KR20150071261A - Waterbone clear binder and energy-saving type glass coating composition containing same - Google Patents

Abstract

The present invention relates to a naturally curable aqueous binder and a naturally curable and energy-saving glass coating paint including the same. The naturally curable aqueous binder is formed by a gel reaction of a mixture. The mixture includes: 1-5 wt% of silane coupling agents having an alkyl group; 20-30 wt% of silane coupling agents having an alkoxy group; 20-30 wt% of silane coupling agents having an epoxy group; 0.01-0.3 wt% of acid stabilizers; and residual water. The binder is made of an inorganic resin to have a high heat resistance rate and has the alcohol which is a product of a sol-gel reaction removed unlike a conventional oil-based binder to have a TVOC content equal to or lower than 200g/L, thereby being environmentally friendly.

Description

TECHNICAL FIELD [0001] The present invention relates to an aqueous clear binder and an energy-saving glass coating material containing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention relates to an aqueous clear binder and an energy-saving glass-coated paint comprising the same, and more particularly to an energy-saving glass-coated paint having an infrared shielding function and an ultraviolet- An aqueous clear binder, and an energy-saving glass-coated paint comprising the same.

The exterior design of a recently constructed building is an important point in the design, especially the interior and exterior materials used for exterior design, and the glass position is unique compared to other materials.

This is because glass is widely used as an interior and exterior material because it is a material capable of securing transparency which is a nature inherent in glass and capable of being formed into a functional glass by changing composition or coating of glass. Among them, energy-saving glass is an environmentally friendly coating glass that prevents heat loss from entering the window. It uses nanoparticles such as ATO and TiO ₂ to transmit light in the visible light region and has little influence on the viewport. In the infrared and ultraviolet It is possible to selectively block the light of the light source.

However, most functional glasses used as interior and exterior materials for construction are not environmentally friendly because they use oil-based binders. In the case of aqueous inorganic binders, they contain transition metal ion compounds, and water resistance and water resistance are poor. The aqueous organic binders such as water-dispersed emulsions and urethanes are also difficult to exhibit physical properties of oily binders due to their low hardness, abrasion resistance, and poor compatibility between the functional additives and the binder.

In order to solve such problems, Korean Patent Laid-Open Nos. 10-2011-0108112 and 10-2010-0129993 disclose a technique of using a glass coating paint using an organic solvent such as alcohol. This method has a problem that it is not environmentally friendly, and has a disadvantage in that the curing process must be used once more in a heat curing type. In addition, Korean Patent Laid-Open Publication No. 10-2012-0029744 discloses a technique for producing a glass coating paint by applying a binder to which a transition metal ion or the like is applied. However, It is vulnerable to physical properties such as weatherability.

Accordingly, the technical problem of the present invention is to recognize and draw attention to such a problem, and it is an object of the present invention to provide a glass composition which has a TVOC value of 200 g / L or less and can naturally cure with a high heat- And to provide an aqueous clear binder to be applied to a coating material.

Another object of the present invention is to provide an energy-saving glass-coated paint having environmental friendliness by including a natural-coloring aqueous clear binder having the above-described characteristics.

 The aqueous clear binder to be applied to the energy saving type glass coating material for realizing the above object of the present invention is a silicate coupling agent having an alkyl group, which comprises 20 to 30% by weight of a silane coupling agent having 1 to 5% by weight of an alkoxy group, 20 to 30% by weight of a ring agent, 0.01 to 0.3% by weight of an acid stabilizer, and excess water.

In one embodiment, the silane coupling agent having an alkyl group may be selected from methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, Ethyl trimethoxysilane, ethyl trimethoxysilane, ethyl trimethoxysilane, ethyl trimethoxysilane, butyl trimethoxysilane, nonafluorobutylethyl trimethoxysilane, trifluoromethyl trimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, (Meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, methyltri (meth) acryloxysilane , Methyl [2- (meth) acryloxyethoxy] silane, methyltris (3-methyl-3-oxetanemethoxy) silane and the like.

In one embodiment, the silane coupling agent having an alkoxy group is selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxy Silane, oxacyclohexyltrimethoxysilane and the like can be used.

In one embodiment, the silane coupling agent having an epoxy group may be selected from 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-clicydoxypropyl (methyl) diethoxysilane, - (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, and the like can be used.

In one embodiment, the natural curing type aqueous clear binder obtained by the sol-gel reaction may have a TVOC value in the range of 50 to 200 g / L due to the removal of the alcohol generated during the sol-gel reaction.

The water-soluble, energy-saving glass coating material for achieving the object of the present invention includes 20 to 30% by weight of a silane coupling agent having an alkyl group, 1 to 5% by weight of an alkoxy group, a silane coupling agent 20 having an epoxy group 30 to 70 parts by weight of a natural curing type aqueous clear binder formed by a sol-gel reaction of excess water and 0.01 to 0.3% by weight of an acid stabilizer, and 30 to 70 parts by weight of a composite metal oxide to be blocked by infrared rays and ultraviolet rays .

Since the natural curing type aqueous clear binder to be applied to such a glass coating paint can proceed from the chemical precursors by the sol-gel synthesis method, it can be made into a highly uniform binder, and is made of inorganic resin, . At the same time, unlike conventional oily binders, alcohol as a reaction product by the sol-gel synthesis is removed, and TVOC A is less than 200 g / L and is eco-friendly. The clear binder is excellent in compatibility with the photo-functional inorganic nanoparticles due to its water-soluble property, and has excellent inherent transparency to glass and excellent functionality such as durability, salt water resistance, storage stability, hardness, ) Coated glass.

1 is a thermogravimetric analysis (TGA) graph for confirming the high heat resistance of the binder obtained in Example 1 of the present invention.

Hereinafter, the present invention will be described in more detail. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

In this application, the terms "comprises" or "having", etc. are intended to specify the presence of stated features, components, steps, processes, compositions, or combinations thereof in the specification, and not to limit the presence or addition of one or more other features or components, Steps, processes, compositions, or combinations thereof, which are not intended to be limiting.

Also, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Aqueous clear binder

The natural curing aqueous clear binder to be applied to the energy saving type glass coating of the present invention is obtained by sol-gel reaction of a silane coupling agent having an alkyl group, a silane coupling agent having an alkoxy group, a silane coupling agent having an epoxy group, do.

More specifically, the natural curing type aqueous clear binder contains 1 to 5% by weight of a silane coupling agent having an alkyl group based on 100% by weight, 20 to 30% by weight of a silane coupling agent having an alkoxy group, 20 to 30% by weight of a silane coupling agent having an epoxy group %, An acid stabilizer in an amount of 0.01 to 0.3% by weight, and a residual amount of water in a sol-gel reaction.

As an example, the water to be applied to the aqueous clear binder may be applied in the range of 30 to 60 wt%.

In one example, the sol-gel reaction temperature for forming the clear binder is preferably 50 to 95 ° C, 80 to 90 ° C, and preferably, for example, 9 to 14 hours.

In particular, since the natural curing type aqueous clear binder obtained by the sol-gel reaction is subjected to the step of removing the alcohol generated during the sol-gel reaction, the natural curing type aqueous clear binder obtained by the sol-gel reaction removes the alcohol generated during the sol- , The TVOC value is in the range of 10 to 200 g / L, preferably in the range of 50 to 200 g / L.

In one embodiment, the silane coupling agent having an alkyl group essentially contains at least one alkyl group such as methyl, ethyl and propyl, and specific examples thereof include methyltrichlorosilane, methyltrimethoxysilane, methyltri Methyltriethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, butyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, (Meth) acryloxypropylsilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, trimethylchlorosilane, (Meth) acryloxyethoxy silane, methyl [2- (meth) acryloxyethoxy] silane, methyl [ , And methyl tris (3-methyl-3-oxetanyl methoxy) silane. These may be used singly or in a mixture of two or more.

In one embodiment, the silane coupling agent having an alkoxy group includes at least one alkoxy group such as methoxy and ethoxy, but does not include an alkyl group and an acrylic group. Specific examples thereof include tetramethyl orthosilicate, tetraethyl Pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, oxacyclohexyltrimethoxysilane, and the like can be given. These may be used singly or in a mixture of two or more. As an example, among these, tetraethyl orthosilicate is preferable.

In one embodiment, the silane coupling agent having an epoxy group may be one which essentially contains at least one alkoxy group such as methoxy and ethoxy, but does not contain an alkyl group and an acrylic group. Specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-clicydoxypropyl (methyl) diethoxysilane, β- (3,4-epoxycyclohexyl) Ethyl trimethoxysilane and the like. These may be used singly or in a mixture of two or more. As an example, 3-glycidoxytrimethoxysilane is preferable among these.

In one embodiment, examples of acid stabilizers applied to form the binder through the sol gel synthesis method include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, citric acid and fumaric acid; And inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, chlorosulfonic acid, para-toluenesulfonic acid, trichloroacetic acid, polyphosphoric acid, iodic acid, iodic acid anhydride and perchloric acid. These may be used alone or in admixture of two or more, and inorganic acids such as hydrochloric acid and nitric acid are more suitable.

The acid stabilizer used in the present invention is used in an amount of 0.01 to 0.3% by weight in order to control the pH of the binder during the sol-gel synthesis to 2 to 6, more preferably 3 to 5. Specifically, the acid stabilizer acts as a peptizer to prevent gelation due to unstable hydrolysis when the above-mentioned silane coupling agent reacts with water and undergoes hydrolysis (sol-gel reaction). This is because when the acid stabilizer is not added, the silane coupling agent becomes very unstable at room temperature and gels even if partial hydrolysis occurs.

For example, if the content of the silane coupling agent having an alkoxy group applied to produce the aqueous clear binder is less than 20% by weight, the hardness of the coating film may be lowered and the scratch resistance may be lowered, It is difficult to form a coating film, and if it exceeds 30 wt%, there is a problem that a coating strength of a coating film is strong and a crack is formed in the coating film. Therefore, 20 to 30% by weight, preferably 22 to 28% by weight, of the silane coupling agent having an alkoxy group to be applied to the binder is used.

 If the content of the silane coupling agent having an alkyl group to be applied to the aqueous clear binder is less than 1% by weight, the leveling property of the coating is poor and an additive such as a leveling agent must be used. If the amount exceeds 5% by weight, It is difficult to use as aqueous clear binder since it is not compatible. Therefore, the silane coupling agent having an alkyl group applied to the binder is used in an amount of 1 to 5% by weight, preferably 2 to 4% by weight.

If the content of the silane coupling agent having an epoxy group to be applied to the aqueous clear binder is less than 20% by weight, the binder tends to gel during the reaction or has a problem in storage stability at 60 캜. When the content exceeds 30% by weight, It is difficult to use it as a coating binder because the coating film is not durable. Therefore, 20 to 30% by weight, preferably 22 to 28% by weight, of the silane coupling agent having an epoxy group to be applied to the binder is used.

The water to which the aqueous clear binder is applied is used for the sol-gel reaction of the coupling agents described above. If the amount of water to be applied is small, the coupling agent is not hydrolyzed completely, and when the amount of water used is too large, the viscosity of the binder resin is rapidly lowered.

The natural curing type aqueous clear binder formed by the above composition has a very uniform state because the reaction can proceed from the silane coupling agents described above by the sol-gel synthesis method, and is made of an inorganic resin and has high heat resistance. At the same time, unlike the conventional oily binders, alcohol as a reaction product due to the sol-gel synthesis is removed and the TVOC particle size is less than 200 g / L.

Water-based energy-saving glass-coated paint

According to one embodiment of the present invention, the aqueous, energy-saving glass-coated paint has a composition comprising 30 to 70 parts by weight of a natural curing type aqueous clear binder, and 30 to 70 parts by weight of a compound metal oxide which is infrared ray and ultraviolet ray blocking agent.

In another embodiment, the aqueous, energy-saving, glass-coated paint comprises 30 to 70 parts by weight of a natural curing aqueous clear binder 30 to an aqueous clear binder, 30 to 70 parts by weight of an infrared and ultraviolet shielding compound metal oxide and 1 to 30 parts by weight of water .

The natural curing aqueous clear binder to be applied to an aqueous energy-saving glass coating is used in an amount of 30 to 70 parts by weight per 100 parts by weight of the composition. If the amount is less than 30 parts by weight, adhesion with glass and durability deteriorate. If the amount is more than about 70 parts by weight, the amount of inorganic oxide used for blocking solar heat is reduced and exposure of binder is increased on the surface of the coating film, .

In addition, the energy-saving glass coating paint having the above-mentioned composition has an infrared ray-shielding composite metal oxide (hereinafter referred to as " ultraviolet ray shielding compound " Is preferably used in the composition described above. At this time, the composite metal oxide may be used in the state of a sol dispersed in water.

The infrared and ultraviolet cutoff composite metal oxide may be selected from the group consisting of titanium oxide, zinc oxide, indium oxide, tin oxide, antimony tin oxide (ATO) and indium tin oxide (ITO) (MoO ₃ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), vanadium pentoxide (V ₂ O ₅ ), and niobium oxide (Nb ₂ O) in a size of about 10 to 500 nm, ₅ ). ≪ / RTI > This can also block strong infrared in the summer.

The infrared and ultraviolet shielding compound metal oxides mainly include an oxide having a property of blocking infrared rays and shielding a certain degree of ultraviolet rays and an oxide mainly shielding ultraviolet rays and shielding a certain amount of infrared rays to effectively block both infrared rays and ultraviolet rays have.

In particular, the composite metal oxide has a very low solar heat gain coefficient (SHGC) value compared to ATO or ITO alone. The SHGC value is a variable indicating the heat acquisition into the room, and is expressed as a number between '0' and '1'. The closer the number is to '0', the less solar heat is injected. The higher the SHGC value, the greater the amount of sunlight entering the room, which is helpful for heating in low-temperature seasons, but less effective for cooling. On the other hand, a lower SHGC value helps air- do.

However, from the viewpoint of energy saving, it is also necessary to increase the heating efficiency in the winter season, but it is a reality that it is more urgently required to improve the cooling efficiency in the summer season. In particular, the response to temperature control in offices and hospitals is also pointed out in the heat that feels the burning sensation of the window in the summer. There is also a desperate need to improve the cooling efficiency in show windows and convenience stores of showrooms, department stores, and the like, which require large openings. Given this requirement, it is necessary to further increase the infrared absorbability while maintaining the visible light transmittance at a high level.

Accordingly, in the present invention, as a component that shields infrared rays with high efficiency while maintaining the transmittance of the visible light ray at a proper level, it is preferable to use titanium oxide, zinc oxide, indium oxide, tin oxide, antimony tin oxide, (MoO ₃ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), vanadium pentoxide (V ₂ 0 ₅ ) and niobium oxide (Nb ₂ O ₅ ) is newly developed and used.

The addition amount thereof is in the range of about 30 to 70 parts by weight based on 100 parts by weight of the composition. If the added amount is less than about 30 parts by weight, it is difficult to obtain an infrared ray blocking effect. If the added amount is more than about 70 parts by weight, the amount of other components to be added is decreased and it is difficult to form a coating film having desired characteristics.

On the other hand, in general, ultraviolet rays from the sunlight cause skin aging, eye fatigue, cataract, and the like as a cause of discoloration of the article, and in the case of vehicles or buildings that occupy a lot of glass, And indoor items are damaged, and strong ultraviolet rays are strongly required to be cut particularly in summer. In order to shield ultraviolet rays, there are cases where a thin film or a metal coating is applied. However, since they block not only ultraviolet rays but also visible rays, there is a problem that the field of view is not secured or the mining is bad.

Accordingly, in the present invention, a composite metal oxide having an infrared shielding property and an ultraviolet shielding property is used. At least one of titanium oxide, zinc oxide, indium oxide, tin oxide, antimony tin oxide and indium tin oxide having a size of about 10 to 500 nm, At least one of molybdenum oxide (MoO ₃ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), vanadium pentoxide (V ₂ 0 ₅ ) and niobium oxide (Nb ₂ O ₅ ) do. Infrared and ultraviolet shielding compound metal oxide is an inorganic substance that not only has excellent durability but also excellent transparency as well as excellent ultraviolet shielding function.

In addition, since a clear binder for natural curing is used for the glass coating paint of the present invention, there is a problem that the coated film after the coating appears as a convex or concave wave shape due to a partial difference in surface tension without using a conventional leveling agent Generally, it has an excellent appearance of glossy surface and clean surface.

The energy saving glass coating paint having the composition described above is applied to windows to shield infrared rays and ultraviolet rays of sun rays and keeps the transmittance of visible rays at a high level so that the heat conductivity The energy saving effect can be obtained.

The glass coating paint containing the aqueous clear binder of the present invention can be efficiently used regardless of the coating method such as spray coating, roll coating, slot coating, spin coating, flow coating and dip coating, and at the same time, Coating on glass, it is possible to form a coating thin film excellent in durability, abrasion resistance, chemical resistance, hardness and water resistance even by a natural hardening process instead of thermosetting.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, the scope of the present invention is not limited to the following examples.

[Example 1]

A 2L four-necked flask equipped with a thermometer, a condenser, and a stirrer was placed in a heater to prepare 499.9 g of water (pure water) and 0.1 g of nitric acid to prepare a highly heat resistant natural curing type aqueous clear binder for glass coating. , And then slowly charged into a separate flask while stirring at a rate of 500 RPM mixed with 235.0 g of tetraethoxysilane, 15.0 g of dimethyldimethoxysilane and 250.0 g of 3-glycidoxytrimethoxysilane. As the sol - gel reaction proceeded, the reaction product, alcohol, was removed using a reflux tube and reacted for 6 hours to synthesize a natural - curing aqueous clear binder for glass coating.

[Example 2]

225.0 g of tetraethoxysilane, 25.0 g of dimethyldimethoxysilane and 250.0 g of 3-glycidoxytrimethoxysilane were used to synthesize a natural-curing aqueous clear binder for glass coating in the same manner as in Example 1.

[Example 3]

A natural curing type aqueous clear binder for glass coating was synthesized in the same manner as in Example 1 except that 285.0 g of tetraethoxysilane, 15.0 g of dimethyldimethoxysilane and 200.0 g of 3-glycidoxytrimethoxysilane were used.

[Comparative Example 1]

A natural curing type aqueous clear binder for glass coating was synthesized in the same manner as in Example 1 except that 220.0 g of tetraethoxysilane, 60.0 g of dimethyldimethoxysilane and 220.0 g of 3-glycidoxytrimethoxysilane were used.

[Comparative Example 2]

A natural curing type aqueous clear binder for glass coating was synthesized in the same manner as in Example 1 except that 300.0 g of tetraethoxysilane, 15.0 g of dimethyldimethoxysilane and 185.0 g of 3-glycidoxytrimethoxysilane were used.

[Experimental Examples 1 to 5]

The aqueous clear binder obtained according to the above Examples and Comparative Examples was mixed with the composite metal oxide (water-dispersed ATO sol) at a ratio of 1: 1 to the solid content to prepare coatings for glass coating. The storage stability of each of the prepared glass coating paints was evaluated. Thereafter, cleaned glass substrates of 100 mm in width and 100 mm in length were prepared, and then each glass coating paint was uniformly coated on the glass substrate using a spin coater at a thickness of 3 탆. Subsequently, a physical property test was carried out after natural curing at a temperature of 20 to 25 ° C for 12 hours. The results are shown in Table 1 below. Here, the respective physical property evaluation methods are as follows.

 (1) Appearance: It was observed whether the appearance of the coated film was clear and haze free.

 (2) Adhesion: 100/100 After 1 mm cross cut, taping with 3M (No. 710) tape was observed and peeling was observed. At this time, the good state is that the coating film is not detached to the tape, and the defective state is the state where the coating film is peeled off.

  (3) Pencil hardness: A pencil was inserted into a device at an angle of 45 ° according to the hardness, and pencil was applied to the coating at a load of 1 kg, and evaluation was confirmed. Five lines are drawn, and when three or more are good, it is indicated that the pencil hardness is satisfied.

 (4) Storage stability: The prepared coating solution was sampled in a 60 ml container and stored in an oven at 60 ° C to observe the change with time. It was judged that it showed stabilization at room temperature for about 6 months at 60 ° C after 7 days, and that the storage stability criterion at 60 ° C was more than 7 days.

 (5) Salt water resistance: After immersing in 5% NaCl aqueous solution at room temperature for 24 hours, the film state was observed. In this case, the good state is the state in which the coating film is not peeled off, and the defective state is the state in which the coating film is peeled off.

(6) Seawater resistance: After immersion for 30 minutes in 100 ° C boiling water, the presence or absence of wrinkles, cracks, expansion, peeling, gloss reduction, fogging, whitening, discoloration and the like were observed. After observing, a 100/100 1 mm cross cut was made and peeling was observed after taping with 3M (No. 710) tape. At this time, the good state is that the coating film is not detached to the tape, and the defective state is the state where the coating film is peeled off.

[Table 1] Test item evaluation result

As shown in Table 1, in the case of the glass coating paints (Experimental Examples 1 to 3) to which the binders of Examples 1 to 3 were applied, in view of appearance, adhesion, pencil hardness, storage stability, Were found to have satisfactory results. On the contrary, when the silane having an alkyl group is present in a large amount in the same manner as the glass coating paint (Experimental Example 4) to which the binder of Comparative Example 1 is applied, the physical properties of the coating appearance, adhesion and pencil hardness are poor, It was confirmed that when the content of silane having an epoxy group was low as in the case of the applied coating composition for glass coating (Experimental Example 5), water resistance such as water resistance and shelf stability and storage stability were poor and it was difficult to use it as a coating composition for glass coating.

Thermogravimetric evaluation

In order to confirm the high heat resistance of the binder obtained in Example 1, thermogravimetric analysis was carried out. The results are shown in the graph of Fig. FIG. 1 is a thermogravimetric analysis (TGA) graph for confirming the high heat resistance of the binder obtained in Example 1 of the present invention. In the binder of Example 1, loss of the binder does not occur at a high temperature of 700 ° C., As shown in Fig.

Claims (8)

In a clear binder applied to an energy saving type glass coating material,
Silane coupling agent having alkyl group 20 to 30% by weight of a silane coupling agent having 1 to 5% by weight alkoxy group, 20 to 30% by weight of a silane coupling agent having an epoxy group, 0.01 to 0.3% by weight of an acid stabilizer, Wherein the binder is a natural curing type aqueous clear binder. The method according to claim 1, wherein the silane coupling agent having an alkyl group is selected from the group consisting of methyl trichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, Ethyl trimethoxysilane, ethyl trimethoxysilane, ethyl trimethoxysilane, ethyl trimethoxysilane, butyl trimethoxysilane, nonafluorobutylethyl trimethoxysilane, trifluoromethyl trimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, (Meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, methyltri (meth) acryloxysilane , Methyl [2- (meth) acryloxyethoxy] silane, methyltris (3-methyl-3-oxetanemethoxy) silane, and mixtures thereof. The natural curing type aqueous clearBinder. The method of claim 1, wherein the silane coupling agent having an alkoxy group is selected from the group consisting of tetramethylorthosilicate, tetraethylorthosilicate, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxy Silane, oxacyclohexyltrimethoxysilane, and mixtures thereof. The natural curing type aqueous clear binder according to claim 1, The method of claim 1, wherein the silane coupling agent having an epoxy group is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-clicydoxypropyl (methyl) diethoxysilane, - (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, and mixtures thereof. The natural-curing aqueous clear binder according to claim 1, [2] The natural curing type aqueous clear binder according to claim 1, wherein the natural curing type aqueous clear binder obtained by the sol-gel reaction does not contain alcohol due to removal of the alcohol generated during the sol-gel reaction. 30 to 70 parts by weight of an infrared ray and an ultraviolet ray blocking compound metal oxide; And
30 to 70 parts by weight of a natural hardening type aqueous clear binder,
Wherein the natural curing type aqueous clear binder comprises 20 to 30% by weight of a silane coupling agent having an alkyl group and 1 to 5% by weight of an alkoxy group, 20 to 30% by weight of a silane coupling agent having an epoxy group, 0.01 to 0.3% Of water is sol-gel-reacted with water. The energy-saving glass-coated paint according to claim 6, wherein the binder has a TVOC value of 50 to 200 g / L. 30 to 70 parts by weight of an infrared ray and an ultraviolet ray blocking compound metal oxide;
30 to 70 parts by weight of a natural curing type aqueous clear binder; And
1 to 30 parts by weight of water,
Wherein the natural curing type aqueous clear binder comprises 20 to 30% by weight of a silane coupling agent having an alkyl group and 1 to 5% by weight of an alkoxy group, 20 to 30% by weight of a silane coupling agent having an epoxy group, 0.01 to 0.3% Of water is sol-gel-reacted with water.

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