KR101377416B1 - Coating composition having transparent and heat-shield property, and Coated material employing the same - Google Patents

Abstract

According to one aspect of the invention, it is characterized in that the conductive inorganic oxide particles surface-modified with a metal alkoxide composite containing a urethane group (or urea group) and acryl, a photoinitiator and a composition of a solvent. According to another aspect of the present invention, the thermal barrier coating composition consisting of the above-described composition is applied to a surface of a substrate selected from plastic, glass, paper, and cloth such as polyethylene terephthalate (PET) with a predetermined thickness and UV-cured coating It is characterized by obtaining water.
Accordingly, according to the configuration of the present invention it is possible to manufacture a heat-transfer coating agent having a high visible light transmittance excellent visibility and excellent UV and infrared ray blocking rate excellent heat insulation.

Description

Coating composition having transparency and heat insulation and coating using the same {Coating composition having transparent and heat-shield property, and Coated material employing the same}

The present invention relates to a coating agent having transparency and thermal insulation, and more particularly, to a coating composition having excellent visible light transmittance, high internal roughness, and excellent ultraviolet blocking properties, which are a major cause of greenhouse effect and heating and heating load, and harmful UV rays to the human body. It relates to a coating using the same.

In recent years, buildings such as apartments, buildings, and residential complexes tend to finish many parts of buildings with transparent materials in order to realize the appearance of luxury and light effect. Since ordinary glass passes most of the sunlight, in summer, radiant heat from the sun enters the room to increase the room temperature, and in winter, the heating heat of the room escapes to the outside and lowers the room temperature. Increasingly, the need for a coating that can effectively block ultraviolet rays and infrared rays is increasing. Solar energy is classified into wavelengths of ultraviolet rays, visible rays, and infrared rays. The biggest factor that raises the temperature is the energy of the near-infrared region, and the energy of these regions is absorbed to increase the temperature. The thermal barrier coating agent refers to a coating agent that can suppress the temperature rise in the room by blocking energy in the infrared region contributing to the temperature rise.

As a way to block the sun's heat, a special glass, Roy glass, has been used to block hot sunlight in the summer. The low glass has low infrared rays and the long wave reflection of the heating wire increases the indoor long wave. Due to blocking the external leakage of radiant heat, the room temperature is increased, so the energy consumption is increased, especially in summer, and the coating film is becoming more preferred due to the high production cost. In addition, the tinting film or the metal coating film is effective in the early stage, but the durability of the film is low, there is a problem that the discoloration or peeling phenomenon occurs after a period of time, the infrared blocking effect function is sharply lowered, blocking not only ultraviolet rays but also visible light This is not suitable as a building film because the field of view is not secured. Therefore, the demand for a non-reflective transparent thermal barrier film that effectively blocks heat rays, that is, infrared rays, which is a major cause of the greenhouse effect and cooling load due to high visible light transmittance is increasing steadily.

Therefore, various studies on the method of manufacturing a thermal barrier coating having such characteristics have been reported. In the patents of Korean Unexamined Patent Publication Nos. 1996-0021518, 2010-0112464, and Japanese Patent Laid-Open No. Hei 9-300516, a vehicle comprising an organic photochromic dye such as an azobenzene compound and a spiropyran compound is used. Manufacturing methods for thermal barrier coatings for shading windows have been published. However, in the above case, the durability is low and the visible light transmittance is low.

In Japanese Patent Application Laid-Open Nos. 56-156606 and 63-281837, a thermal barrier coating was prepared by mixing a binder resin and a surfactant with antimony doped tin oxide (ATO). Since the coating film is to be thickly coated, a disadvantage occurs that the visible light transmittance is greatly lowered.

In addition, Korean Patent Nos. 1019498 and 0525307 describe a method for manufacturing a thermal barrier film containing a tungsten bronze compound or another type of metal oxide, but the visible light transmittance and the blocking effect in the vicinity of near infrared rays are low.

An object of the present invention for improving the conventional problems as described above, by modifying the surface of the conductive inorganic oxide particles with a metal alkoxide composite containing a urethane group (or urea group) and acrylic visible light transmittance, UV blocking rate and infrared ray blocking rate It is to provide this excellent UV curable thermal barrier coating.

In order to achieve the above object, according to an aspect of the present invention, a urethane group or a urea group is characterized by consisting of a conductive inorganic oxide particles surface-modified with a metal alkoxide complex containing an acryl, a photoinitiator and a composition.

In this case, the metal alkoxide complex is characterized in that the compound represented by the following <Formula 2>.

(2)

Meanwhile, the present invention is a conductive inorganic oxide selected from indium tin oxide (ITO), antimony tin oxide (ATO), aluminum doped zinc oxide (Al-dopped ZnO), gallium doped zinc oxide (Ga-dopped ZnO). 100 to 300 parts by weight of the metal alkoxide complex compound for surface modification, 1 to 10 parts by weight of a photoinitiator selected from benzophenone and 1-hydroxycyclohexyl phenyl ketone, 200 to 400 parts by weight of an organic solvent, And 2 to 10 parts by weight of a catalyst for surface modification selected from potassium hydroxide and amine which are acid catalysts or basic catalyst aqueous solutions selected from hydrochloric acid, sulfuric acid, acetic acid and phosphoric acid.

According to another aspect of the present invention, a coating composition having transparency and heat insulating properties comprising the above compounding composition is applied to a surface of a substrate selected from plastic, glass, paper, and cloth such as polyethylene terephthalate (PET) at a predetermined thickness, and subjected to ultraviolet rays. It is characterized by hardening and obtaining a coating.

As described above, according to the present invention, it is possible to provide an ultraviolet curable thermal barrier coating composition and a coating material coated with excellent optical properties such as visible light transmittance, ultraviolet ray and infrared ray blocking rate, and cured film properties such as hardness and wear resistance.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a thermal barrier coating composition having high visible light transmittance and high internal roughness and excellent infrared and ultraviolet ray blocking properties and mechanical properties of a cured coating film. More specifically, the present invention relates to a metal including a urethane group (or urea group) and acryl. Consists of the composition of conductive inorganic oxide particles, photoinitiators and solvents surface-modified with an alkoxide composite, it has excellent transparency and excellent thermal insulation properties due to high UV and infrared blocking rate.

More specifically, the UV-curable thermal barrier coating composition of the present invention 100 to 300 parts by weight of the compound for surface modification, 2 to 10 parts by weight of catalyst for surface modification, 1 to 10 parts by weight of photoinitiator with respect to 100 parts by weight of the conductive inorganic oxide It is characterized by using 200 to 400 parts by weight of an organic solvent.

Referring to each component of the ultraviolet curable thermal barrier coating composition and the surface treatment method in more detail as follows.

Metal oxides used in the manufacture of UV-curable thermal barrier coatings of the present invention can be used in most of the nanoparticles having infrared blocking properties, in the present invention is doped with indium tin oxide (ITO), antimony tin oxide (ATO), aluminum It is preferable to use metal oxides such as zinc oxide (Al-dopped ZnO) and gallium doped zinc oxide (Ga-dopped ZnO).

The metal alkoxide complex of the acrylic group terminal for surface modification of the conductive inorganic oxide particles of the present invention is prepared by the following method.

First, a metal alkoxide having a compound Y containing a non-covalent electron pair such as a mercapto group, an amino group, an alcohol group, an epoxy group, etc. which can react with an isocyanate and diisocyanate is reacted at a temperature of room temperature to 80 ° C. for 1 to 2 hours. The alkoxide compound containing terminal isocyanate group is prepared.

&Lt; Formula 1 >

In Formula 1, M is a metal selected from silicon, titanium, and aluminum, and R ¹ represents a C1 to C10 linear or crushed alkyl group, an alicyclic alkyl group, or an aromatic alkyl group. Such compounds include methyl, ethyl, propyl, butyl, hexamethyl, cyclohexyl, phenyl groups and the like. Suitable compounds for R ² include C ² to C 15 aliphatic, cycloaliphatic and aromatic alkyl groups, for example butylene, hexamethylene, octamethylene, isophorone, cyclohexylene, phenylene, naphthalene, diphenylmethyl, toluylene, etc. There is this. R4 represents a hydrogen atom or an alkyl or aryl group of C1 to C5, and examples thereof include methyl group, ethyl group, butyl group and propyl group.

Then, by reacting the <Chemical Formula 1> and the acrylic compound in the reaction to prepare a <Formula 2> which is a metal alkoxide complex of the acrylic group terminal. The reaction temperature is from room temperature to 60 ℃ and stirred for 2 to 24 hours until all the isocyanate reacts. R 3 is a compound having an aliphatic, cycloaliphatic or aromatic structure of C 1 to C 15.

(2)

For the surface modification of the conductive inorganic oxide particles, it is mixed with the synthesized metal alkoxide complex of the terminal of the acrylic group and the inorganic oxide, and strong acids such as hydrochloric acid, sulfuric acid and nitric acid, weak acids such as acetic acid and phosphoric acid or basic acids such as potassium hydroxide, sodium hydroxide and amine. The catalyst and water are added to react the surface of the inorganic oxide by reacting for 24 hours at room temperature ~ 60 ℃. The alkoxide composite compound used for the surface treatment is preferably used in an amount of 100 to 300 parts by weight based on 100 parts by weight of the conductive inorganic oxide, and when less than 100 parts by weight, the dispersion characteristics of the inorganic oxide particles are poor, resulting in low transparency and 300 parts by weight. When exceeded, the particle dispersibility is excellent, but the thermal barrier properties are deteriorated.

The photoinitiator used in the present invention is preferably used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the conductive inorganic oxide. When the content of the photoinitiator is less than 1 part by weight, the curing rate is slow and the curing is insufficient. , There is a problem that the hardening speed is fast but only the surface of the coating film is hardened. Examples of the photoinitiator include benzophenone, benzion, benzion methyl ether, benzion-n-butyl ether, benzion-isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2,2-diethoxyacetophenone, Phenol, methylphenylglyoxylate, and ethylphenylpyloxylate, which may be used alone or in combination of two or more.

The organic solvent used in the present invention is used for dispersion of the inorganic oxide particles and for controlling the solid content, and includes aromatic hydrocarbon type solvents such as toluene and xylene, ketone type solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, Propyl alcohol, ethanol and the like are used alone or in combination. And the usage amount is 200 to 400 parts by weight based on 100 parts by weight of the conductive inorganic oxide. If the solvent is less than 200 parts by weight, the dispersing effect is insufficient, and if the solvent exceeds 400 parts by weight, the coating agent has a high viscosity, making it difficult to form a coating film having a uniform thickness.

Hereinafter, the present invention will be described in detail with reference to Production Examples and Examples, but the present invention is not limited to these Production Examples and Examples.

<Production of Metal Alkoxide Composites Used for Surface Treatment>

25 g of methylene diphenyl diisocyanate and 22 g of aminopropyltrimethoxysilane were reacted in a reactor at a rate of 300 rpm at room temperature for 2 hours to prepare a silane compound including an isocyanate group at the terminal. To 47 g of the compound, 0.1 g of dibutyltin dilaurate was added to 53 g of 2-hydroxyethyl methacrylate and a reaction catalyst, followed by stirring in a 50 ° C. oil bath under a nitrogen atmosphere for 12 hours to prepare a metal alkoxide complex at the acrylic end.

(Example 1)

100 parts by weight of aluminum doped ZnO (AZO) and 150 parts by weight of the metal alkoxide complex for surface treatment described below, 10 g of 0.1N triethylamine aqueous solution, 3 parts by weight of an initiator (Irgacure 184, ciba chemical), iso 300 parts by weight of propyl alcohol was added and reacted at room temperature for 24 hours to prepare a thermal barrier coating including surface treated AZO particles. Then, using a bar coater to coat the PET film with a thickness of 30㎛, and dried at 60 ℃ for 10 minutes, using a UV curing device to cure the coating film at a light amount of 700mJ / cm2 to produce a heat shielding film to coat the film properties and train However, the characteristics were evaluated.

(Example 2)

Except that 250 parts by weight of the metal alkoxide composite compound for surface treatment in Example 1 was prepared in the same manner as in Example 1 UV curable thermal barrier coatings were evaluated for coating properties and thermal barrier properties.

(Comparative Example 1)

Except for not using a metal alkoxide composite compound, catalyst, initiator for the surface treatment in Example 1 was prepared in the same manner as in Example 1 UV curable thermal barrier coatings were evaluated for coating properties and thermal barrier properties.

(Comparative Example 2)

Ultraviolet curing type thermal barrier coating agent in the same manner as in Example 1 except that 150 parts by weight of methacryloxypropyltrimethoxysilane, a silane coupling agent having an acryl group, in place of the metal alkoxide composite compound for surface treatment in Example 1 And the coating properties and thermal barrier properties were evaluated.

(Comparative Example 3)

Except for using 50 parts by weight of the metal alkoxide composite compound for the surface treatment in Example 1 was prepared in the same manner as in the ultraviolet curable thermal barrier coating was evaluated for coating properties and thermal barrier properties.

<Test Method>

The properties of the thermal barrier coatings prepared in Examples and Comparative Examples were evaluated in the following manner.

Hardness

The surface hardness of the cured coating film was measured using a pencil hardness meter according to JIS K5600. The degree of scratches on the coated surface was checked with naked eyes, and pencil hardness of at least 3 mm was observed. The evaluation was carried out three times or more until the same result was obtained.

Scratch resistance

A steel wool having a load of 1 kg was reciprocated 20 times on the surface of the cured coating film to determine the degree of occurrence of scratch as a haze value.

Hayes

The haze of the pressure-sensitive adhesive itself and the total light transmittance were evaluated using a haze meter.

Visible light transmittance, infrared / ultraviolet ray blocking rate

UV / VIS / NIR spectrometer (cary 5000).

The results of the above experiment are shown in the following table.

 Formulation Table (Preparation Example-Preparation of Alkoxide Composites Used for Surface Treatment) Manufacturing example Methylenediphenyl diisocyanate 25 Aminopropyltrimethoxysilane 22 2-hydroxyethyl methacrylate 53 Dibutyl tin dilaurate 0.1

Formulation table (Examples 1 to 2, Comparative Examples 1 to 4) Example
One Example
2 Comparative Example
One Comparative Example
2 Comparative Example
3 Zinc Oxide Doped Aluminum (AZO) 100 100 100 100 100 Metal alkoxide complexes 150 250 - - 50 Methacryloxypropyltrimethoxysilane - - - 150 - 0.1N triethylamine aqueous solution 10 10 - 10 10 Irgacure 184 3 3 - 3 3 Isopropyl alcohol 300 300 300 300 300

Thermal Short Film Properties (Examples 1 to 2, Comparative Examples 1 to 4) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Visible light transmittance
(550 nm,%) 83 85 60 66 74 UV protection rate
(350 nm,%) 99.4 99.1 99 88.8 99.1 infrared ray 1,500 nm 60 57 56 53 56 Blocking rate
(%) 2,000 nm 97 96 95 93 96 Haze 2.8 2.6 12.5 10.1 6.2 Film hardness 3H 3H 1H or less 1H 2H Steelwool-
rubbing, haze) 0.4 0.37 26 15 3.2

As a result of excluding the metal alkoxide complex in Comparative Example 1 and Comparative Example 2 and reducing the content of the metal alkoxide complex in Comparative Example 3, it can be seen that physical properties deteriorate on the test evaluation items.

According to another aspect of the present invention, the thermal barrier coating composition consisting of the above-described composition is applied to the surface of the substrate selected from resin, glass, paper, and cloth with a predetermined thickness and UV cured to produce a coating. The resin is not particularly limited, but may be selected from acrylic resins, polycarbonate resins, polyolefin resins, polyvinyl resins, polyurethane resins, nylon resins, and the like, in addition to polyester resins such as polyethylene terephthalate (PET). .

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore intended that such variations and modifications fall within the scope of the appended claims.

Claims (4)

A coating composition having transparency and heat insulation, characterized in that the composition is composed of a conductive inorganic oxide particles surface-modified with a metal alkoxide composite containing an acryl in a urethane group or urea group, a photoinitiator and a solvent. The method of claim 1,
The metal alkoxide complex is a coating composition having transparency and heat insulation, characterized in that the compound represented by the formula (2).
(2)

In <Formula 2>, Y is a compound containing a non-covalent electron pair such as mercapto group, amino group, alcohol group and M represents a metal selected from silicon, titanium, aluminum. R ¹ represents a C1 to C10 linear or pulverized alkyl group, an alicyclic alkyl group or an aromatic alkyl group, etc., R ² is a C2 to C15 aliphatic, alicyclic or aromatic alkyl group, and R ³ is C1 to C15 aliphatic, alicyclic or It is a compound which has an aromatic structure, and R <^4> represents a hydrogen atom or C1-C5 alkyl group or an aryl group. The method of claim 1,
100 weight parts of conductive inorganic oxides selected from indium tin oxide (ITO), antimony tin oxide (ATO), aluminum doped zinc oxide (Al-dopped ZnO), and gallium doped zinc oxide (Ga-dopped ZnO) 100 to 300 parts by weight of the metal alkoxide complex compound for surface modification, 1 to 10 parts by weight of a photoinitiator selected from benzophenone and 1-hydroxycyclohexyl phenyl ketone, 200 to 400 parts by weight of an organic solvent, hydrochloric acid, sulfuric acid, A coating composition having transparency and heat insulating property, comprising adding 2 to 10 parts by weight of an acid catalyst selected from acetic acid, phosphoric acid or potassium hydroxide, which is an aqueous solution of basic catalyst, and an amine. A coating composition having transparency and heat insulation, which is obtained by applying a coating composition having transparency and heat insulation made of the compounding composition of claim 1 to a surface of a substrate selected from resin, glass, paper, and cloth at a predetermined thickness and curing under UV light. Used coatings.