KR20120078637A - Coating composition and uses thereof - Google Patents

Abstract

PURPOSE: A coating composition is provided to efficiently prevent infrared ray, thereby capable of materially decreasing indoor temperature, and reducing power consumption. CONSTITUTION: A coating composition comprises 1-70 weight% of optical catalyst composite, and silicon resin. The optical composite comprises an insulative material, and a photocatalytic material. The insulative material is selected from a group consisting of an antimony tin-oxide(ATO), indium tin oxide(ITO), aluminum zinc oxide(AZO), indium zinc oxide(IZO), gallium zinc oxidate(GZO), and a mixture. The photocatalytic material is selected from a group consisting of titanium dioxide, zinc oxide, strontium titanate, tin oxide, and mixtures thereof. The content of the photocatalytic material is about 10-90 weight% based on the total weight of the photocatalytic composite. The silicon resin is manufactured through a sol-gel method. The coating composition additionally comprises organic solvent.

Description

Coating Compositions and Their Uses {COATING COMPOSITION AND USES THEREOF}

The present invention relates to a coating composition that can be coated on a substrate so that the surface of the substrate can have self-cleaning and heat insulation effects. The invention also relates to an energy-saving material containing a film formed from the coating composition of the invention.

For example, there are many materials to block the thermal effects of infrared radiation available on the market such as glass curtains of automobiles, automotive glass and insulating paper. In short, these materials are provided for the purpose of allowing sunlight to pass through and supply light, while a heat source (ie, the thermal effect of infrared light) is insulated. However, for example, with glass having current infrared blocking properties, the manufacturing cost is too expensive and the effect is less satisfactory. For example, it is known that ultra-thin infrared absorption silver films can be inserted into glass to block infrared light; However, the manufacturing cost is high, and the silver is easily oxidized and the infrared blocking effect is lost.

In addition, in order to form a film capable of blocking infrared rays, materials capable of blocking infrared rays (for example, high refractive index titanium dioxide and low refractive index silica) may be applied to the glass or the lens by vacuum deposition. However, the film thus produced has disadvantages of high cost, complicated manufacturing process and unsatisfactory effect, and thus does not satisfy the demand of economic advantage.

In addition to the two methods described above, alternative low cost solutions have been proposed, in which a pigment or dye is mixed into the glass to absorb infrared light in the sun. However, when strong sunlight or scattered light is irradiated, this kind of glass containing pigments or dyes generates smoke-like haze, and infrared absorption performance is affected, and after a long time of use, the pigment or dye decomposes. The effect will be lost.

It is also known that the photocatalyst has a function of absorbing light (especially UV light) to excite electrons and having photocatalytic performance. The photocatalytic material is excited by light and then activates water or oxygen molecules in the air to form hydroxyl radicals or oxygen anions for redox reactions, thereby degrading contaminants in the environment. Thereby, the photocatalytic material can be used to remove contaminants in air or waste water, and can suppress the adhesion of bacteria to the surface, thereby exhibiting an antibacterial effect. Moreover, when light is irradiated, due to the presence of hydrogen atoms, free radicals or oxygen anions are formed and released from the photocatalyst surface, and empty positions are formed at positions originally occupied by oxygen. In this case, if present, water molecules in the environment occupy empty positions and lose protons, forming hydroxyl groups, so that the photocatalytic material exhibits superhydrophilic properties, thereby self-cleaning and anti-fog You get an effect.

In general, in a heat insulating film or window glass coating having infrared blocking and UV light absorption functions, a multilayer process is required to form a composite film, the manufacturing process is complicated, and the manufacturing cost is expensive. Therefore, continuous efforts are currently made to provide materials having infrared blocking and UV light absorbing functions.

In order to achieve the above object, the present invention provides a coating composition comprising a photocatalyst composite and a silicone resin, wherein the content of the photocatalyst composite is about 1 to 70% by weight based on the total weight of the composition , Photocatalytic complexes include:

(1) an insulating material selected from the group consisting of antimony tin oxide (ATO), indium tin oxide (ITO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), and mixtures thereof; And

(2) a photocatalytic material selected from the group consisting of titanium dioxide, zinc oxide, strontium titanate, tin oxide, and mixtures thereof, wherein the content of the photocatalytic material is about 10 to 90% by weight based on the total weight of the photocatalyst composite. .

The present invention also provides an energy-saving material comprising a substrate and a film applied to at least one of the surfaces of the substrate, wherein the film is formed from the coating composition of the present invention and is self-cleaning And an insulating effect.

The coating composition of the present invention significantly reduces the transmittance of infrared rays by effectively insulating or reflecting heat-causing infrared rays. This photocatalyst material exhibits UV light absorbing ability, self cleaning function, and anti-fog, antibacterial, and deodorizing effect. In addition, since the coating composition of the present invention can be applied to the substrate through a conventional coating method, the manufacturing process is relatively simple and inexpensive.

1 is a comparative chart of light transmittance according to Example 1. FIG.
2 shows the degradation rate of the coating composition of the present invention against methylene blue, which shows the photocatalytic properties of the coating composition.
Figure 3 shows the measured value of the contact angle of the coating composition of the present invention and water at the time of UV light irradiation.

As used herein, the term "about" means a change of ± 10% of the indicated value.

The coating composition of the present invention comprises a photocatalyst composite and a silicone resin, wherein the content of the photocatalytic composite is about 1% to about 70% by weight, preferably about 40% to about 60% by weight based on the total weight of the composition %to be. If the content of the photocatalytic composite is less than 1% by weight, the infrared blocking and UV light absorbing effects of the composition are not sufficient, and if the content is more than about 70% by weight, the dispersion of the photocatalytic complex in the resin is sharply lowered and coated. There is a fear that the quality of the composition is degraded.

The photocatalytic composite includes an insulating material and a photocatalytic material, wherein the content of the photocatalytic material is about 10 wt% to about 90 wt%, preferably about 40 wt% to about 85 wt%, based on the total weight of the photocatalyst composite. .

The photocatalytic composite generally has a particle size of about 2 to about 100 nm, preferably about 5 to about 45 nm, more preferably 10 to 35 nm. If the particle size is smaller than 2 nm, it is not easy and practical to manufacture the photocatalytic composite. If the particle size is larger than 100 nm, the total surface area is small, the transmittance of visible light is low, and the thermal insulation effect is not good. Since the particle size of the photocatalytic composite of the present invention is smaller than the wavelength of visible light (about 380 nm to about 780 nm), when light is irradiated onto the photocatalytic composite, the transmitted light is not scattered severely, thereby preventing a detrimental effect on the quality of the transmitted light. do.

The thermal insulation material of the photocatalytic composite of the present invention is required to have an infrared reflectance of about 70% or more, antimony tin oxide (ATO), indium tin oxide (ITO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium Zinc oxide (GZO), and mixtures thereof.

According to a preferred embodiment of the present invention, when ITO or ATO is used as the heat insulating material of the photocatalyst composite, the photocatalytic composite is more ratio efficient since substantially the same heat insulating effect can be obtained with a smaller amount of material compared with other materials. It has also been found that when the coating composition comprises ITO, it not only effectively reflects infrared rays but also exhibits better visible light transmittance, which can be advantageously used as a transparent insulating material.

According to a preferred embodiment of the present invention, when ITO is used as the heat insulating material of the photocatalyst composite, a preferable transparency can be obtained. In addition, it has been found that when ITO is used in the coating composition of the present invention, infrared rays are effectively reflected and substantially the same thermal insulation effect can be obtained with a lower amount of material compared to other materials, thereby making it more cost effective.

In addition to the insulating material capable of blocking or reflecting infrared light, the photocatalytic composite of the coating composition of the present invention further comprises a photocatalytic material. The photocatalytic material has a function of absorbing UV light to excite electrons and thus has photocatalytic properties. When excited by light, the photocatalytic material decomposes contaminants in the environment by activating water or oxygen molecules in the air to form hydroxyl free radicals or oxygen anions for redox reactions. Therefore, the photocatalytic material can be used to remove contaminants in air or wastewater, and can suppress the adhesion of bacteria to the surface, thereby exerting an antibacterial effect. Moreover, the photocatalytic material exhibits superhydrophilic properties, and moisture can form into the aqueous film between the deposit and the photocatalytic material, reducing the adhesion of the deposit, and deposits on the aqueous film can be easily removed after washing with water or rainwater. . As such, the photocatalytic material has UV light absorbing ability and self-cleaning function, and exhibits antifogging, antibacterial and deodorizing effect.

Suitable photocatalytic materials for the photocatalytic composite of the present invention may be those well known to those skilled in the art, for example, titanium dioxide, zinc oxide, strontium titanate (SrTiO ₃ ), tin oxide, or mixtures thereof. And, preferably, titanium dioxide, which is relatively harmless to the environment or human body. In terms of catalyst performance, titanium dioxide having an anatase crystal structure is preferred. In addition, in order to exert the photocatalytic effect, the particle size of the photocatalytic material is required to be less than about 100 nm. For example, the particle size of titanium dioxide is suitably about 1 to about 100 nm, preferably about 5 to about 30 nm; If the particle size is smaller than 1 nm, it is difficult to produce titanium dioxide and not easy to disperse. If the particle size is larger than 100 nm, the catalytic effect is greatly reduced.

The coating composition of the present invention may be, for example, an acrylic resin, a fluorocarbon resin or a silicone resin, but includes a binder, but is not limited thereto. In order to prevent the photocatalyst from being oxidized and decomposed, the binder is preferably a silicone resin. The silicone resin contained in the coating composition of the present invention is present in an amount of about 30% to about 99% by weight, preferably about 40% to about 60% by weight, based on the total weight of the coating composition.

, 또는 페닐이며; n은 실리콘 원자에 결합된 수소 원자 또는 유기라디칼의 수로, 0 내지 3의 범위이며; m은 중합도를 나타내며 2 이상의 정수이다]의 유기 폴리실록산 수지이다. 폴리실록산의 화학 구조를 구성하는 단계는 중합 사슬의 길이를 결정하는 단계, 가지화 단계 및 수소 또는 유기기를 부착하기 위한 위치를 정하는 단계를 포함한다. 화학 구조 측면에서, 문자 M (단관능기를 나타냄), D (이관능기), T (삼관능기), 및 Q (사관능기)가 중합 분자 내에 도입된 구조적 관능기를 나타내는데 이용될 수 있다.The silicone resin used in the present invention is not particularly limited, and is well known to those skilled in the art, that is, a main chain composed of repeated Si-O bonds in which a hydrogen atom or an organic radical is directly bonded to a silicon atom. have, the general formula _{[R n SiO 4-n /} 2] m ( wherein, R is a hydrogen or an organic radical independently selected from the group consisting of hydrogen, C _{1 -6} alkyl, C _{2 -5} epoxy, or C _{6 -14} aryl, Preferably hydrogen, methyl, ethyl,

Or phenyl; n is the number of hydrogen atoms or organic radicals bonded to silicon atoms, in the range of 0 to 3; m represents a degree of polymerization and is an integer of 2 or more]. Constructing the chemical structure of the polysiloxane includes determining the length of the polymerization chain, branching and positioning the hydrogen or organic groups. In terms of chemical structure, the letters M (which represent monofunctional groups), D (bifunctional groups), T (trifunctional groups), and Q (tetrafunctional groups) can be used to denote the structural functional groups introduced into the polymerization molecule.

Examples of commercially available silicone resins include KBM-1003, KBE-402, KBE-403, KBM-502, KBM-04, KBE-13, and KBE-103 manufactured by Shin Etsu Company; And Z-6018 and 3037, manufactured by Dow Corning Company.

이다. 이러한 올리고머는 본 발명의 코팅 조성물에 더 우수한 필름 형성 특성, 분산도 및 연성, 및 경화된 후 높은 표면 경도를 부여한다.Silicone resins may be used alone and in combination of two or more kinds. Silicone resins that may be used in the present invention may be an oligomer of the formula R ¹ O— [SiR ₂ O] _w —SiR ₂ (OR ¹ ), wherein w is an integer from 1 to 1000, R is the definition above a the same as, R ¹ are independently H, C _{1 -3} alkyl, C _{2 -5} epoxy, preferably methyl, ethyl, or

to be. Such oligomers impart better film forming properties, dispersion and ductility, and high surface hardness after curing to the coating compositions of the present invention.

Suitable production methods for the silicone resin of the present invention are not particularly limited. In a preferred form of the invention, the silicone resin is formed through a sol-gel process. The sol-gel process involves suspending a raw material (generally an inorganic metal salt) of solid particles about 100 nanometers in size in a liquid. In a representative sol-gel process, the reactants undergo a series of hydrolysis and polymerization reactions to produce a colloidal suspension, wherein the material obtained in the colloidal suspension is condensed into a new phase of the solid polymer containing solution, ie gel. The properties of the prepared sol-gel depend on the kind of raw material, the kind and concentration of catalyst, pH value, temperature, the amount of solvent, the kind and concentration of alcohol and salt.

The coating composition of the present invention has a surface of the photocatalyst composite in order to prevent direct contact between the photocatalyst and the substrate when the coating composition is coated on the surface of the substrate, and to prevent degradation of the substrate, which may easily occur due to the oxidizing properties of the photocatalyst. Nano-sized inorganic fine particles may be optionally included to be coated with a layer of the inorganic fine particles. If present, the amount of inorganic particulates is from about 0.1% to about 40% by weight based on the total weight of the composite material. The inorganic fine particles that can be used in the present invention are not particularly limited, and generally silica (SiO ₂ ), alumina (Al ₂ O ₃ ), cadmium sulfide (CdS), zirconia (ZrO ₂ ), calcium phosphate (Ca ₃ (PO) ₄ ) ₂ ), calcium oxide (CaO), and mixtures thereof, with SiO ₂ being preferred. According to a preferred form of the invention, the photocatalytic composite is coated with a layer of porous inorganic fine particles. In particular, the photocatalytic composite in the composite material of the present invention is coated with a layer of porous inorganic fine particles so that it is not in direct contact with the substrate and does not destroy the substrate, and external impurities (eg odor molecules and bacteria) are porous through diffusion. It can penetrate into the inorganic particles to reach and absorb the photocatalytic material, and can be decomposed photocatalytically to achieve cleaning, antibacterial and deodorizing purposes.

Depending on the requirements of the application, an organic solvent may be further added to the coating composition of the present invention. When an organic solvent is used in the coating composition of the present invention, the amount is about 1% to about 95% by weight, preferably about 65% to about 90% by weight based on the total weight of the coating composition. The organic solvent may be any that is well known to those skilled in the art, for example, but may not be limited to, alkanes, aromatic hydrocarbons, esters, ketones, alcohols, or ether alcohols. Alkanes solvents that may be used in the present invention may be selected from the group consisting of n-hexane, n-heptane, iso-heptane, and mixtures thereof. The aromatic hydrocarbon solvent that can be used in the present invention can be selected from the group consisting of benzene, toluene, xylene, and mixtures thereof. Ketone solvents that may be used in the present invention are selected from the group consisting of methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and mixtures thereof Can be. Ester solvents that may be used in the present invention are isobutyl acetate (IBAC), ethyl acetate (EAC), butyl acetate (BAC), ethyl formate, methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, ethyl iso-butyrate , Propylene glycol monomethyl ether acetate, pentyl acetate, and mixtures thereof. Alcohol solvents that may be used in the present invention may be selected from the group consisting of ethanol, iso-propanol, n-butanol, and iso-pentanol, and mixtures thereof. Ether alcohol solvents that may be used in the present invention include ethylene glycol monobutyl ether (BCS), ethylene glycol monoethyl ether acetate (CAC), ethylene glycol monoethyl ether (ECS), propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate (PMA), propylene glycol monomethyl propionate (PMP), and mixtures thereof.

The present invention provides an energy-savng material comprising a substrate and a film formed from the coating composition as described above on at least one surface of the substrate. The coating composition of the present invention may be applied to at least one surface of the substrate by conventional application methods, for example by drying after coating, spraying or dipping to form a smooth film. Existing energy-saving materials generally have the disadvantage of low coating hardness and easy scratching, which is very susceptible to scratching the coating after a long time, and such scratched coatings have a serious effect on the aesthetic appearance of articles such as windows. Go crazy. According to a preferred aspect of the present invention, the film of energy saving material has a pencil hardness of H or higher, preferably 3H or higher, measured according to the JIS K5400 standard method, and can effectively solve the above-mentioned problems.

The above-mentioned substrates include glass, plastic, building insulation plates, metals, ceramic tiles, wood, leather, stones, concrete, walls, fibers, cotton fabrics, appliances, lighting devices, and computers. Including, but not limited to, casings, building insulation plates are preferred.

According to a particular aspect of the present invention, the energy saving material comprises glass and a film formed by applying the aforementioned coating composition by coating, spraying or dipping on at least one surface of the glass. The film has a thickness of about 0.5 to about 50 micrometers. The energy saving material according to the invention has a visible light transmittance of at least about 70%, preferably at least about 90%, at a wavelength of 550 nm. The energy saving material of the present invention has an excellent visual effect and an infrared (heat radiation) reflectance of about 70% or more, and exhibits an excellent thermal insulation effect, which can substantially lower room temperature and reduce energy consumption. The advantages of greater energy savings and higher visible light transmission compared to glass with conventional insulating films available on the market, resulting in significantly reduced costs, simple application and wide application in glass curtains for building or automotive glass Has Moreover, almost all thermally insulating materials (such as lanthanum hexaboride) contained in the coating compositions for energy saving materials available on the market absorb rather than reflect infrared light in the sun, and the absorbed infrared light is converted into thermal energy. And stored in the glass, there is a risk of cracking the glass as the surface temperature of the glass rises.

In addition, the photocatalytic composite of the coating composition of the present invention has superhydrophilic properties, attracts moisture in the air to form an ultrathin aqueous film between the deposit and the photocatalyst composite, and reduces the adhesion of the deposit. In addition, the photocatalyst may oxidize the organic deposit particles and destroy their structure, so that the particles do not adhere to the glass surface. At rainfall, due to the effect of the superhydrophilic properties, the rainwater penetrates evenly at the contact point between the deposit and the photocatalyst, and when the rainwater accumulates in a sufficient amount, the deposit on the aqueous film can be easily washed away, with the aid of manpower The frequency of keeping the surface of conventional glass clean is low, and a self-cleaning effect is obtained.

In the past, in order to obtain an energy saving material, a treatment for blocking infrared rays and a treatment for absorbing UV light had to be performed on the substrate, and the infrared blocking and UV light absorption effects were performed on a substrate by a multilayer process. It could only be obtained afterwards. However, by using the coating composition of the present invention, energy saving materials having infrared blocking and UV light absorbing effects can be obtained through one application treatment to the surface of the substrate. Since the film applied on the substrate contains a photocatalytic material, it can absorb UV light, providing self cleaning, antifogging, antibacterial, and deodorizing efficacy; By the presence of the insulating material, the film can effectively reflect infrared light, allowing infrared light to pass while reducing the transmission. In addition, since the size of the particles contained in the film is smaller than the wavelength of visible light, the particles do not scatter transmitted light, do not affect the quality of the transmitted light, and the transparency of the substrate can be maintained.

The present invention provides a method for preparing a coating composition, wherein the method obtains an intermediate product of titanium sulfate through hydrolysis of titanium tetrachloride, and then adds an insulating material to obtain a photocatalytic composite powder at low temperature, and then the obtained photocatalyst. Mixing and pulverizing the composite powder and the silicone resin to obtain the coating composition of the present invention.

According to certain preferred embodiments of the present invention, an appropriate proportion of the sol-gel silicone resin and the photocatalyst composite powder are mixed, optionally added with a solvent and then ground to obtain a coating composition of the present invention. The photocatalyst composite powder described above can be obtained by a process comprising the following steps:

(a) obtaining a white gel hydrate through hydrolysis of titanium tetrachloride;

(b) adding concentrated sulfuric acid to the obtained hydrate in the reactor and stirring for 10-50 minutes to obtain a titanium sulfate solution;

(c) sufficiently mixing the titanium sulfate solution and stirring at normal temperature for 0.5 to 5 hours;

(d) heating to 80-100 ° C. and reacting at constant temperature for 2-7 hours; And

(e) ITO powder was added in an appropriate ratio, stirred and mixed for 1 to 4 hours, 4 to 6 M aqueous sodium hydroxide solution was added dropwise, filtered, washed and dried at room temperature to form a photocatalytic composite powder (TiO ₂ + ITO). Step to get it.

The invention is further illustrated through the following examples. It is to be understood that the following examples are merely used to illustrate the invention and are not intended to limit the scope of the invention. Any change or modification which is obvious to those skilled in the art and made without departing from the spirit and principles of the present invention should fall within the scope of the present invention.

Example

In the following examples and comparative examples, by weight unless otherwise indicated.

Example  One

200 ml of 3.9 M titanium tetrachloride solution was diluted with water to a total volume of 2000 ml and then 500 ml (5 M) of aqueous ammonia was added dropwise to produce a white titanium hydroxide precipitate which was filtered off, Titanium hydroxide [Ti (OH) ₄ ] was obtained with a white gel by washing with deionized water (200 mL × 3) to remove residual water.

100-150 g of concentrated sulfuric acid (18M) was added to 250 g of the titanium hydroxide and stirred for 30 minutes to obtain a clear and clear titanium sulfate solution. The titanium sulfate solution was added to the reactor, 32.2 g of SiO ₂ aqueous solution (20%) was added thereto, stirred at room temperature for 4 hours, and then heated to 100 ° C. for 2 hours. 100 g of aqueous solution of ITO (10%) were added and the reaction was stirred at room temperature for 2 hours to give a mixture.

After dropping 600 mL (5 M) aqueous sodium hydroxide solution, the obtained solution was adjusted to neutral pH, and the obtained precipitate was filtered, washed and dried at room temperature to obtain a grayish blue powder, which was obtained through XRD. It was detected to be a photocatalytic complex of anatase type photocatalyst and ITO.

The obtained photocatalytic composite was added to the silicone resin (having a solid content of 27%) in a ratio of photocatalytic composite: resin = 1: 3 (weight ratio), and stirred, pulverized, dispersed and applied on a glass plate to have a thickness of 5 micrometers. A coating was formed. Light transmittance measurements, organic (methylene blue) decomposition tests, hydrophilic property tests, and adiabatic tests were performed.

The blank glass plate and the coating were put in a UV / visible / near infrared spectrometer (manufactured by JASCO Incorporation, Model V-570), respectively, and the light transmittance was measured in the UV to near infrared range. The test results are shown in FIG. 1 (wherein the range between the two vertical lines represents visible light). The zigzag line shows the transmittance value of the uncoated glass plate (transmittance is about 100%), the continuous line shows the transmittance value of the glass plate coated on one surface, and the dotted line shows the transmittance value of the glass plate coated on both surfaces. Indicates. From the test results, it can be seen that the coating of the present invention can greatly reduce the transmittance of UV light and near infrared rays, and can effectively block UV light and near infrared rays.

(35 ± 0.3) ml of methylene blue was added to a cylindrical test column with an inner diameter of 40 mm and a height of 30 mm, then a rectangular glass with a side length of (60 ± 2) mm and a coating was placed thereon. UV light of (1.00 ± 0.05) μs / cm 2 was irradiated to the coating for a total of 6 hours and the decomposition rate of methylene blue was measured every 1 hour. The test results are shown in FIG. From the test results, it can be confirmed that, upon UV light irradiation, the coating of the present invention can effectively decompose organic matter (methylene blue), and has photocatalytic properties.

A square plate of side length (100 ± 2) mm with a coating was taken into the test plate, 1 μl of water was contacted to the test plate, the image was captured and the contact angle was measured with a contact angle tester. UV light of (1.0 ± 0.1) dB / cm 2 was irradiated to the coating and the contact angle was measured every 50 hours. The test results are shown in FIG. From the test results, it can be seen that the coating of the present invention has superhydrophilic properties upon UV light irradiation.

Place the coating at approximately 20 cm below the infrared bulb (PHILIPS Corporation), place a beaker containing 100 g of water at approximately 15 cm below the glass coating, and irradiate with an infrared bulb to illuminate the infrared thermometer (TES series, TES Electrical Electronic Corp.) regularly measured the surface temperature every 5 minutes. The test results are shown in Table 1 below, and the surface temperature of the coating after 30 minutes of irradiation is shown in Table 2 below.

Example  2

200 ml of 3.9 M titanium tetrachloride solution was diluted with water to 2000 ml total volume, and then 500 ml (5 M) of aqueous ammonia was added dropwise to produce a white titanium hydroxide precipitate which was filtered off and deionized water. Titanium hydroxide [Ti (OH) ₄ ] was obtained with a white gel by washing with (200 mL × 3) to remove residual water.

100-150 g of concentrated sulfuric acid (18M) was added to 250 g of the aforementioned titanium hydroxide and stirred for 30 minutes to give a clear and clear titanium sulfate solution. The titanium sulfate solution was added to the reactor, 32.2 g of SiO ₂ aqueous solution (20%) was added thereto, stirred at room temperature for 4 hours, and then heated to 100 ° C. for 2 hours. 100 g of aqueous ATO solution (15%) was added and the reaction was stirred at room temperature for 2 hours to give a mixture.

After dropping 600 mL (5 M) aqueous sodium hydroxide solution, the obtained solution was adjusted to neutral pH, and the obtained precipitate was filtered, washed and dried at room temperature to obtain a dark blue powder, which was obtained through anatase through XRD. It was detected to be a photocatalyst complex of fluorescent photocatalyst and ATO.

The obtained photocatalytic composite was added to the silicone resin (having a solid content of 27%) in a ratio of photocatalytic composite: resin = 1: 3 (weight ratio), and was stirred, pulverized, dispersed and applied on a glass plate to have a thickness of 5 micrometers. A coating with was formed. Insulation test was performed.

The coating is placed about 20 cm below an infrared bulb (PHILIPS Corporation), a beaker containing 100 g of water is placed about 15 cm below a glass coating, irradiated with an infrared bulb and the surface temperature is irradiated every 5 minutes. Regular measurements were taken with a thermometer (TES series, TES Electrical Electronic Corp.). The test results are shown in Table 1 below, and the surface temperature of the coating after 30 minutes of irradiation is shown in Table 2 below.

Comparative example  One

200 ml of 3.9 M titanium tetrachloride solution was diluted with water to 2000 ml total volume, and then 500 ml (5 M) of aqueous ammonia was added dropwise to produce white titanium hydroxide precipitate, which was filtered and deionized water. Titanium hydroxide [Ti (OH) ₄ ] was obtained with a white gel by washing with (200 mL × 3) to remove residual water.

100-150 g of concentrated sulfuric acid (18M) was added to 250 g of the aforementioned titanium hydroxide and stirred for 30 minutes to give a clear and clear titanium sulfate solution. The titanium sulfate solution was added to the reactor, 32.2 g of SiO ₂ aqueous solution (20%) was added thereto, stirred at room temperature for 4 hours, and then heated to 100 ° C. for 2 hours. 100 g of lanthanum hexaboride aqueous solution (10%) was added, and the reaction was stirred at room temperature for 1 hour to obtain a mixture.

600 mL (5 M) aqueous sodium hydroxide solution was added dropwise, and the obtained precipitate was filtered, washed and dried at room temperature to obtain a gray blue powder, which was obtained through XRD of the anatase type photocatalyst and lanthanum hexaboride. It was detected to be a photocatalytic complex.

The obtained photocatalyst composite was added to the silicone resin (having a solid content of 27%) in a ratio of photocatalytic composite: resin = 1: 3 (weight ratio), and stirred, dispersed and applied on a glass plate to have a thickness of 5 micrometers. A coating was formed. Insulation test (using an infrared bulb, PHILIPS Corporation) was performed.

The coating is placed at about 20 cm below the infrared bulb, a beaker containing 100 g of water is placed at 15 cm below the glass coating, irradiated with an infrared bulb and the surface temperature is measured every 5 minutes with an infrared thermometer (TES series, TES Electrical Electronic Corp.) was regularly measured. The test results are shown in Table 1 below, and the surface temperature of the coating after 30 minutes of irradiation is shown in Table 2 below.

Comparative example  2

Commercially available insulating paper (manufactured by Top Color Film Co. Ltd., trade name; SD series Top Color) is affixed to the glass surface, placed about 20 cm below the infrared bulb, and a beaker containing 100 g of water is placed under the glass attachment. Placed at a position of about 15 cm, irradiated with an infrared bulb, the surface temperature was measured regularly by an infrared thermometer (TES series, TES Electrical Electronic Corp.) every 5 minutes. The test results are shown in Table 1 below, and the surface temperature of the deposit after 30 minutes of irradiation is shown in Table 2 below.

Temperature test (℃) Time (minutes) Glass Example 1 Example 2 Comparative Example 1 Comparative Example 2 0 24 24 24 24 24 5 34 34 33.8 34 34.8 10 39.8 35.3 34.7 38.3 39.3 15 42.6 39.8 38.5 40.1 40.9 20 45 42.3 39.8 43.1 44.1 25 46.1 43.6 42 45.8 44.8 30 48.6 43.6 43 46.5 45.1

30 minutes after irradiation temperature of glass Time (minutes) Glass Example 1 Example 2 Comparative Example 1 Comparative Example 2 30 70.8 60 61.4 86 68.4

From the comparison of the results of Table 1, it can be confirmed that the thermal insulation is effectively applied when the coating having the coating composition of the present invention is applied to the glass surface.

From the comparison of Examples 1, 2 and Comparative Example 1, it can be seen that the coating composition of the present invention can effectively reflect the infrared rays, thereby lowering the surface temperature of the glass, thereby preventing the risk of cracking the glass. have.

From the comparison of Examples 1, 2 and Comparative Example 2, it can be seen that the coating composition of the present invention provides a lower surface temperature of the glass coating as compared to the insulating paper. The present coating composition can be applied more easily than thermally insulating paper and can provide a better thermal insulation effect because of less chance of accumulation of thermal energy or generation of thermal convection.

Claims (11)

A coating composition comprising a photocatalyst composite and a silicone resin,
The content of the photocatalyst complex is about 1 to 70% by weight based on the total weight of the composition,
The photocatalyst complex,
(1) an insulating material selected from the group consisting of antimony tin oxide (ATO), indium tin oxide (ITO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), and mixtures thereof; And
(2) a photocatalyst material selected from the group consisting of titanium dioxide, zinc oxide, strontium titanate, tin oxide, and mixtures thereof,
The content of the photocatalytic material is about 10 to 90% by weight based on the total weight of the photocatalyst composite.
Coating composition.
The method of claim 1,
The silicone resin is prepared through a sol-gel process
Coating composition.
The method of claim 1,
Containing more organic solvent
Coating composition.
The method of claim 1,
The insulating material is ATO or ITO
Coating composition.
The method of claim 1,
The content of the photocatalytic material is about 40 to 85% by weight based on the total weight of the photocatalyst composite.
Coating composition.
The method of claim 1,
The photocatalyst material is titanium dioxide
Coating composition.
The method of claim 1,
The photocatalytic composite has a particle size of about 2 to 100 nm.
Coating composition.
The method of claim 1,
Group consisting of silica (SiO ₂ ), alumina (Al ₂ O ₃ ), cadmium sulfide (CdS), zirconia (ZrO ₂ ), calcium phosphate (Ca ₃ (PO ₄ ) ₂ ), calcium oxide (CaO), and mixtures thereof Further comprising inorganic fine particles selected from
Coating composition.
materials; And
A film formed from the coating composition of claim 1 on at least one surface of the substrate.
Energy saving materials.
10. The method of claim 9,
The film is formed by coating, spraying or dipping the coating composition of claim 1 on at least one surface of the substrate.
Energy saving materials.
10. The method of claim 9,
The film has a pencil hardness of at least H measured according to the JIS K5400 standard method
Energy saving materials.

Images