KR102370533B1 - Polyurea paint for interior and exterior of buildings with excellent thermal insulation performance and thermal shock resistance, and manufacturing method thereof - Google Patents

Abstract

The present invention relates to polyurea paint for interior and exterior of a building having excellent thermal insulation performance and thermal shock resistance, and a manufacturing method therefor. According to the present invention, the polyurea paint for interior and exterior of a building having excellent thermal insulation performance and thermal shock resistance comprises: a first agent including an isocyanate group-terminated prepolymer; and a second agent including a polyamine mixture including polyetheramine and polyaspartic amine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified thermal insulation particles.

Description

Polyurea paint for interior and exterior of buildings with excellent thermal insulation performance and thermal shock resistance, and manufacturing method thereof

The present invention relates to a polyurea paint for interior and exterior use of a building having excellent thermal insulation performance and thermal shock resistance, and a method for manufacturing the same.

Paint has been widely used as a finishing material for construction for a long time due to the protection of materials inside and outside the building, the aesthetics of the exterior, the convenience of construction, and the convenience of maintenance.

The constituent components of the paint composition are binder resins and pigments, and it is difficult to sufficiently satisfy various physical properties required for architectural finishing materials alone.

Although only small amounts of these functional additives are formulated, they play a very important role in paints. In order for the functional additive to exhibit a stable effect with only a small amount, it must be compatible with the binder resin or have a property of being dispersed into fine particles, and a functional additive that improves certain physical properties may reduce other properties. It is necessary to properly select a specific material and required amount by grasping the physical properties and the reduced physical properties.

On the other hand, as a similar prior literature thereto, Korean Patent Registration No. 10-17680811 has been proposed.

Republic of Korea Patent Publication No. 10-17680811 (2017.08.08.)

In order to solve the above problems, an object of the present invention is to provide a polyurea paint for interior and exterior of a building excellent in heat shielding performance and thermal shock resistance, and a method for manufacturing the same.

Another object of the present invention is to provide a polyurea paint for interior and exterior use of a building, which is less yellowing and has excellent mechanical strength such as tensile strength, and a method for manufacturing the same.

However, the above purpose is illustrative, and the technical spirit of the present invention is not limited thereto.

One aspect of the present invention for achieving the above object is a first agent comprising an isocyanate group-terminated prepolymer; and a second agent comprising a polyamine mixture comprising polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat-insulating particles; Containing, Thermal insulation performance and thermal shock resistance It relates to this excellent polyurea paint for interior and exterior use of buildings.

In one aspect, the surface-modified graphene oxide, the surface-modified cordierite, and the surface-modified heat shielding particles may be surface-modified with an amine group-containing silane compound.

In one aspect, the polyamine mixture may have a weight ratio of polyetheramine:polyasparticamine of 100:10 to 50.

In one aspect, the isocyanate group-terminated prepolymer may be prepared from aliphatic diisocyanate, aromatic diisocyanate, polyetheramine and polyhexamethylene carbonate diol.

In one aspect, the molar ratio of the aliphatic diisocyanate to the aromatic diisocyanate may be 1:0.1 to 0.5.

In one aspect, the molar ratio of the polyetheramine: polyhexamethylene carbonate diol may be 1: 0.01 to 0.2.

In addition, another aspect of the present invention is a first agent comprising an isocyanate group-terminated prepolymer; and a second agent including a polyamine mixture including polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat-insulating particles; preparing a coating composition by mixing It relates to a method for producing a polyurea paint for interior and exterior of a building having excellent thermal insulation performance and thermal shock resistance, including.

The polyurea paint for interior and exterior use of a building according to the present invention includes a first agent including an isocyanate group-terminated prepolymer; a polyamine mixture including polyetheramine and polyasparticamine, surface-modified graphene oxide, and surface-modified cordierite and a second agent including surface-modified heat-insulating particles; by using the mixture, not only excellent waterproof performance, but also excellent heat-shielding performance and thermal shock resistance can be achieved.

In addition, since the heat shielding performance and thermal shock resistance are excellent, the coating film can be stably maintained for a long period even when exposed to ultraviolet rays and heat for a long period of time, and the change in physical properties according to the temperature change is small, so it can have excellent durability and adhesion.

Hereinafter, the polyurea paint for interior and exterior of a building excellent in thermal insulation performance and thermal shock resistance according to the present invention and a manufacturing method thereof will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

One aspect of the present invention is a first agent comprising an isocyanate group-terminated prepolymer; and a second agent comprising a polyamine mixture comprising polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat-insulating particles; Containing, Thermal insulation performance and thermal shock resistance It relates to this excellent polyurea paint for interior and exterior use of buildings.

As such, the polyurea paint for interior and exterior of a building according to the present invention includes a first agent including an isocyanate group-terminated prepolymer; a polyamine mixture including polyetheramine and polyasparticamine, surface-modified graphene oxide, and surface-modified cody By mixing and using a second agent including errite and surface-modified heat-shielding particles, it has excellent waterproof performance, and excellent heat-shielding performance and thermal shock resistance can be achieved.

In addition, since the heat shielding performance and thermal shock resistance are excellent, the coating film can be stably maintained for a long period even when exposed to ultraviolet rays and heat for a long period of time, and the change in physical properties according to the temperature change is small, so it can have excellent durability and adhesion.

Hereinafter, each component of the polyurea paint for interior and exterior of a building according to an example of the present invention will be described in more detail.

First, the first agent, which is the subject part, will be described.

As described above, the first agent according to an embodiment of the present invention may include an isocyanate group-terminated prepolymer, and specifically, an isocyanate prepared from aliphatic diisocyanate, aromatic diisocyanate, polyetheramine and polyhexamethylene carbonate diol. group-terminated prepolymers.

As such, polyurea having excellent tensile strength and adhesion while reducing yellowing when reacting with polyhexamethylene carbonate diol and polyetheramine using aromatic diisocyanate without using only aliphatic diisocyanate as the diisocyanate paint can be provided.

For this purpose, it is preferable to appropriately adjust the ratio of each component. When too much aromatic diisocyanate is added, the effect of reducing the yellowing phenomenon may be insignificant. When too much aliphatic diisocyanate is added, the yellowing phenomenon is reduced, but tensile strength Strength and adhesion may be reduced.

Preferably, the molar ratio of the aliphatic diisocyanate to the aromatic diisocyanate may be 1:0.1 to 0.5, more preferably 1:0.1 to 0.3, even more preferably 1:0.2 to 0.3. In this range, it is possible to effectively prevent yellowing and maintain excellent tensile strength and adhesion.

At this time, even when the aliphatic diisocyanate is used in the molar ratio range, when the polyhexamethylene carbonate diol is added too little, the tensile strength may decrease, and when the polyhexamethylene carbonate diol is added too much, a lifting phenomenon may occur after polyurea construction. It's not good to be able

Preferably, the molar ratio of the polyetheramine: polyhexamethylene carbonate diol may be 1: 0.01 to 0.2, more preferably 1: 0.01 to 0.1, even more preferably 1: 0.05 to 0.1. In this range, the polyurea prepared from the prepolymer reacted with the aliphatic diisocyanate and the aromatic diisocyanate satisfying the molar ratio range can maintain excellent tensile strength, and the lifting phenomenon after construction may not occur.

In addition, the diisocyanate compound composed of the aliphatic diisocyanate and the aromatic diisocyanate must be reacted with an active hydrogen group-containing compound composed of polyetheramine and polyhexamethylene carbonate diol in an appropriate molar ratio to synthesize the isocyanate group-terminated prepolymer. For example, the molar ratio of the diisocyanate compound: the active hydrogen group-containing compound may be 1:0.5 to 1, more preferably 1:0.7 to 0.9.

Meanwhile, in one embodiment of the present invention, the aliphatic diisocyanate is any one or two or more selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate, and the aromatic diisocyanate is toluene diisocyanate. And it may be any one or two or more selected from the group consisting of diphenylmethane diisocyanate. By using these as a diisocyanate compound, it is possible to improve the adhesion to the substrate after construction.

In one embodiment of the present invention, the polyetheramine may be used without particular limitation as long as it is a polyetheramine commonly used in the art, and preferably has a weight average molecular weight of 200 to 5000 g/mol, and a functional group of 2 to Three aliphatic polyetheramines can be used, and more preferably, an aliphatic polyetheramine having a weight average molecular weight of 500-3000 g/mol and having 2-3 functional groups is used to form a polyurea paint with excellent tensile strength. it is preferable to have

In an example of the present invention, the polyhexamethylene carbonate diol may have a weight average molecular weight of 500 to 5000 g/mol, and more preferably, use a weight average molecular weight of 1000 to 3000 g/mol for durability. It is preferable for forming an excellent polyurea paint.

Next, the 2nd agent which is a hardening|curing agent part is demonstrated. As described above, the second agent according to an embodiment of the present invention is a polyamine mixture comprising polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat shielding particles. may include Through this, it is possible to provide a polyurea paint having higher water-repellent properties and heat-shielding properties.

The second agent may be mixed in an amount of 50 to 200 parts by weight based on 100 parts by weight of the first agent, preferably 70 to 180 parts by weight, more preferably 100 to 150 parts by weight, but the first agent and the second agent It goes without saying that the mixing ratio can be adjusted according to the content of reactive groups (isocyanate groups and amine groups, etc.) contained in the agent.

On the other hand, in an example of the present invention, the second agent may include polyetheramine and polyasparticamine in terms of securing better waterproofness and workability. Preferably, the polyamine mixture may have a weight ratio of polyetheramine: polyasparticamine of 100: 10 to 50, and more preferably, 100: 20 to 30. When the amount of polyasparticamine is added in an amount of less than 10 parts by weight based on 100 parts by weight of the polyetheramine, the curing rate is too slow and the tensile strength may be lowered. This may decrease, and the brittleness of the coating film increases after construction, which may cause problems with waterproofing.

In this case, the polyetheramine according to an example of the present invention may be the same as or different from the polyetheramine of the first agent, specifically, for example, a weight average molecular weight of 200 to 5000 g/mol, and a functional group Two to three aliphatic polyetheramines can be used, and more preferably, an aliphatic polyetheramine having a weight average molecular weight of 500 to 3000 g/mol and two to three functional groups is used to obtain a polyurea paint with excellent tensile strength. It is preferable to form.

In an example of the present invention, the polyaspartic amine is a secondary amine having a bulky three-dimensional structure, and when used by mixing with polyetheramine in an appropriate ratio, the curing rate of polyurea is appropriately controlled to work Not only the performance is improved, but it is possible to achieve better tensile strength and elongation, thereby securing better waterproof properties. The amine value of the polyaspartic amine may be 180 to 220 mg KOH/g, and more preferably 190 to 210 mg KOH/g. Also, the viscosity at 25° C. may be 500 to 5000 cP, and more preferably 800 to 2500 cP.

In one embodiment of the present invention, the surface-modified graphene oxide is added to improve the waterproof and thermal insulation effect of the polyurea paint, and specifically, the surface-modified graphene oxide is an amine group-containing silane compound. It may be modified. As such, by using graphene oxide surface-modified with an amine group-containing silane compound, a covalent bond between graphene oxide and polyurea is induced, so that the graphene oxide in the coating film is uniformly dispersed, thereby securing excellent waterproof and thermal insulation properties, It is possible to effectively prevent defects such as pinholes due to improved compatibility.

In this case, the graphene oxide may be prepared by exfoliating graphite through the Hummer method, and may be single-layer graphene oxide or similar graphene (graphite) in which several to tens of graphene oxide layers are stacked. As such graphene oxide is manufactured through a simple process of exfoliating graphite using a strong acid and an oxidizing agent, it is possible to reduce manufacturing costs compared to graphene or reduced graphene oxide. Since the oxygen functional group is formed, the surface can be easily modified with an amine group-containing silane compound later, so that the graphene oxide in the second agent can be more uniformly dispersed.

On the other hand, the amine group-containing silane compound used for surface modification of graphene oxide is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-amino Ethyl)-3-aminopropyl trimethoxysilane, 2-aminopropyl-3-aminopropyl trimethoxysilane, 2-aminopropyl-3-aminopropyl triethoxysilane, 2-aminoethyl-2-aminoethyl- It may be any one or two or more selected from the group consisting of 3-aminopropyl trimethoxysilane and 2-aminoethyl-2-aminoethyl-3-aminopropyltriethoxysilane.

The surface-modified graphene oxide may be added in an amount of 1 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the polyetheramine of the second agent. In such a range, the waterproof and thermal insulation effect is excellent. On the other hand, when the surface-modified graphene oxide is added in an amount of less than 1 part by weight, the improvement effect of waterproof and thermal insulation properties is insignificant. It is not good because it may deteriorate and the waterproofness may decrease.

In one embodiment of the present invention, the surface-modified cordierite is for improving the thermal shock resistance of the coating film, and the pullulurea coating film formed after painting the paint has a large coefficient of thermal expansion, so that cracks are prevented when external thermal shock is repeatedly applied. Although there is a disadvantage in that durability is deteriorated, such as occurrence, thermal shock resistance can be improved by including cordierite having a very small coefficient of thermal expansion.

Specifically, the surface-modified cordierite may be surface-modified with an amine group-containing silane compound. As such, by using the surface-modified cordierite with an amine group-containing silane compound, a chemical bond between the cordierite and polyurea is induced, so that the cordierite in the coating film is uniformly dispersed, thereby ensuring excellent thermal shock resistance.

In this case, the cordierite may have a chemical formula of 2MgO-2Al ₂ O ₃ -5SiO ₂ . By using cordierite that satisfies this, it provides excellent thermal shock resistance even when exposed to UV rays and seasonal temperature changes for a long period of time, thereby suppressing the problem of cracks or adhesion deterioration in the coating film, thereby improving durability. there is. In addition, it is preferable that the cordierite powder has a purity of 90% or more and a particle size of 10 to 50 μm, but is not necessarily limited thereto.

On the other hand, the amine group-containing silane compound used for surface modification of cordierite is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-amino Ethyl)-3-aminopropyl trimethoxysilane, 2-aminopropyl-3-aminopropyl trimethoxysilane, 2-aminopropyl-3-aminopropyl triethoxysilane, 2-aminoethyl-2-aminoethyl- It may be any one or two or more selected from the group consisting of 3-aminopropyl trimethoxysilane and 2-aminoethyl-2-aminoethyl-3-aminopropyltriethoxysilane.

The surface-modified cordierite may be added in an amount of 3 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of the polyetheramine of the second agent. In such a range, the waterproof and thermal insulation effect is excellent. In this range, the thermal shock resistance is excellent, and the adhesion and crack resistance of the coating film may not be deteriorated.

In one embodiment of the present invention, the surface-modified heat shielding particles effectively reflect infrared rays that generate thermal energy in sunlight to suppress the conversion of infrared rays into thermal energy, which is also surface-modified with an amine group-containing silane compound. it could be As such, by using the heat shielding particles surface-modified with an amine group-containing silane compound, a covalent bond between the heat shielding particles and polyurea is induced, so that the heat shielding particles in the coating film are uniformly dispersed, thereby securing excellent heat shielding properties.

In this case, the heat shielding particles may be used without particular limitation as long as they are commonly used in the art, and it is preferable to use metal oxide particles having excellent infrared reflection effect. As a specific example, the heat shielding particles are selected from the group consisting of antimony tin oxide (ATO), indium tin oxide (ITO), cesium tungsten oxide (CWO) and antimony trioxide-zinc oxide (Sb ₂ O ₃ -ZnO). It may be one or two or more. Such metal oxide particles have an advantage in that they can effectively reflect infrared rays that generate thermal energy to provide excellent heat shielding performance.

The shape of such heat-shielding particles may be a particle shape such as a spherical shape, a rod shape, a needle shape, or a hollow shape, and the average particle size of the heat-shielding particle may be 2 to 200 nm, more preferably 5 to 100 nm can In such a range, the heat shielding effect is particularly excellent.

On the other hand, the amine group-containing silane compound used for surface modification of the heat shielding particles is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl). )-3-Aminopropyl trimethoxysilane, 2-aminopropyl-3-aminopropyl trimethoxysilane, 2-aminopropyl-3-aminopropyl triethoxysilane, 2-aminoethyl-2-aminoethyl-3 It may be any one or two or more selected from the group consisting of -aminopropyl trimethoxysilane and 2-aminoethyl-2-aminoethyl-3-aminopropyltriethoxysilane.

The surface-modified heat shielding particles may be added in an amount of 5 to 30 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the polyetheramine of the second agent. In such a range, the heat shielding effect is excellent. On the other hand, when the surface-modified heat shielding particles are added in less than 5 parts by weight, the heat shielding effect due to infrared reflection is insignificant. not.

Furthermore, the second agent according to an embodiment of the present invention may further include an antioxidant and a UV stabilizer, and through this, it is possible to further suppress yellowing of the polyurea coating film caused by sunlight.

In one embodiment of the present invention, the antioxidant may be a hindered phenol-based antioxidant, and as a specific example, 4,4'-methylene-bis(2,6-di-t-butylphenol), octadecyl -3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)prop cionate] may be any one or two or more selected from the group consisting of.

The antioxidant may be added in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyetheramine of the second agent. In such a range, the desired effect can be achieved.

In one embodiment of the present invention, the ultraviolet stabilizer may use a hindered amine-based ultraviolet stabilizer, as a specific example, 2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-n -Butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3 ,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)ceba Kate, consisting of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate It may be any one or two or more selected from the group.

The ultraviolet stabilizer may be added in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyetheramine of the second agent. In such a range, the desired effect can be achieved.

In addition to this, the first or second agent may further include any one or two or more additives selected from the group consisting of catalysts, color pigments, plasticizers and defoamers, etc., if necessary, and specific types and contents are conventional may be selected within the range.

In addition, another aspect of the present invention relates to a method for producing the above-described polyurea paint, specifically, a first agent comprising an isocyanate group-terminated prepolymer; and a second agent including a polyamine mixture including polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat-insulating particles; preparing a coating composition by mixing ; may be included.

At this time, since each component of the first agent and the second agent is the same as described above, a redundant description is omitted, and the mixing method and coating method of each component may be performed by a method commonly used in the art. .

Hereinafter, the polyurea paint for interior and exterior of a building excellent in heat shielding performance and thermal shock resistance according to the present invention and a manufacturing method thereof will be described in more detail through Examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention. In addition, the unit of additives not specifically described in the specification may be weight %.

1) Surface-modified inorganic particles

[Surface-modified graphene oxide]

After dissolving 1 ml of 3-aminopropyl triethoxysilane in 100 ml of ethylcellusolve, 250 ml of graphene oxide dispersed in water (4 mg/ml, in H ₂ O, D ₅₀ 14.3 to 16.6 μm) was dispersed 12 stirred for hours. Thereafter, it was filtered and dried to prepare surface-modified graphene oxide.

[Surface modified cordierite]

After dissolving 1 ml of 3-aminopropyl triethoxysilane in 100 ml of ethyl cellusolve, 20 g of cordierite (2MgO-2Al ₂ O ₃ -5SiO ₂ , average particle size 20 μm) was mixed and stirred for 24 hours. Thereafter, the surface-modified ATO was prepared by filtration and drying.

[Surface-modified heat shielding particles]

After dissolving 1 ml of 3-aminopropyl triethoxysilane in 100 ml of ethyl cellusolve, 15 g of antimony tin oxide (ATO) nanosol (30 wt%, particle size 53.9 nm, in ethyl cellusolve) was mixed for 12 hours. stirred. Thereafter, the surface-modified ATO was prepared by filtration and drying.

2) Prepolymer Synthesis

[Production Example 1]

Hexamethylene diisocyanate (HDI) 1 mol, toluene diisocyanate (TDI) 0.25 mol, polyetheramine (weight average molecular weight 2,000 g / mol) 0.93 mol and polyhexamethylene carbonate diol (PHCD, weight average molecular weight 2,000) 0.07 mol After mixing, the mixture was reacted at 60° C. for 2 hours and at 90° C. for 3 hours, and then cooled to room temperature to prepare a prepolymer.

[Production Example 2]

Hexamethylene diisocyanate (HDI) 0.625 mol, toluene diisocyanate (TDI) 0.625 mol, polyetheramine (PEA, weight average molecular weight 2,000 g/mol) 0.93 mol and polyhexamethylene carbonate diol (PHCD, weight average molecular weight 2,000) 0.07 After mixing mol, the reaction was carried out at 60° C. for 2 hours and at 90° C. for 3 hours, and then cooled to room temperature to prepare a prepolymer.

[Production Example 3]

Hexamethylene diisocyanate (HDI) 0.25 mol, toluene diisocyanate (TDI) 1 mol, polyetheramine (PEA, weight average molecular weight 2,000 g/mol) 0.93 mol and polyhexamethylene carbonate diol (PHCD, weight average molecular weight 2,000) 0.07 After mixing mol, the reaction was carried out at 60° C. for 2 hours and at 90° C. for 3 hours, and then cooled to room temperature to prepare a prepolymer.

[Production Example 4]

After mixing 1.25 mol of hexamethylene diisocyanate (HDI) and 1 mol of polyetheramine (PEA, weight average molecular weight of 2,000 g/mol), reacted at 60°C for 2 hours and 90°C for 3 hours, then cooled to room temperature to obtain a prepolymer prepared.

[Production Example 5]

After mixing 1.25 mol of toluene diisocyanate (TDI) and 1 mol of polyetheramine (PEA, weight average molecular weight of 2,000 g/mol), reacted at 60° C. for 2 hours and 90° C. for 3 hours, followed by cooling to room temperature to prepare a prepolymer did

[Production Example 6]

After mixing 1 mol of hexamethylene diisocyanate (HDI), 0.25 mol of toluene diisocyanate (TDI) and 1 mol of polyetheramine (PEA, weight average molecular weight of 2,000 g/mol), at 60°C for 2 hours, at 90°C for 3 hours After the reaction was cooled to room temperature, a prepolymer was prepared.

(number of moles, mol) prepolymer HDI MDI PEA1 PHCD Preparation Example 1 One 0.25 0.93 0.7 Preparation 2 1.2 0.05 0.93 0.7 Preparation 3 0.25 One 0.93 0.7 Preparation 4 1.25 - One - Preparation 5 - 1.25 One - Preparation 6 One 0.25 One -

[Example 1]

A polyurea coating composition was prepared by mixing 100 parts by weight of the second agent with respect to 100 parts by weight of the prepolymer prepared in Preparation Example 1.

At this time, the second agent is based on 100 parts by weight of polyetheramine (PEA, weight average molecular weight 2,000 g / mol), polyaspartic amine (PAA, amine value 201 mg KOH / g, viscosity at 25 ° C. 1500 CP, density 1.08 g/ml, equivalent weight 276) 25 parts by weight, 1 part by weight of the surface-modified graphene oxide, 3 parts by weight of the surface-modified cordierite, 15 parts by weight of the surface-modified ATO, 4,4'-methylene- Bis(2,6-di-t-butylphenol) (antioxidant) 1.5 parts by weight and (2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-n-butylmalonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl (ultraviolet stabilizer) was prepared by mixing 2 parts by weight.

[Examples 2 to 7]

All processes were performed in the same manner as in Example 1 except that the amount of surface-modified graphene oxide, surface-modified cordierite, and heat-shielding particles was changed.

[Examples 8 to 12]

All processes were performed in the same manner as in Example 1 except for using the prepolymers prepared in Preparation Examples 2 to 6, respectively.

[Comparative Examples 1 to 3]

All processes were performed in the same manner as in Example 1 except that the amount of surface-modified graphene oxide, surface-modified cordierite, and heat-shielding particles was changed.

[Comparative Example 4]

All processes except for using non-surface-modified graphene oxide, cordierite and ATO particles were performed in the same manner as in Example 1.

First agent (100 parts by weight) Second agent (100 parts by weight) prepolymer PEA PAA graphene oxide cordierite heat shielding particles Example 1 Preparation Example 1 100 25 One 9 15 Example 2 Preparation Example 1 100 25 5 9 15 Example 3 Preparation Example 1 100 25 10 9 15 Example 4 Preparation Example 1 100 25 5 3 15 Example 5 Preparation Example 1 100 25 5 15 15 Example 6 Preparation Example 1 100 25 5 9 5 Example 7 Preparation Example 1 100 25 5 9 30 Example 8 Preparation 2 100 25 5 9 15 Example 9 Preparation 3 100 25 5 9 15 Example 10 Preparation 4 100 25 5 9 15 Example 11 Preparation 5 100 25 5 9 15 Example 12 Preparation 6 100 25 5 9 15 Comparative Example 1 Preparation Example 1 100 25 0 9 15 Comparative Example 2 Preparation Example 1 5 0 15 Comparative Example 3 Preparation Example 1 100 25 5 9 0 Comparative Example 4 Preparation Example 1 100 25 5
(unmodified) 9
(unmodified) 15
(unmodified)

[Characteristic evaluation]

1) Heat shielding properties: The compositions of Examples and Comparative Examples were coated on a concrete substrate to a thickness of 5 mm, respectively, and then cured for 24 hours to prepare a test piece. The test piece was installed on the floor, and a 100W incandescent lamp was installed at a height of 27 cm. The temperature of each test piece was measured when the incandescent lamp was turned on and the test piece reached 60° C., and the temperature difference (ΔT) between the test piece and the test piece was shown in Table 3 below.

2) Thermal shock resistance: Each of the compositions of Examples and Comparative Examples was applied to a thickness of 5 mm on a concrete substrate and cured for 24 hours to prepare a test piece. In order to evaluate the thermal shock resistance of the Examples and Comparative Examples, a rapid temperature change environment was created. According to ASTM D-1647, the test piece was subjected to a thermal shock test 100 times at -40°C to 85°C for 30 minutes each, and whether defects (wrinkles, cracks, swelling, peeling) occurred were confirmed with an optical microscope. The evaluation results are shown in Table 2 below as (number of defective specimens)/(total number of specimens).

3) Tensile strength (N/mm2): The compositions of Examples and Comparative Examples were coated on a concrete substrate to a thickness of 5 mm, respectively, and cured for 24 hours to prepare a test piece. The tensile strength of the test piece was measured in accordance with KS F 4922: 2007.

4) Adhesive strength (N/㎟): The compositions of Examples and Comparative Examples were coated on a concrete substrate to a thickness of 5 mm, respectively, and then cured for 24 hours to prepare a test piece. The adhesion strength of the test piece was measured according to KS F 4922: 2007.

5) Yellowing properties: For the yellowing properties of the polyurea specimens, after exposure for 200 hours in a QUV weatherometer, the degree of discoloration was visually checked, and it was judged as acceptable if there was little or no yellowing, and as unsuitable if yellowing occurred.

thermal insulation performance
(ΔT, ℃) thermal shock resistance tensile strength
(N/㎟) Adhesive strength
(N/㎟) yellowing Example 1 12.9 0/100 21 2.6 fitness Example 2 17.3 0/100 22 2.9 fitness Example 3 17.7 0/100 20 2.5 fitness Example 4 17.1 1/100 23 3.0 fitness Example 5 16.5 0/100 20 2.7 fitness Example 6 5.6 1/100 21 2.9 fitness Example 7 20.0 0/100 15 2.2 fitness Example 8 18.4 0/100 16 2.4 fitness Example 9 17.8 0/100 19 3.1 incongruity Example 10 18.3 0/100 12 2.7 fitness Example 11 17.7 0/100 19 3.3 incongruity Example 12 18.1 0/100 17 2.9 fitness Comparative Example 1 11.6 0/100 21 2.7 fitness Comparative Example 2 17.5 7/100 24 3.0 fitness Comparative Example 3 2.3 2/100 19 2.9 fitness Comparative Example 4 10.2 4/100 15 2.5 fitness

Examples 1 to 7 of Table 3 showed superior heat shielding performance, thermal shock resistance, tensile strength and adhesion strength compared to Comparative Examples, and in particular, surface-modified graphene oxide, cordierite, and heat shielding particles participated in an appropriate amount. In the case of Example 2, it was confirmed that the thermal shock resistance, tensile strength, and adhesion were excellent while showing high heat-shielding performance, and there was almost no yellowing phenomenon.

On the other hand, in the case of Comparative Example 1 to which the surface-modified graphene oxide was not added, the heat shielding performance was somewhat lower than that of Example 2, and in the case of Comparative Example 2 to which the surface-modified cordierite was not added, the thermal shock resistance was significantly lowered, In Comparative Example 3 in which the surface-modified heat-shielding particles were not added, the heat-shielding performance was insignificant, and in Comparative Example 4 using non-surface-modified graphene oxide, cordierite and heat-shielding particles, each particle was not homogeneously dispersed. , especially in the case of graphene oxide, the aggregation phenomenon due to pi-pi bonding was severe, so that both the heat shielding performance and the adhesion strength were not as good as in Example 2.

On the other hand, in Example 8 and Nabi 12 in which the urethane prepolymer was used differently, in Examples 8 and 10 in which too little aromatic isocyanate was added, tensile strength and adhesion strength were somewhat lowered, and in Example 9 and in which too much aromatic isocyanate was added, In the case of 11, there was a problem in which yellowing occurred.

In addition, even in the case of Example 12 in which polyhexamethylene carbonate diol was not added in an appropriate amount, the tensile strength was somewhat decreased.

Although the present invention has been described with reference to specific matters and limited examples as described above, these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention belongs to Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (7)

a first agent comprising an isocyanate group-terminated prepolymer prepared from aliphatic diisocyanate, aromatic diisocyanate, polyetheramine and polyhexamethylene carbonate diol; and
a second agent comprising a polyamine mixture including polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat-insulating particles;
Polyurea paint for interior and exterior of buildings with excellent thermal insulation performance and thermal shock resistance, including
The method of claim 1,
The surface-modified graphene oxide, the surface-modified cordierite and the surface-modified heat-insulating particles are surface-modified with an amine group-containing silane compound.
The method of claim 1,
The polyamine mixture has a weight ratio of polyetheramine: polyasparticamine of 100: 10 to 50, and is a polyurea paint for interior and exterior of buildings with excellent thermal insulation performance and thermal shock resistance.
delete The method of claim 1,
The aliphatic diisocyanate: the molar ratio of the aromatic diisocyanate is 1: 0.1 to 0.5, a polyurea paint for interior and exterior of a building having excellent thermal insulation performance and thermal shock resistance.
The method of claim 1,
The polyetheramine: polyhexamethylene carbonate diol molar ratio of 1: 0.01 to 0.2, a polyurea paint for interior and exterior of a building excellent in thermal insulation performance and thermal shock resistance.
a first agent comprising an isocyanate group terminated prepolymer prepared from aliphatic diisocyanate, aromatic diisocyanate, polyetheramine and polyhexamethylene carbonate diol; and a second agent including a polyamine mixture including polyetheramine and polyasparticamine, surface-modified graphene oxide, surface-modified cordierite, and surface-modified heat-insulating particles; preparing a coating composition by mixing A method for producing a polyurea paint for interior and exterior of a building, which has excellent thermal insulation performance and thermal shock resistance, including.