization of the hydroxyl terminal phosphorus polyol in a weight ratio of 9: 1 to 8: 2: Waterproofing material.
The method according to claim 1,
The silane coupling agent is a polyurea-urethane hybrid waterproofing material, characterized in that 0.2 to 1.0 parts by weight, based on 100 parts by weight of the ether polyol of the amine terminal.