KR101680353B1 - Urethane membrane material for waterproofing having insulation functions - Google Patents

Abstract

The present invention relates to an environmentally-friendly urethane membrane waterproofing material having a thermal insulation effect, comprising a main agent including an isocyanate prepolymer including polyoxypropyleneglycol, polyester polyol, aromatic diisocyanate, 1,4-butadiol, dimethyl carbonate, a non-phthalate plasticizer and nano-type ceramic balls; and a curing agent including polyoxypropyleneglycol, polyester polyol, 2,2-dichloro-4,4-methylenedianiline, tetraethyl N,N-(methylene di-4,1- cyclohexanediyl)bis(aspartate), a non-phthalate plasticizer, a pigment, calcinum carbonate, dimenthyl carbonate, and bismuth. According to the present invention, the urethane membrane waterproofing material has not only an excellent waterproofing effect but also an excellent thermal insulation effect and therefore, can significantly reduce the indoor temperature of a building during the summertime and prevent aging of the building by suppressing membrane deformation caused by heat expansion. Also, the present invention does not use volatile organic compounds and thus, has the advantage of preventing environmental pollution.

Description

TECHNICAL FIELD [0001] The present invention relates to an eco-friendly urethane coating material having a heat-shielding effect,

The present invention relates to an eco-friendly urethane coating material composition having a heat-shielding effect, and more particularly, to an eco-friendly urethane coating material composition having an excellent heat-insulating effect as well as excellent physical properties and waterproofness of a coating film.

In general, waterproofing of a concrete structure such as a roof or an upper slab of a building structure is generally performed by a cold waterproofing method as a conventional waterproofing method.

As a waterproof material used for this purpose, cement, silica sand and other aggregates are mainly used, and a mixture of an ethylene vinyl resin and an acrylic resin is mixed with an inorganic filler and an acrylic resin, and an inorganic filler and a dispersing agent are mixed Acrylic emulsion rubber emulsion coating system waterproofing material, asphalt-based coating film waterproofing material in which synthetic rubber is emulsified by emulsifying asphalt, a prepolymer made by polymerizing with polyester or polyether isocyanic acid, etc., and the inorganic filler, stabilizer, colorant , An emulsion-type denaturing agent prepared by emulsifying, dispersing, and reacting a urethane rubber prepolymer prepared by adding a crosslinking agent to an acrylic rubber emulsion, which is free-mixed, and then adding an inorganic filler, a dispersant, Acrylic urethane rubber coating film waterproofing material, polymer Cement coating film and waterproofing material.

However, the conventionally used coating film waterproofing material for construction has merely limited waterproofing properties, and thus does not contribute to cooling and heating the inside of the building because it has no function of blocking light (heat) against the solar energy irradiated to the building There was a disadvantage. In addition, as the temperature rises due to solar energy (rising to a surface temperature of 80 ° C in summer), deterioration of the waterproof layer occurs, resulting in a decrease in durability and an increase in the cost of repair work for the waterproof layer.

Further, such a coating film waterproofing material has disadvantages that it uses a volatile organic compound such as toluene, xylene and phosphoric acid as a solvent and uses a phthalate plasticizer to adversely affect the human body and the environment.

KR 10-1439298 B1 KR 10-0918085 B1

Accordingly, an object of the present invention is to provide an environmentally friendly coating film-free waterproofing material without using a volatile organic compound, a solvent such as phosphoric acid, and a phthalate plasticizer.

In addition, by using a nano-type ceramic ball or the like, excellent reflectance of solar light is exhibited and an excellent heat shielding effect is obtained.

The urethane coating film waterproofing material composition having heat shielding and heat insulating effect according to the present invention is characterized by containing polyoxypropylene glycol, aromatic diisocyanate, polyesters polyol, 1,4-butadiol, dimethyl carbonate, non-phthalate plasticizer and nano- Wherein the polyol is selected from the group consisting of polyoxypropylene glycol, polyester polyol, 2,2'-dichloro-44'-methylenedianiline, tetraethyl N, N'-methylenedi-4,1-cyclohexane Dibasic asphalt, a nonphthalate plasticizer, a pigment, calcium carbonate, dimethyl carbonate, and bismuth.

The above-mentioned subject and the curing agent are mixed in a weight ratio of 1: 3.

The nano-type ceramic balls are made of aluminum silicate and have a particle size of 5 to 100 nm.

The above-mentioned subject matter includes 100 parts by weight of polyoxypropylene glycol, 40 to 100 parts by weight of aromatic diisocyanate, 2 to 6 parts by weight of polyester polyol, 1 to 4 parts by weight of 1,4-butadiol, 20 to 50 parts by weight of dimethyl carbonate, 40 to 60 parts by weight of a phthalate plasticizer and 5 to 20 parts by weight of a nano-type ceramic ball, wherein the curing agent comprises 100 parts by weight of polyoxypropylene glycol, 0.5 to 5 parts by weight of a polyester polyol, 8 to 20 parts by weight of methylene dianiline, 2 to 10 parts by weight of tetraethyl N, N'-methylenedi-4,1-cyclohexanediylbisaspart, 40 to 100 parts by weight of a nonphthalate plasticizer, 15 to 15 parts by weight of calcium carbonate, 160 to 300 parts by weight of calcium carbonate, 8 to 25 parts by weight of dimethyl carbonate, and 2 to 8 parts by weight of bismuth.

The nonphthalate plasticizer of the above-mentioned subject matter and the hardener is a mixture containing one single substance or two or more selected from the group consisting of C8-C20 alcohol type, ester type, carboxylate type, aliphatic type and benzoate type plasticizers, Further comprises 5 to 10 parts by weight of cerium oxide.

According to the present invention, it is possible to prevent the aging of buildings by suppressing the deformation of the coating film due to thermal expansion while significantly reducing the room temperature of the summer building structure by having waterproofing and excellent heat shielding effect. In addition, there is an advantage of preventing environmental pollution because volatile organic compounds are not used.

Hereinafter, the present invention will be described in detail.

The eco-friendly urethane coating material waterproofing composition having a heat shielding effect according to the present invention not only exhibits excellent waterproof property but also excellent heat shielding property, thereby lowering the indoor temperature of a summer building, thereby contributing to energy saving.

To this end, the eco-friendly urethane coating material composition of the present invention having a heat-shielding effect is provided in a two-pack form of a base and a curing agent. Here, the subject and the curing agent are mixed at a weight ratio of 1: 3, which takes into account the physical properties of the subject, the functional group in the curing agent, and physical properties of the coating film.

First, the subject matter of the present invention will be described.

The subject of the present invention is an isocyanate prepolymer which is selected from the group consisting of polyoxypropyleneglycol, aromatic diisocyanate, polyester polyol, 1,4-butadiol, dimethylacarbonate, Non-phthalate plasticizers and nano-type ceramic balls.

As the polyoxypropylene glycol, those having a molecular weight of 400 to 3,000 can be used. Here, the reason for limiting the molecular weight of the polyoxypropylene glycol is to improve the physical properties such as elongation of the coating film. Hereinafter, the 'weight part' in the subject will be described based on 100 parts by weight of the polyoxypropylene glycol.

Also, the aromatic diisocyanate includes at least one of monomeric diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate. The monomeric diphenylmethane diisocyanate may be 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate. ). ≪ / RTI > The modified diphenylmethane diisocyanate may be modified methylene bisphenyl isocyanate, and the polymeric diphenylmethane diisocyanate may be polymethylene polyphenyl isocyanate.

If the content of the aromatic diisocyanate is too small or too large, the urethane reaction can not proceed smoothly or the physical properties of the coating film are poor due to the residual curing agent.

In the present invention, the polyoxypropylene glycol and the aromatic diisocyanate are basic components for forming an isocyanate prepolymer and are well known in the field to which this technology belongs. Therefore, the polyoxypropylene glycol and the aromatic diisocyanate are not limited Do not.

The polyester polyol and 1,4-butadiol are used as a chain extender. The polyester polyol may be methyl propanediol, tetramethylene glycol or the like, 2 to 6 parts by weight. The 1,4-butadiol is contained in the range of 1 to 4 parts by weight in the subject. If the content of the chain extender is too small, it is difficult to exert the function of chain expansion, and if it is excessive, the physical properties of the coating film deteriorate.

The dimethyl carbonate is used as a solvent, and it replaces volatile organic compounds such as toluene, xylene, and phosphoric acid. That is, conventional solvents such as toluene and xylene have been disadvantageously affected by the environment and human body, and the present invention has solved the problems caused by the volatile organic compounds by using dimethyl carbonate as an eco-friendly raw material Thereby enhancing environmental friendliness. The content of the dimethyl carbonate is in the range of 20 to 50 parts by weight. When the content of the dimethyl carbonate is out of the above range, the workability and physical properties of the coating film are deteriorated.

In addition, the present invention uses a non-phthalate plasticizer, which is an environmentally friendly plasticizer, as a plasticizer, and the phthalate plasticizer has been controversial because it is suspected to be an endocrine disruptor that interferes with or disrupts the action of a hormone in an animal or a human body , But the use of such a phthalate plasticizer is limited in the present invention.

The nonphthalate plasticizer may be a mixture of one or more selected from the group consisting of C8-C20 alcoholic, esteric, carboxylate, aliphatic and benzoate plasticizers. Examples of the nonphthalate ester plasticizers include phosphoric acid ester plasticizers, polyester plasticizers, tetrabromophthalic acid bis esters, alkylaryl phosphate esters and the like. Examples of the nonphthalate carboxylate plasticizers include dinonylcyclohexanedicar And non-phthalate aliphatic plasticizers include DOA, DOS and the like. Examples of the nonphthalate-based benzoyl plasticizers include benzoate ester plasticizers such as Benzoflex®, but are not limited thereto .

The nonphthalate plasticizer is contained in an amount of 40 to 60 parts by weight in the base. When the content of the plasticizer is out of the range, the viscosity of the nonphthalate plasticizer can not be controlled and the reaction rate of the base and the curing agent can not be controlled.

The nano-type ceramic ball is a component for imparting heat resistance to the coating film waterproofing material of the present invention, and is composed of aluminum silicate. That is, since such a nano-type ceramic ball has porosity, it has an excellent effect on heat reflection and heat resistance through the ceramic coating of the micro closed air layer, thereby ensuring an excellent heat shielding effect of the coating film.

In this case, the particle size of the ceramic ball is preferably 5 to 100 nm. If the particle size is too large, the workability of the coating film is deteriorated. If the particle size is too small, the scattering effect of light is reduced. The ceramic ball is contained in an amount of 5 to 20 parts by weight. If the content of the ceramic ball is too small, the effect of heat shielding is poor. If the content of the ceramic ball is excessive, the physical properties of the coating film are deteriorated.

In addition, the ceramic ball may include 5 to 10 parts by weight of cerium oxide, which is a high-refraction material, together with the ceramic ball. If the ceramic ball and the cerium oxide are included together, the reflectance can be improved at the propagation zone. The particle size of the cerium oxide is not limited, and the average particle size thereof may be 10 to 50 탆.

And 5 to 10 parts by weight of cericite. If the cericite is further included, the weathering resistance of the coating film is improved. The average particle size of the sericite may be about 5 to 50 mu m.

In addition, it may contain siloxanes (Siloxanes) and silicones (Silicones) in an amount of 0.001 to 0.01 parts by weight, respectively, for the physical properties of the coating film.

Hereinafter, the curing agent according to the present invention will be described.

The curing agent according to the present invention may be selected from the group consisting of polyoxypropylene glycol, polyester polyol, 2,2'-dichloro-4,4'-methylenedianiline, tetraethyl N, N Methylene di-4,1-cyclohexanediyl bisasparate, nonphthalate plasticizer, free pigmen, calcium carbonate, dimethyl carbonate, and bismuth.

Hereinafter, the "part by weight" in the curing agent is based on 100 parts by weight of the polyoxypropylene glycol contained in the curing agent. The polyoxypropylene glycol may have a functionality of 2 to 3, a molecular weight of 200 to 5,000, and a hydroxyl value of 20 to 300. The polyoxypropylene glycol reacts with an isocyanate group in the subject to form a urethane coating.

The polyester polyol and 2,2'-dichloro-4,4'-methylenedianiline are used as a chain extender, and can be used in the range of 0.5 to 5 parts by weight and 8 to 20 parts by weight in the curing agent, respectively. The polyester polyol may be methyl propanediol, tetramethylene glycol, or the like.

The above tetraethyl N, N'-methylenedi-4,1-cyclohexanediyl bis (aspartate) has a cyclic structure. The tetraethyl N, N'- When the tetraethyl N, N'-methylenedi-4,1-cyclohexanediylbisaspart is used as the cyclic structure, the crosslinking density of the coating film is higher than that of the conventional coating material, and mechanical N'-methylene di-tert-butyldimethoxysilane, which is excellent in strength, chemical resistance, heat resistance, water resistance, abrasion resistance and the like, is less affected by external environment and external stress, Since 4-cyclohexanediylbisaspart is composed of a cyclic structure, viscosity is low even when there is no peculiar odor of amine, so that it is easy to control viscosity when applied to a product and reactivity can be controlled. When the content of N, N'-methylene di-4,1-cyclohexanediylbisaspart is in the range of 2 to 10 parts by weight in the curing agent, the above-described functions are not sufficiently exhibited, The physical properties of the coating film deteriorate.

The non-phthalate plasticizer is the same as that used in the above-mentioned subject, and is contained in an amount of 40 to 100 parts by weight in the curing agent.

As the pigment, it is preferable to use an eco-friendly material that does not contain a heavy metal, and it is included in an amount of 4 to 15 parts by weight in the curing agent.

The calcium carbonate is used as an inorganic filler to reduce the cost of the waterproofing material and to increase the physical strength thereof. The calcium carbonate is contained in a range of 160 to 300 parts by weight in the curing agent. If the content is less than 160 parts by weight, the cost reduction and the strength increase effect are not sufficient. When the amount exceeds 300 parts by weight, It can not be manufactured.

The dimethyl carbonate is used as a solvent and is contained in a range of 8 to 25 parts by weight in the curing agent.

The bismuth is used as a catalyst and is contained in a range of 2 to 8 parts by weight in the curing agent.

In addition, the present invention may further include various additives in any of the above-mentioned bases or hardeners in addition to the above-mentioned components. In general, a water absorbent, a blocking agent, an antifoaming agent, a yellowing inhibitor and the like which can be used as an additive for a polyurethane film- .

As the water absorbing agent, at least one of bentonite, lime, and silica gel may be used in an amount of 1 to 3 parts by weight. Examples of the blocking agent include caprolactam, 3,5-dimethyl pyrazole, 1,2,4-triazole, imidazole, At least one of 2-butanone diethyl malonate, ethylacetoacetate and methylethyl ketoxime can be used in an amount of 2 to 10 parts by weight, May be used in an amount of 0.01 to 0.01 part by weight based on 100 parts by weight of a silicone antifoaming agent or a polyalkylene oxide methyl siloxane copolymer. The antifouling agent may be a UV stabilizer such as formamidine-based UV-V in an amount of 0.1 to 0.5 parts by weight .

The coating film waterproofing composition according to the present invention can be applied by using rollers or the like in various kinds of waterproof coating compositions of the prior art, and the amount of the waterproofing coating composition can be, for example, 2 to 3 kg / m 2. The drying time is about 1 to 10 hours.

In addition, the preparation of the above-mentioned subject matter and the curing agent is performed according to a conventional method of producing a urethane coating material waterproofing material, which is conventionally known, and a detailed description thereof will be omitted.

Hereinafter, the present invention will be described in detail with reference to specific examples.

(Example 1)

The base and the curing agent were prepared in the same ratios as in Table 1, and then the base and the curing agent were mixed at a weight ratio of 1: 3 to prepare a coating film waterproofing agent.

The mixing ratio of Example 1 subject Weight portion Hardener Weight portion Polyoxypropylene glycol
(Molecular weight about 2000) 100 Polyoxypropylene glycol
(Molecular weight about 3000) 100 2,4-diphenylmethane diisocyanate 50 - - Methyl propanediol 4 Methyl propanediol One 1, 4-butadiol 2.5 2,2'-dichloro-44'-methylenedianiline 12 Dimethyl carbonate 35 Tetraethyl N, N'-methylenedi-4,1-cyclohexanediylbisaspart 6 Nonphthalate-based
Plasticizer (Benzoflex®) 30 Nonphthalate-based
Plasticizer (Benzoflex®) 60 Nano-type ceramic balls
(50 nm)

10

Pigment 8 Calcium carbonate 200 Dimethyl carbonate 20 Bismuth 4

The subject was charged with polyoxypropylene glycol and 2,4-diphenylmethane diisocyanate at a blending ratio as shown in Table 1, heated to 80 to 100 占 폚, and reacted for 3 hours while maintaining the temperature at 80 to 100 占 폚. When the reaction was completed, the remaining components were added and stirred at a low speed using an agitator.

The curing agent was mixed with the components of Table 1 at the above mixing ratios and stirred at a low speed using a stirrer.

(Example 2)

The procedure of Example 1 was repeated to further include 7 parts by weight of cerium oxide having an average particle size of 30-50 μm in the subject.

(Comparative Example 1)

A coating film waterproofing material was prepared in the ratio shown in Table 2 below. The base and the curing agent were mixed at a weight ratio of 1: 2.5.

The mixing ratio of Comparative Example 1 subject Weight portion Hardener Weight portion Poly (oxypropylen) Glycol 100 Poly (oxypropylen) Glycol 100 1.3-BUTANDIOL 4 4,4-methylenebis 9 Toluene Diisocynate 32 Calcium Carbonate 200 H3PO4 0.006 Toluene 18 Xylene 15 Mineral Spirit 6 Toluene 21 24% Pb / OCP 6 Dioctyl Phthalate 16 Dioctyl Phthalate 8 2,6-Di-tert-butyl-P-cresol
0.1
Hydrocarbon Resin 16 Pigment 8

(Test Example 1)

Example 1, Example 2 and Comparative Example 1 were applied to the surface of a steel sheet to form a coating film, respectively. The coating was applied by roller and the amount of waterproofing applied was 2kg / ㎡.

Then, each metal plate was placed on the building roof, and the temperature was measured with time, and the results are shown in Table 3 below.

Results of Test Example 1 (unit: 占 폚) time External temperature Example 1 Example 2 Comparative Example 1 12 o'clock 30.2 38.8 37.2 58.2 14:00 31.9 39.1 38.2 62.2 16:00 30.3 37.6 36.8 64.2 18:00 28.5 32.2 30.6 66.2 24 hours 24.0 28.8 28.5 42.1 6 o'clock 23.5 28.0 28.2 42.5 12 o'clock 31 37.6 36.5 59.3

As can be seen from Table 3, it was confirmed that the surface temperatures of Examples 1 and 2 of the present invention were significantly reduced as compared with Comparative Example 1. In addition, it was confirmed that Example 2, which further contains cerium oxide, has better heat shielding effect than Example 1.

In addition, according to KS F 4918: 2003, the adhesion strength, the skid resistance, the amount of absorption, the compressive strength and the like were measured.

Therefore, it was confirmed that the coating film-protecting material of the present invention is not only excellent in physical properties but also excellent in heat shielding effect without using volatile organic solvents and phthalate plasticizers.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents. Should be judged.

Claims (5)

A subject comprising an isocyanate prepolymer comprising polyoxypropylene glycol, a polyesters polyol, an aromatic diisocyanate, 1,4-butadiol, dimethyl carbonate, a non-phthalate plasticizer and a nano-type ceramic ball,
Polyoxypropylene glycol, polyester polyol, 2,2'-dichloro-4,4'-methylenedianiline, tetraethyl N, N'-methylenedi-4,1-cyclohexanediylbisaspart, nonphthalate plasticizer , A pigment, a calcium carbonate, a dimethyl carbonate, and a curing agent including bismuth.
The method according to claim 1,
Wherein the base and the curing agent are mixed in a weight ratio of 1: 3.
3. The method of claim 2,
Wherein the nano-type ceramic balls are made of aluminum silicate and have a particle size of 5 to 100 nm.
The method of claim 3,
The above-mentioned subject matter includes 100 parts by weight of polyoxypropylene glycol, 40 to 100 parts by weight of aromatic diisocyanate, 2 to 6 parts by weight of polyester polyol, 1 to 4 parts by weight of 1,4-butadiol, 20 to 50 parts by weight of dimethyl carbonate, 40 to 60 parts by weight of a phthalate plasticizer and 5 to 20 parts by weight of a nano-type ceramic ball,
Wherein the curing agent is selected from the group consisting of 100 parts by weight of polyoxypropylene glycol, 0.5 to 5 parts by weight of polyester polyol, 8 to 20 parts by weight of 2,2'-dichloro-4,4'-methylene dianiline, 4 to 15 parts by weight of a pigment, 160 to 300 parts by weight of calcium carbonate, 8 to 25 parts by weight of dimethyl carbonate, And 2 to 8 parts by weight of bismuth.
5. The method of claim 4,
The nonphthalate plasticizer of the above-mentioned subject matter and the curing agent is a mixture containing one single substance or two or more selected from the group consisting of C8-C20 alcohol type, ester type, carboxylate type, aliphatic type and benzoate type plasticizers,
The subject matter of the present invention further comprises 5 to 10 parts by weight of cerium oxide.