KR20190015775A - Composition for coating a glass film and method for fabricating a glass coating film - Google Patents

Abstract

The present invention discloses: a composition for coating a glass film, which contains a silica particle as a glass coating film-forming material and a bonding site material thereof, wherein the silica particles are a room temperature curable oligomeric silsesquioxane; a production method thereof; and a coating method. The composition for coating the glass film of the present invention has excellent water repellency, abrasion resistance, antifouling properties, durability and heat resistance, can be used for various purposes such as a coating material, a film and the like which require water repellency, abrasion resistance, and antifouling properties, and increases the convenience in processes since no separate crosslinking process is required during manufacturing processes.

Description

Technical Field [0001] The present invention relates to a composition for coating a glass film and a method for manufacturing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a composition for coating a glass film and a method for manufacturing the same, and more particularly to a coating composition for forming a glass coating film on an automobile body or the like, To a composition for coating a glass film and a method for producing a glass coating film which are excellent in various physical properties including water repellency, abrasion resistance and antifouling property and can be easily used because of coating workability and room temperature curing ability.

The coating composition proposed for forming a glass coating film on an automobile body or the like can be largely classified into a siloxane system, a silane system, a silane system, a silica system, and a fluorine system depending on the main component used. The siloxane-based coating composition has a predetermined effect such as water repellency and stainproofing by forming a coating film of a composition containing a raw material of -Si-O-bonding structure such as siloxane, polyorganosiloxane, dimethylsiloxane, etc., The silane-based coating composition may contain silane, disilane, trisilane, trisilane, trisilane, trisilazane, and the like. The silane-based coating composition may contain silane, disilane, trisilane, A composition including a hydrogenated silicon Si _n H _{2n + 2} bonding structure such as silanol, and a raw material of a Si-OH structure exhibits a predetermined effect such as water repellency and stainproofness by forming a coating film, and the silica- A composition containing a silica-based raw material forms a coating film to exhibit predetermined effects such as water repellency and antifouling, and the fluorine-based coating composition has a silicon compound and a fluorine-based material hybrid The composition containing the charge to form a coating film shows a water repellent, antifouling deungso defined effect.

In the silica-based coating composition, there has been developed a technique relating to a glass coating agent using silica particles, which are not sol-gel-type particles, in a binder, but there is a problem that a uniform film can not be formed due to the aggregation due to the lowering of the dispersibility of the silica particles. And US Patent Publication No. 2013-0089670 can be cited as a related document.

Therefore, it can be used as a coating agent for forming a glass coating film on the automobile itself, and it can be used in various outdoor environments such as a temperature change and a humidity change in the summer and winter season, while securing the durability of the glass coating, and in view of various physical properties including water repellency, abrasion resistance and antifouling property There is still a demand for a composition for coating a glass film ensuring physical properties that can be commercialized.

The present invention has been made in order to overcome the problems of the above-described coating composition. The present invention can be used as a coating agent for forming a glass coating film for improving water repellency, abrasion resistance, antifouling property and durability in automobiles, A composition for coating a glass film and a composition for coating a glass film which are excellent in various properties including water repellency, abrasion resistance, antifouling property and the like and can be conveniently used because of coating workability and room temperature curing property, and to improve durability that can be shortened in various outdoor environments such as temperature change and humidity change. And a method for producing a coating film. That is, it shows that excellent pencil hardness of 7H or more and water contact angle shows water repellency of 100 degrees or more and durability can be ensured as a result of measuring thickness change of coating layer after repeated washing process while providing antifouling property measured by fingerprint adhesion Which is capable of producing a glass coating film capable of forming a glass coating film.

The glass coating film of the present invention can be used not only for automobile body coating but also for various applications such as coating compositions and coating methods which can be used for other applications requiring wear resistance, water repellency, antifouling property and durability.

According to an aspect of the present invention, there is provided a composition for coating a glass film, which comprises silica particles as a glass coating film-forming material and a bonding site thereof, and the silica particles are room temperature curable oligomeric silsesquioxane.

According to another aspect of the present invention, there is provided a method of manufacturing a glass substrate, comprising: coating a substrate with a mixed solution of the glass coating film forming material and room temperature curable oligomeric silsesquioxane; And a room temperature curing treatment of the coated mixture, wherein the room temperature curable oligomeric silsesquioxane is incorporated in the glass coating film forming material as a crosslinking site or a dispersion bonding site to exist as a three-dimensional structure A manufacturing method is provided.

According to still another aspect of the present invention, there is provided a film having water repellency, abrasion resistance, antifouling property and durability produced by the above method.

According to another aspect of the present invention, there is provided a coating material having water repellency, abrasion resistance, antifouling property and durability produced by the above method.

According to another aspect of the present invention, there is provided a method for coating a glass substrate, comprising the steps of: coating a substrate with a composition for coating a glass substrate based on a silane-based glass coating film forming material; and curing the coating at room temperature to form a room temperature curable oligomeric A silane starting compound that forms a silane-based glass coating film-forming material by using silsesquioxane as a crosslinking site, or a stereogenic structure in which another room-temperature-curable oligomeric silsesquioxane is linked at the crosslinking site to form a skeleton A first step of forming a glass film to provide a glass substrate; And coating a glass film coating composition based on a siloxane-based glass coating film-forming material different from the glass-film coating composition used in the first step on the glass film formed in the first step, and curing the coating at room temperature A room temperature curable oligomeric silsesquioxane contained in the composition for coating a glass film may be used as a dispersion binding site to form a polyorganosiloxane constituting a salicylic acid glass coating film forming material or a room temperature curable oligomeric silsesquioxane And a second step of forming a second glass film to provide a dispersed three-dimensional structure.

In the composition for coating a glass membrane of the present invention, not only the specific silsesquioxane compound acts as a crosslinking site or a dispersion bonding site but also the crosslinking density is increased because the silsesquioxane compound itself is a siloxane bond. The silsesquioxane compound may be modified by various substituents depending on the required physical properties. For example, the silsesquioxane compound may be used as a substituent having high miscibility with the glass-forming material or a substituent capable of improving the water- Thereby providing a glass coating film with desired properties of improvement. As a result, it is possible to secure durability as a result of measuring the pencil hardness of 7H or more and the thickness change of the coating layer after repeated washing process when modified with a substituent having high miscibility with the glass-film forming material, Further, since it is improved, it is possible to provide a glass coating film which is easy to apply even in the summer, the temperature change in the winter season, and the humidity change. Also, it is possible to provide a glass coating film which, when modified with a substituent capable of improving water solubility and antifouling property, exhibits water repellency of 100 deg. Or more at a water contact angle and provides antifouling property measured by fingerprint adhesion. Furthermore, since the silsesquioxane compound has various structures, the cage structure is specifically used so as to provide a constant skeleton structure, so that it is easy to control the physical properties of the silsesquioxane compound relative to other structures.

When the composition for coating a glass film is used as a coating agent for forming a glass coating film on an automobile body or the like, durability which is inevitably shortened in a variety of outdoor environments such as a temperature change and a humidity change in a winter season and a winter season is improved and water repellency, It has excellent physical properties and can be easily used because of coating workability and room temperature curing ability.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a glass coating film formed by coating a composition for coating a glass substrate according to an embodiment of the present invention on a vehicle body and forming a skeleton at a crosslinking site when the substrate is cured at room temperature.
FIG. 2 is a schematic view showing a glass coating film serving as a dispersion bonding site when a composition for coating a glass film according to another embodiment of the present invention is applied to an automobile body and dried.
3 is a flow chart illustrating a method of manufacturing a glass membrane using a composition for coating a glass film according to an embodiment of the present invention.

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

The composition for coating a glass film of the present invention may include a room temperature curable oligomeric silsesquioxane which can act as a crosslinking site or a dispersed bond site when coated on an automobile body and cured at room temperature, .

FIG. 1 is a schematic view showing a case where a composition for coating a glass substrate according to an embodiment of the present invention (Example 1) is coated on an automobile body and cured at room temperature, a room temperature curable oligomeric silsesquioxane silane- (Cross-linking point: a network bonding point of a molecular chain) in a curing (condensation reaction) process of a forming material.

The room temperature curable oligomeric silsesquioxane is a base material constituting a -Si-O- linkage constituting a skeleton in a glass coating film (hereinafter referred to as a glass film), and as the room temperature curable oligomeric silsesquioxane, Lt; / RTI > is preferred.

1, in the curing (condensation polymerization) step of the silane-based glass coating film forming material, the room temperature curable oligomeric silsesquioxane (specifically, the R site in the following formula) is used as a cross- The silane starting compound constituting the glass coating film forming material of the glass transition temperature, or another room temperature curable oligomeric silsesquioxane at the crosslinking site may be connected to each other to form a skeleton. The skeleton of the composition for coating a glass film can be irreversibly fixed. As a result, it not only functions as a crosslinking site but also has a siloxane structure itself, so that the crosslinking density in the composition can also be increased. In particular, when cage-type nanoparticles are used, the physical properties can be stably maintained.

2 is a graph showing the relationship between the shape of the room temperature curable oligomeric silsesquioxane and the siloxane-based coating film forming material acting as dispersion bond sites during the drying (dispersion) process of the composition for coating a glass membrane according to another embodiment of the present invention 2, the room temperature curable oligomeric silsesquioxane (specifically, the R site in the following chemical formula) is dispersed in the dispersion bonding site during drying (dispersion) of the siloxane-based glass coating film forming material And the polyorganosiloxane constituting the siloxane-based glass-coating-film-forming material is bonded or the room-temperature-curable oligomeric silsesquioxane is dispersed. The dispersion- In particular, when cage-type nanoparticles are used, the physical properties can be stably maintained.

The composition for coating a glass film according to an embodiment of the present invention includes silica particles as a material for forming a glass coating film and a bonding site thereof, and the silica particles are the above-mentioned room temperature curable oligomeric silsesquioxane .

As used herein, the term " room temperature curing type " refers to a form showing a phenomenon of curing at room temperature without heating, but not particularly limited thereto.

As described above, the room temperature curable oligomeric silsesquioxane has a random structure, a linear (ladder) structure, a cage structure, and a partial cage structure as a material constituting the skeleton (crosslinking site or dispersed binding site) . However, it is possible to provide a cage-type structure for providing a constant skeletal structure with an advantage that the physical properties of the cage-type structure can be easily controlled compared to other structures. However, the cage type silsesquioxane itself has a crystalline structure, which has a limitation in solubility in solution processing and causes a problem that the reproducibility of the performance is not ensured due to the reformation of molecular units such as a recrystallization phenomenon in the cage type structure itself. Linear silsesquioxane is excellent in solution processability and has a structure capable of compensating for the disadvantages of the cage-type structure, but has a disadvantage that the physical properties thereof are insufficient compared to the cage-type structure having a crystal structure. In addition, since the random silsesquioxane is polymerized in a free form, there is a problem that it is difficult to secure the limit and reproducibility to be applied by gelation using Si-OH, Si-alkoxy or the like which is unstable in the polymer.

Accordingly, the present invention is characterized in that an organic functional group is used in the side chain of the cage silsesquioxane compound to act as a bonding site for a coating film forming material, thereby inducing an easy curing or dispersion process to be introduced without a separate crosslinking process.

For reference, the following Reaction Scheme 1 shows a process for synthesizing a cage silsesquioxane compound according to an embodiment of the present invention. As shown in Reaction Scheme 1, hydrolysis and condensation polymerization can be sequentially performed according to the following Reaction Scheme 1 using organic-trichlorosilane and organic-trialkyloxysilane as starting materials. At this time, the alkoxysilane can be converted into a resin-based product by hydrolysis and condensation using a titanate catalyst such as tetrabutyl titanate, an acid catalyst such as acetic acid, or a basic catalyst such as triethanol amine. The starting materials shown in the reaction schemes may be commercially prepared and commercially available, or they can be generally prepared and used according to methods known in the literature. Such cage silsesquioxane compound and the like OctaSilane POSS ^ⓡ SH310 sold by Bulk Chemical LTD..

[Reaction Scheme 1]

In the above reaction formula, R may be methyl, phenyl, vinyl, etc., and R 'may be methyl, ethyl, and the like.

Here, the substituent R in the above Reaction Scheme 1 may be modified by various substituents depending on the physical properties required as a glass coating film obtained by coating and curing the automobile body. For example, it is possible to provide a glass coating film with improved physical properties by appropriately modifying it with a substituent having a high miscibility with a coating film forming material, or a substituent capable of improving water solubility and antifouling property.

[Reaction formula 2] represents a substituent modification process of a room temperature curable oligomeric silsesquioxane (cage structure) according to an embodiment of the present invention, and may be performed through coupling reaction using, for example, a platinum catalyst. An example of the coupling reaction includes a material obtained by partially modifying a room temperature curable oligomeric silsesquioxane (cage structure) by grafting using a platinum catalyst.

Here, the substituent introduced into the modification may serve as a bonding site having high miscibility with the coating film forming material without requiring a separate crosslinking process. Substituents described herein mean, by way of example, that one or more hydrogen atoms are each independently replaced with the same or different substituents. For example, the terminal group of the crosslinking structure may be selected from a hydroxyl group or an alkoxy group. The hydroxy group or the alkoxy group may be introduced by a siloxane oligomer group, respectively. The crosslinking structure may be a three-dimensional structure in which a glass coating material including a silane-based or siloxane-based material and the room temperature-curable oligomeric silsesquioxane are connected to each other by -Si-O- linkage. That is, the Si of the silane-based oligomer or the polysiloxane and the Si of the room-temperature-curable oligomeric silsesquioxane are linked by -Si-O- bond to form a crosslinked structure. For example, such a crosslinking structure can be obtained by reacting a mixed solution at 25 DEG C under a solvent.

[Reaction Scheme 2]

Substituents having high miscibility with the coating film forming material may include, but are not limited to, hydroxy, alkoxy of 1 to 3 carbon atoms, amino, mercapto, vinyl, isocyanate or (meth) acrylate, More preferably hydroxy, or alkoxy of 1 to 3 carbon atoms in which the skeleton can be connected by -Si-O- bond.

The structure modified with the substituent can be represented as follows, for example.

,

,

,

,

,

,

,

,

,

,

,

,

등을 들 수 있고, 여기서 n은 0 내지 20의 정수, 혹은 1 내지 6의 정수일 수 있다. 이들 치환기로 개질할 경우 7H 이상의 탁월한 연필경도와 반복되는 세차 공정 이후 코팅층의 두께변화를 측정한 결과로서 내구성 또한 확보가 가능하고 상승된 가교밀도로 인하여 내열성 또한 개선되므로 하절기, 동절기의 온도변화, 습도변화에도 적용하기 용이한 유리 코팅막을 제공할 수 있다. As a specific example, a substituent having high miscibility with the above-mentioned coating film-

,

,

,

,

,

,

, Wherein n may be an integer of 0 to 20, or an integer of 1 to 6. When these substituents are modified, excellent durability can be ensured as a result of excellent pencil hardness of 7H or more and a change in thickness of the coating layer after repeated washing process, and heat resistance is also improved due to increased crosslink density, It is possible to provide a glass coating film that is easy to apply even to changes.

Examples of the substituent capable of improving water solubility and antifouling property include, but are not limited to, a halogen substituent. Particularly, the use of a fluorine substituent lowers the surface energy of the coating film and increases the mechanical properties of a coating film such as alkoxysilane, Not only improves abrasion resistance but also improves antifouling properties by imparting surface roughness to the coating film. That is, by controlling the surface roughness of the surface of the coating film, it is possible to reduce the contact area with contaminants due to bending and enlarge the exposed area to the air, thereby making it difficult to adhere contaminants and to easily remove contaminants already adhered. Specifically, as an example of the coupling reaction, a substance having a double bond including fluorine in a room temperature curable oligomeric silsesquioxane (kage type) molecule is grafted using a platinum catalyst to partially fluorine-modify the substance . The functional group of the polymer having a double bond includes, for example, a vinyl group, an allyl group, an acryl group or a methacryl group, and in the modification process, 10 to 90% of the functional groups contained in the room temperature curable oligomeric silsesquioxane, It may be preferable that the water-repellent layer is modified within the range of 10 to 70%, or 50 to 90%, since the water-repellent and antifouling performance is exhibited. Modified siloxane in which alkoxymetal (Mt (OR ₃ ) ₄ ) is added to the fluorine-modified siloxane obtained by the coupling reaction and partially cross-linked and the sol-gel reaction between the silane molecules is used, or the coupling reaction (TEOS) and ethanol (EtOH) is added to the fluorine-modified siloxane obtained in the step (1) and stirred to prepare an antifouling hybrid coating material.

As a specific example, the structure modified with a fluorine substituent can be represented as follows, for example.

를 들 수 있고, 여기서 n은 0 내지 20의 정수, 혹은 1 내지 6의 정수일 수 있다. 이들 치환기로 개질할 경우 물 접촉각이 100도 이상의 발수력, 혹은 115도 이상의 초발수력을 나타내고, 지문부착성으로 측정한 방오성을 제공하는 것으로 확인되는 유리 코팅막을 제공할 수 있다. Examples of the substituent capable of improving the water-repelling ability and antifouling property include,

, Wherein n may be an integer of 0 to 20, or an integer of 1 to 6. It is possible to provide a glass coating film which, when modified with such a substituent, exhibits water repellency of 100 degrees or more at a water contact angle, or initial water repellency of 115 degrees or more and is found to provide antifouling property measured by fingerprint adhesion.

The room temperature curable oligomeric silsesquioxane is a base material constituting a -Si-O- linkage constituting a skeleton in the glass membrane. The room temperature curable oligomeric silsesquioxane is, for example, 10 nm or less, 1 to 10 nm, The smaller the particle size, the easier it is to perform the function as the cross-linking site (cross-linking point: the network-joining point of the molecular chain) and the cross-linking density can be further increased within the same area.

The room temperature-curable oligomeric silsesquioxane of the formula (RSiO _{1. 5)} is represented by m, wherein R is hydroxy, alkoxy of 1 to 3 carbon atoms, amino, mercapto, vinyl, halogen, isocyanate or (meth) acrylic Wherein the repeating unit (m) is an integer of 8 to 16, or 8, 10, 12, or 16, which is an alkyl of 1 to 20 carbon atoms or an aryl of 6 to 20 carbon atoms substituted with a functional group independently selected from the group consisting of At this time, not only the compatibility with the coating film forming material is maximized, but also the chemical and thermal stability is very good and various characteristics such as hardness, water resistance, weather resistance, gas barrier property, heat resistance and insulation property can be improved or exhibited.

The room temperature-curable oligomeric silsesquioxane modified according to the present invention can impart excellent physical properties, heat resistance characteristics and the like to a predetermined substrate through simple room temperature curing (condensation polymerization) or drying (dispersion) processes. Also, although not specifically disclosed, when an organic functional group capable of post-curing is introduced, various curing using heat or light is possible, and when an unsaturated hydrocarbon or the like is introduced into an organic functional group, a radical initiator can be used. When an organic functional group contains an epoxy, a sulfonium-based or diazonium-based photopolymerization initiator may be used. Ethylenediamine, which is an amine curing agent, may be used depending on the type of the organic functional group.

The room temperature curable oligomeric silsesquioxane may have a weight average molecular weight of 50,000 g / mol or less, 27,000 g / mol or 11,000 to 27,000 g / mol, for example, So that the coating workability is excellent. The room temperature curable oligomeric silsesquioxane may have a viscosity of 100 to 100,000 mPs / s or a viscosity of 100 to 10,000 mPs / s measured at 25 ° C.

For example, the room temperature curable oligomeric silsesquioxane may have a polydispersity (PDI) of 1 to 5, or 1.9 to 2.5. The flatness of the glass coating film formed within these ranges can be excellent.

The glass coating film forming material may be at least one selected from the group consisting of a siloxane glass coating film forming material, a silane glass coating film forming material, a silane glass coating film forming material, a silica glass coating film forming material and a fluorine glass coating film forming material.

As specific examples, the silane-based glass coating film forming material as the glass coating film forming material, and the formula as its binding site material (RSiO _{1. 5)} m (wherein R is hydroxy, alkoxy, amino, mercapto of 1 to 3 carbon atoms, Is an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms and substituted with a functional group independently selected from the group consisting of a vinyl, halogen, isocyanate or (meth) acrylate group, and the repeating unit (m) Wherein the room temperature curable oligomeric silsesquioxane (specifically, the R site in the above formula) is bonded to the crosslinking site in the condensation polymerization process of the silane-based glass coating film-forming material, wherein the room temperature curable oligomeric silsesquioxane A silane raw material compound constituting the silane-based glass coating film-forming material, or another room temperature curing type oligomeric raw material Quinone is a dioxane can be provided a three-dimensional structure forming the skeleton are connected to each other in the cross-linking binding site.

The silane-based glass coating film-forming material may be, for example, a) a silane raw material compound for condensation; b) silane coupling agents; c) a hydrocarbon solvent; And d) an alcohol solvent.

The silane starting compound for condensation of a) may be a conventional silane starting compound used for condensation such as diorganodialkoxysilane, organotrialkoxysilane and tetraalkoxysilane. Specific examples include cyclic dialkyl (aryl) siloxanes including octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetraphenylcyclotetrasiloxane, dimethyldimethoxysilane, dimethyldiethoxysilane, di (Aryl) dialkoxy silane, including phenyl dimethoxy silane and methylphenyl dimethoxy silane.

The b) silane coupling agent includes, for example, methacryloxypropyl trimethoxysilane (MATS), acryloxypropyltrimethoxysilane, vinyltriethoxysilane (VTES), vinyltriethoxysilane And may be at least one reactive silane selected from the group consisting of vinyltrimethoxysilane (VTMS) and allyltrimethoxysilane.

The c) hydrocarbon solvent is a diluent solvent for improving the coating property. Examples of the diluent solvent include monoglyme, diglyme, butyl carbitol, alpha-terpineol, glycerin, ethyl acetate, butyl acetate, ethyl The organic solvent may be selected from the group consisting of lactate, carbitol acetate, acetone, methyl ethyl ketone, cyclohexanone, chloroform, methylene chloride, diethyl ether, tetrahydrofuran, dioxane, hexane, cyclohexane, heptane, dimethylformamide, dimethylacetamide And may be at least one selected from the group consisting of N-methylpyrrolidone, benzene, toluene, xylene, terpine, white spirit, petrol and ligroin.

The d) alcohol solvent is a diluent solvent for improving the dispersibility and storage stability of the silane starting compound, and examples thereof include methanol, ethanol, isopropanol, butanol, benzyl alcohol, diacetone alcohol, methoxy ethanol, ethoxy ethanol, butoxy ethanol , Ethylene glycol, butylene glycol, diethylene glycol, and propylene glycol monomethyl ether.

Tinuvin 292, Tinuvin 144, Tinuvin 622LD (Shiba Kagi article, Japan), sanol LS-770, sanol LS-765 (Japan), and the like can be added, , sanol LS-292, and sanol LS-744 (Sankyo, Japan). Also, various kinds of dispersants, reducing agents and leveling agents used in this field can be applied without being limited.

Specific examples of the silane-based glass coating film-forming material include a) octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetraphenylcyclotetrasiloxane, dimethyldimethoxysilane, dimethyldiethoxysilane, di 0.1 to 10% by weight, or 0.5 to 4% by weight, of at least one silane starting compound for condensation selected from the group consisting of phenyldimethoxysilane and methylphenyldimethoxysilane; b) methacryloxypropyl trimethoxysilane (MATS), acryloxypropyltrimethoxysilane, vinyltriethoxysilane (VTES), vinyltrimethoxysilane (VTMS), vinyltrimethoxysilane 0.1 to 10% by weight, or 0.5 to 4% by weight, of at least one reactive silane coupling agent selected from the group consisting of allyltrimethoxysilane; c) a mixture of monoglyme, diglyme, butyl carbitol, alpha-terpineol, glycerine, ethyl acetate, butyl acetate, ethyl lactate, carbitol acetate, acetone, methyl ethyl ketone, cyclohexanone Methylene chloride, diethyl ether, tetrahydrofuran, dioxane, hexane, cyclohexane, heptane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, benzene, toluene, xylene, 1 to 25% by weight, or 5 to 15% by weight, of at least one hydrocarbon solvent selected from the group consisting of terpine, white spirit, petroleum and ligroin; And d) a solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, benzyl alcohol, diacetone alcohol, methoxyethanol, ethoxyethanol, butoxyethanol, ethylene glycol, butylene glycol, diethylene glycol and propylene glycol monomethyl ether And a remaining amount of at least one selected alcohol solvent. The alcohol solvent may be, for example, 40 to 85% by weight or 45 to 98% by weight of isopropyl alcohol and 1,4-butanediol.

Specific examples of the silane-based glass coating film-forming material include a) octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetraphenylcyclotetrasiloxane, dimethyldimethoxysilane, dimethyldiethoxysilane 0.5 to 20% by weight, or 1 to 6% by weight, of at least one silane starting compound for condensation selected from the group consisting of diphenyldimethoxysilane and methylphenyldimethoxysilane; b) methacryloxypropyl trimethoxysilane (MATS), acryloxypropyltrimethoxysilane, vinyltriethoxysilane (VTES), vinyltrimethoxysilane (VTMS), vinyltrimethoxysilane 0.1 to 15% by weight, or 1 to 8% by weight of at least one reactive silane coupling agent selected from the group consisting of allyltrimethoxysilane; c) a mixture of monoglyme, diglyme, butyl carbitol, alpha-terpineol, glycerine, ethyl acetate, butyl acetate, ethyl lactate, carbitol acetate, acetone, methyl ethyl ketone, cyclohexanone Methylene chloride, diethyl ether, tetrahydrofuran, dioxane, hexane, cyclohexane, heptane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, benzene, toluene, xylene, 5-40 wt%, or 10-20 wt% of at least one hydrocarbon solvent selected from the group consisting of terpine, white spirit, petrol and ligroin; And d) a solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, benzyl alcohol, diacetone alcohol, methoxyethanol, ethoxyethanol, butoxyethanol, ethylene glycol, butylene glycol, diethylene glycol and propylene glycol monomethyl ether And a remaining amount of at least one selected alcohol solvent. As the alcohol solvent, for example, isopropyl alcohol and 1,4-butanediol may be blended to give a total amount of 20 to 95% by weight or 30 to 80% by weight.

As a specific further example, the glass as a coating film forming materials siloxane-based glass a coating film forming material, and the formula as its binding site material (RSiO _{1. 5)} m (wherein R is hydroxy, alkoxy, amino, Murray having 1 to 3 carbon atoms Is an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms and substituted with a functional group independently selected from the group consisting of a vinyl, a halogen, an isocyanate or a (meth) acrylate group, and an integer of 20 or less ), Wherein the room temperature curable oligomeric silsesquioxane (specifically, the R position in the above formula) is reacted with the siloxane oligomeric silsesquioxane represented by the general formula A polyorganosiloxane constituting the siloxane-based glass coating film-forming material is bonded to a dispersed (dry) bonding site, The curable oligomeric silsesquioxane is possible to provide a three-dimensional structure to be dispersed.

Examples of the siloxane-based glass coating film-forming material include (a) a polyorganosiloxane; (b) a water-soluble aliphatic amine compound; (c) a surfactant; (d) a hydrocarbon solvent; And (e) emulsions, specifically water as a dispersion medium for microemulsions. That is, in the case of the aqueous composition, the remaining amount to make the solution or emulsion 100% consists of water, while in the case of the oily composition as described above, the remaining amount to make the solution 100% consists of the solvent except water. In general, the amount of the solid content in the composition according to the present invention may be from 0.1 to 90% by weight, or from 5 to 50% by weight.

It can be formulated into a concentrate or emulsion having a high solids content for subsequent dilution and direct application to automobile bodies or as a ready-to-use solution or emulsion for low solids content for direct application to automobile bodies. Here, a film containing 3 to 40% by weight of solids in the composition for coating a glass film may be sufficient.

The (a) polyorganosiloxane may be a conventional siloxane polymer including an alkoxy-terminated dimethylpolysiloxane and an aminoalkoxy-terminated dimethylpolysiloxane. For example, it may be at least one condensate selected from diorganodialkoxysilane, organotrialkoxysilane, and tetraalkoxysilane. As a specific example, 68037-58-1 (Siloxanes and Silocones, di-Me, (dimethoxymethylsilyl) oxy-terminated), or CAS No. 68037-58-1. (3-trimethoxysilyl) propyl) -1,2-ethanediamine), which is a polyorganosiloxane of the formula , Wherein the alkoxysilyl group corresponds to a hydrolyzable functional group capable of forming a linking or crosslinking structure.

Examples of the water-soluble aliphatic amine compound (b) include monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, triisopropanolamine, dibutylamine, tributylamine, diisopropanolamine, methylmonoethanolamine, And may be at least one member selected from the group consisting of ethanolamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, dimethylethanolamine, isopropylamine, cyclopentylamine, cyclohexylamine and diamylamine .

The surfactant (c) is used for stabilizing the emulsion, specifically, the microemulsion. Examples thereof include malonic acid, itaconic acid, naphthenic acid, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 5-norbornene- Acetic acid, acetic acid, 2-methyl-2-oxo-2-methyl-2-oxo-3-dicarboxylic acid, 1-adamantanecarboxylic acid, trifluoroacetic acid, pentafluoropropionic acid, There may be mentioned acetic acid, acetic acid, oxalic acid, pivalic acid, 2-ethylhexanoic acid, sobic acid, malic acid, maleic acid, fumaric acid, glyoxylic acid, pyruvic acid, succinic acid, glutaric acid, gluconic acid, , Neodecanoic acid, stearic acid, oleic acid, linoleic acid, abietic acid, sulfonamide, succinic acid, sulfonate, sodium lauryl sulfate, alkyl glyceryl ether sulfonate, ethoxy ether sulfonate, alkyl sulfosuccinate, Nate, alpha sulfo Nitrated fatty acids, alpha olefin sulfonates, and alkyl alkoxy sulfates. Siloxane in the form of a condensate is generally stabilized in the form of an aqueous emulsion through cationic and nonionic surfactants and the like. When such an emulsion form is destroyed, the condensed siloxane is no longer stable, So as to be cured. Since the hydrocarbon solvent (d) is the same as that described above, a detailed description thereof will be omitted.

Specific examples of the siloxane-based glass coating film-forming material include (a) 0.1 to 40% by weight or 0.5 to 35% by weight of a polyorganosiloxane; (b) at least one compound selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, triisopropanolamine, dibutylamine, tributylamine, diisopropanolamine, methylmonoethanolamine, methyldiethanolamine, ethylenediamine, diethylene tri 0.1 to 10% by weight of at least one water-soluble aliphatic amine compound selected from the group consisting of amine, triethylenetetramine, tetraethylenepentamine, dimethylethanolamine, isopropylamine, cyclopentylamine, cyclohexylamine and diamylamine, 0.5 to 4% by weight; (c) at least one compound selected from the group consisting of malonic acid, itaconic acid, naphthenic acid, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 5-norbornene 2-carboxylic acid, 5-norbornene 2,3-dicarboxylic acid, Acetic acid, acetic acid, 2-methyl-acetoacetic acid, oxalic acid, pivalic acid, 2-ethylhexanoic acid, malic acid, malic acid, maleic acid, But are not limited to, acid, maleic acid, fumaric acid, glyoxylic acid, pyruvic acid, succinic acid, glutaric acid, gluconic acid, picric acid, citric acid, benzoic acid, neodecanoic acid, stearic acid, oleic acid, linoleic acid, abietic acid, Alkyl sulfosuccinates, alkyl sulfosuccinates, alkyl ethoxylated caprosinates, alpha-sulfonated fatty acids, alpha olefin sulfonates and alkyl sulfates such as alkyl sulfosuccinates, Selected from the group consisting of alkoxy sulfates From 0.1 to 10% by weight, alternatively from 0.5 to 4% by weight of at least one surfactant; (d) monoglyme, diglyme, butyl carbitol, alpha-terpineol, glycerin, ethyl acetate, butyl acetate, ethyl lactate, carbitol acetate, acetone, methyl ethyl ketone, cyclohexane A solvent such as methanol, ethanol, propanol, isopropanol, butanol, isopropanol, butanol, isopropanol, butanol, isopropanol, 5 to 25% by weight, or 1 to 25% by weight of at least one hydrocarbon solvent selected from the group consisting of terpine, white spirit, petroleum and ligroin; And (e) 40 to 85% by weight, or 50 to 95% by weight of water.

The molar ratio of the room temperature curable oligomeric silsesquioxane to the glass coating film forming materials (a) and (b) may be, for example, 1: 0.1 to 0.5 or 1: 0.1 to 0.35, It acts as a bonding site in the microemulsion, so that it is possible to provide a sufficient effect of improving physical properties without requiring a separate crosslinking step. The molar ratio of the additive c), c), d), d), and e) excluding the room temperature curable oligomeric silsesquioxane to the glass coating film forming material a) 1 does not adversely affect the bonding sites of the room temperature curable oligomeric silsesquioxane in the solvent dispersion coating liquid or microemulsion (b) and (b).

The glass coating film may be produced according to various embodiments. FIG. 3 is a process flow chart showing a method of manufacturing a composition for coating a glass film according to an embodiment of the present invention. Referring to FIG. 3, in step S1, a mixed solution of the above-mentioned glass coating film forming material and room temperature curable oligomeric silsesquioxane is prepared. Subsequently, the mixed solution is coated on a substrate (automobile body) as step S2. If the room temperature curing type oligomeric silsesquioxane is used as the crosslinking site shown in FIG. 1 or the dispersion bonding site shown in FIG. 2 as the room temperature curing type oligomeric silsesquioxane, And are present as a three-dimensional structure.

In a specific embodiment, the mixed solution of the glass coating film-forming material and the room temperature-curable oligomeric silsesquioxane is a solvent dispersion coating solution (further, a coupling reaction solution), and the room temperature curable oligomeric silsesquioxane is used as a cross- A silane starting compound constituting the silane-based glass coating film-forming material or another room-temperature-curable oligomeric silsesquioxane may be connected to each other at the crosslinking site to form a skeleton.

In another specific embodiment, the mixed solution of the glass coating film-forming material and the room temperature-curable oligomeric silsesquioxane is a microemulsion, and the room temperature curable oligomeric silsesquioxane is used as a dispersion binding site to form the siloxane- A polyorganosiloxane constituting the material may be bonded or the room temperature curable oligomeric silsesquioxane may be dispersed.

As a specific example of the production of the glass membrane, a room-temperature-curable oligomeric silsesquioxane modified to act as a bonding site in the glass coating film is prepared as step S1-1 in FIG. The modification can be carried out by selecting a miscible substituent or a solubility function and an antisun substituent according to the physical properties to be provided and performing a coupling reaction under a suitable catalyst.

Next, as a step S1-2, the room temperature curable oligomeric silsesquioxane and silane raw material are mixed in a hydrocarbon solvent to form a solution, and a silane coupling agent and an alcohol solvent are added to the solution to form a mixed solution. Alternatively, as a modified example of Step S1-2, the mixed solution may be formed by mixing the room temperature curable oligomeric silsesquioxane and the silane raw material with a hydrocarbon solvent, a silane coupling agent and an alcohol solvent. When mixing the raw materials to form a mixed solution, the mixing time can be adjusted to 5 seconds or more and 10 hours or less. When the mixing time is less than 5 seconds, the mixing is not performed well. On the other hand, when the mixing time is longer than 10 hours, the gelation proceeds and the reaction proceeds in a state where the drying is not carried out to reduce the surface area of the formed structure, can do.

If necessary, the mixed solution is further reacted as step S1-3. The reaction time is preferably 5 seconds or more and 50 hours or less. When the reaction time is less than 5 seconds, the reaction is not performed well. When the reaction time exceeds 50 hours, the complete reaction proceeds, and the reaction is meaningless. It is usually preferable to carry out the reaction for 10 seconds to 1 hour. The reaction temperature may be from 0 to 70 ° C, and it is usually from room temperature to 50 ° C or less in terms of surface structure formation depending on the reaction rate.

Subsequently, as the step S2, the reaction liquid is coated on the automobile body.

Thereafter, as the step S3, the coated reaction solution is cured at room temperature (condensation polymerization) to obtain a room temperature curable oligomeric silsesquioxane (specifically, the R position in the formula) as a cross-linking site, , And the other room temperature curable oligomeric silsesquioxane is connected to each other by a -Si-O- linkage to form a skeleton (see Fig. 1). In addition, depending on the type of substituent at the R position in the above formula, miscibility can be improved or the water-solubility and disinfecting ability can be further improved.

Here, the coating method is preferably by local treatment including local coating on an automobile body, and includes spin, bar, slit, spray, curtain, gravure coating and the like.

After the coating, drying at a temperature near room temperature can cure the reaction product in which the gelation proceeds, and in some cases, even when the temperature is raised to room temperature or higher and dried, high crosslinking density can be obtained and high temperature stability can be imparted. If the drying time is less than 1 hour, the desired properties can not be obtained because the drying process and the completion degree of the reaction are lowered. It is advantageous in that it can be manufactured only by drying without washing and filtering steps by the curing method.

According to the present invention, the conventional solid silicone particles can be uniformly cured (dispersed) in a coating solution without requiring a mechanical mixing process consuming a lot of energy, which is preferable in terms of coating workability and economy.

For example, a modified room temperature curable oligomeric silsesquioxane is prepared. The modification can be carried out by selecting a miscible substituent or a solubility function and an antisun substituent according to the physical properties to be provided and performing a coupling reaction under a suitable catalyst.

Next, the room temperature curable oligomeric silsesquioxane and polyorganosiloxane are mixed in a hydrocarbon solvent to form a solution, and a surfactant and water are added to the solution to form a mixed solution.

If necessary, the mixed solution is stirred to form an emulsion.

The emulsion is then coated on the automobile body.

Then, the coated emulsion is dried at room temperature to provide the siloxane-based starting material as a dispersion bond site at room temperature-curable oligomeric silsesquioxane (specifically, the R-position in the formula) (See FIG. 2). Also, depending on the kind of the substituent at the R position in the above formula, miscibility can be improved or the water-solubility and antifouling performance can be improved.

 Here, the coating method is preferably by local treatment including local coating on an automobile body, and includes spin, bar, slit, spray, curtain, gravure coating and the like.

In this case, the drying temperature is from 0 ° C to 100 ° C. If the drying temperature is lower than 0 ° C, the crosslinking reaction does not occur sufficiently due to slow reaction and drying, and crosslinking does not occur sufficiently due to rapid drying at temperatures exceeding 100 ° C. Generally, it is preferable to dry at a temperature near the room temperature, and even if the temperature is raised to room temperature or higher, the crosslinking density is high and high temperature stability can be imparted. If the drying time is less than 1 hour, the desired properties can not be obtained because the drying process and the completion degree of the reaction are lowered. It is advantageous in that it can be manufactured only by drying without washing and filtering steps by the curing method.

The composition for coating a glass film may have excellent water-repellency. Thus, according to one embodiment of the present invention, there is provided a water repellent coating film comprising the composition for coating a glass film. For example, in the case of the water-repellent coating film, the measured water contact angle may be 100 degrees or more.

The composition for coating a glass film may have excellent abrasion resistance. Thus, according to another embodiment of the present invention, there is provided an abrasion-resistant coating film comprising the composition for coating a glass film. For example, in the case of the abrasion-resistant coating film, the pencil hardness measured may be 7H or more.

 The composition for coating a glass film may have excellent antifouling properties. Thus, according to another embodiment of the present invention, there is provided an antifouling coating film comprising the composition for coating a glass film. For example, in the case of the antifouling coating film, fingerprint adhesion after palm contact can be visually evaluated.

The composition for coating a glass film may have excellent durability. Thus, according to another embodiment of the present invention, there is provided a durable coating film comprising the composition for coating a glass film. For example, in the case of the above-described durability coating film, the change in thickness of the coating layer after the repeated washing process can be measured and confirmed from the reduction of the thickness reduction ratio (%).

The composition for coating a glass film may have excellent high temperature stability. Thus, according to another embodiment of the present invention, there is provided a heat-resistant coating film comprising the composition for coating a glass film.

According to another embodiment of the present invention, there is provided a film having water repellency, abrasion resistance, antifouling property, durability and further heat resistance produced by the above method.

According to another embodiment of the present invention, there is provided a coating material having water repellency, abrasion resistance, antifouling property, durability, and further heat resistance produced by the above method.

The coating method using the composition for coating a glass film of the present invention may include a step of forming a glass coating film having a crosslinking structure on the substrate by applying and curing the condensation polymerization final product of the composition for coating a glass film, Wherein the glass coating film has a skeleton formed of a stereocrosslinking structure in which a glass-forming reaction material is formed to be connected to each other. Here, the coating method is preferably by local treatment including local coating on an automobile body, and includes spin, bar, slit, spray, curtain, gravure coating and the like.

According to another embodiment of the present invention, there is provided a method for coating a glass coating, comprising the steps of applying an emulsion of the composition for coating a glass coating, particularly a microemulsion, to an automobile body and drying the coating at room temperature to form a glass coating layer, A coating method of providing sesquioxane as a dispersion binding site can be provided.

According to another embodiment of the present invention, there is provided a method for coating a glass substrate, comprising the steps of: coating a substrate with a composition for coating a glass substrate based on a silane-based glass coating film-forming material; and curing the coating at room temperature to form a room temperature curable oligomer A silane starting compound constituting the silane-based glass coating film-forming material, or another room-temperature-curable oligomeric silsesquioxane constituting the silane-based glass coating film-forming material, A first step of forming a glass film providing a structure; And coating a glass film coating composition based on a siloxane-based glass coating film-forming material different from the glass-film coating composition used in the first step on the glass film formed in the first step, and curing the coating at room temperature A room temperature curable oligomeric silsesquioxane contained in the composition for coating a glass film may be used as a dispersion binding site to form a polyorganosiloxane constituting a salicylic acid glass coating film forming material or a room temperature curable oligomeric silsesquioxane And a second step of forming a second glass film that provides a three-dimensional structure to be dispersed.

The second step may be performed intermittently at a time when reinforcement of the glass film formed in the first step is required. Here, it is preferable that the reinforcement is required to be repeatedly applied every one to three months after the formation of the first glass film, depending on the temperature change, the humidity change, etc., in the summer and winter season.

As described above, the composition for coating a glass film according to one embodiment of the present invention can be used as a coating agent that can overcome the disadvantages of the conventional composition and improve various physical properties. In addition, the above-described composition for coating a glass film can be used for various purposes other than coating. And exhibits high temperature stability due to high crosslinking density.

In addition, because there is a bonding site in the structure of the glass coating film, the manufacturing process does not require a separate crosslinking process, thereby increasing the convenience in the process. That is, according to the method of manufacturing a glass film according to an embodiment of the present invention, a specific glass film coating composition can be used to manufacture the glass film by a simple process, and improved physical properties can be obtained as compared with a glass film produced by a conventional method.

Hereinafter, the present invention will be described with reference to specific embodiments, but the technical idea of the present invention is not limited by the following embodiments.

Manufacturing example

1) Cage type silsesquioxane compound preparation:

K as terrain silsesquioxane compound was prepared OctaSilane POSS ^ⓡ SH310 sold by Bulk Chemical LTD..

이고, 반복단위(m)이 8인 화합물이다. For reference, the cage-like silsesquioxane compound is represented by the formula (RSiO _{1. 5)} m, where R is

, And the repeating unit (m) is 8.

2) Kage-type silsesquioxane compound modified with miscible substituent Preparation:

, n=6)가 50% 개질된 케이지형 실세스퀴옥산 화합물을 준비하였다. A polymer having a hydroxy group, which is a kind of miscible substituent, is added to the cage-type silsesquioxane compound prepared in 1) above, and a coupling reaction is carried out under a platinum catalyst to form a hydroxy group

, n = 6) was modified to 50%.

3) Kage type silsesquioxane compound modified with miscible substituent Preparation:

, n=1)가 40% 개질된 케이지형 실세스퀴옥산 화합물을 준비하였다. A polymer having a methoxy group, which is one kind of miscible substituent, is added to the cage-type silsesquioxane compound prepared in 1) above and a coupling reaction is carried out under a platinum catalyst to obtain an alkoxy group

, n = 1) was prepared in a 40% modified form of cage silsesquioxane compound.

4) Preparation of cationic silsesquioxane compound modified with water repellent and antifouling substituent:

, n=6)가 50% 개질된 케이지형 실세스퀴옥산 화합물을 준비하였다. 그런 다음 발수성 및 방오성 치환기의 일종인 불소기를 갖는 고분자를 첨가하고 백금 촉매 하에 커플링 반응을 수행하여 치환된 비닐기의 80%가 불소기(

, n=6)로 개질된 케이지형 실세스퀴옥산 화합물을 준비하였다. A polymer having a vinyl group, which is one kind of miscible substituent, is added to the cage silsesquioxane compound prepared in 1) above, and a coupling reaction is carried out under a titanium catalyst to obtain a vinyl group

, n = 6) was modified to 50%. Then, a polymer having a fluorine group, which is a kind of water-repellent and antifouling substituent, is added and a coupling reaction is carried out under a platinum catalyst, whereby 80% of the substituted vinyl groups are substituted with a fluorine group

, n = 6) was prepared as the cage silsesquioxane compound.

i) Silane-based organic coating material-1 Preparation:

0.5 to 4 wt% of octamethylcyclotetrasiloxane, 5 to 15 wt% of butyl cellosolve, 40 to 85 wt% of isopropyl alcohol, 0.5 to 1 wt% of 1,4-butanediol, and 0.5 to 4 wt% of trimethoxyvinylsilane %.

ii) Silane-based organic coating material-2 Preparation:

1 to 8 wt% of octamethylcyclotetrasiloxane, 10 to 20 wt% of butyl cellosolve, 30 to 80 wt% of isopropyl alcohol, 0.5 to 1 wt% of 1,4-butanediol, and 1 to 8 wt% of trimethoxyvinylsilane %.

iii) Siloxane Organic Coating Material Preparation:

0.5 to 4 wt% of N, N-dimethyl ethanolamine, 5 to 25 wt% of xylene, 0.5 to 4 wt% of oleic acid, 0.5 to 4 wt% of sodium lauryl sulfate, polysiloxane (CAS 68037-58-1, Siloxanes and Silicones 1 to 8% by weight of di- Me, (dimethoxymethylsilyl) oxy-terminated, 40 to 65% by weight of water, polysiloxane (CAS 69430-37-1, Siloxanes and Silicones, di-Me, hydroxy-terminated (reaction products with trimethoxymethylsilane and 10 to 35% by weight of N1- (3- (trimethoxysilyl) propyl) 1-2, -ethanediamine.

Examples 1 to 7 and Comparative Examples 1 to 3

The three kinds of cage silsesquioxane compounds 1) to 4) prepared in the above Preparation Example were added to the organic coating materials of i), ii) and iii) at a molar ratio of 1: 0.2 (organic coating The molar ratio of the material to the cage silsesquioxane compound) was added to each of the compositions to prepare a total of nine compositions for coating a glass film. Specific compositions are shown in Table 1 below.

After the addition, the mixture was thoroughly mixed at 25 ° C. The mixing time was 5 minutes. A total of 9 kinds of mixed liquids thus obtained were cured or dried on a standard coating plate for automobile under the conditions shown in Table 1 to prepare a glass coating.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Kage Silsesquioxane Compound Type 2) 3) 3) 3) 4) 4) 4) One) One) One) Organic coating material i) i) ii) iii) i) ii) iii) i) ii) iii) Reaction conditions Room temperature curing 6hr Room temperature curing 6hr Room temperature curing 6hr Drying 1 hr Room temperature curing 6hr Room temperature curing 6hr Drying 1 hr Room temperature curing 6hr Room temperature curing 6hr Drying 1 hr

Examples 8 to 9, Comparative Examples 4 to 5

In Example 6, a three-kind cage silsesquioxane compound was mixed with the three kinds of organic coating materials i), ii) and iii) in an amount of 1: 0.01 (organic coating material: (Organic coating material: cage silsesquioxane compound, molar ratio of cage-type silsesquioxane compound: 1: 0.1) (moles of cage silsesquioxane compound, (Example 9) and 1: 0.7 (organic coating material: cage-type silsesquioxane compound, as a molar ratio of Comparative Example 5) as molar ratios of the compounds The same procedure as in Example 6 was repeated to further prepare a glass coating on a standard coating plate for an automobile.

Examples 10 to 11 and Comparative Examples 6 to 7

4) water-repellent and antifouling effect modifiers Kage type (Comparative Example 6), 10% modification (Example 10), 90% modification (Example 11), and 95% modification (Comparative Example 7) in the silsesquioxane compound preparation item The same procedure as in Example 6 was repeated except that this was added to Example 5 to further prepare a glass coating on a standard coating plate for an automobile.

Reference Examples 1 to 3

The above-2) Miscibility Substituent Reformed Kage type Silsesquioxane Compound preparation, The cage silsesquioxane compound was replaced with a random type (reference example 1), a linear (ladder) type (reference example 2) and a partial cage type (reference example 3) , And then the same process as in Example 1 was repeated to prepare a glass coating on a standard coating plate for an automobile.

Random type

(여기서 R은 탄소수 4의 알킬기이다)

(Wherein R is an alkyl group having 4 carbon atoms)

Linear (ladder type)

(여기서 R은 탄소수 4의 알킬기이다)

(Wherein R is an alkyl group having 4 carbon atoms)

Partial Kage type

(여기서 R은 탄소수 4의 알킬기이다)

(Wherein R is an alkyl group having 4 carbon atoms)

Reference Example 4

2 ) modified with an incompatible substituent used in Example 1 Kage type The same procedure as in Example 2 was repeated except that the silsesquioxane compound was replaced with the usual colloidal silica and the mixture was added to Example 1 to further prepare a glass coating on a standard coating plate for an automobile. The resultant glass coating film was difficult to obtain a uniform coating film due to the lowered dispersibility of the silica particles.

<Evaluation>

Each of the glass coating films obtained in Examples 1 to 11, Comparative Examples 1 to 7, and Reference Examples 1 to 3 was evaluated by the following items.

(1) Abrasion resistance test: The obtained coating film was placed in an oven set at a temperature of 200 캜 for 30 minutes, heated, and then cooled to measure pencil hardness.

(2) Water repellency test: The obtained coating film was placed in an oven set at a temperature of 200 캜 for 30 minutes, heated and then cooled. The contact angle was measured according to a water contact angle measurement method for a commonly used coating film. 100 degrees or more were evaluated as having hydraulic power.

(3) Antifouling test: Fingerprint adhesion after palm contact was visually evaluated and classified into A, B, C and D grades. A is the case where no fingerprint is attached (very good), B is the fingerprint of some of the fingers is blurry (good), C is the fingerprint of all the fingers is blurred (normal) And indicates remaining (defective).

(4) Durability test: After 1 to 10 times of washing, the coating layer thickness change was measured and the thickness reduction ratio was converted into a percentage. When the thickness reduction rate is less than 10%, it is evaluated as having durability.

The abrasion resistance, water repellency, antifouling property and durability test results of Examples 1 to 10, Comparative Examples 1 to 7, and Reference Examples 1 to 3 are shown in Table 2.

division Abrasion resistance (pencil hardness) Water repellency (water contact angle) Antifouling durability Example 1 8H 103 A fitness Example 2 9H 104 A fitness Example 3 9H 105 A fitness Example 4 8H 101 B fitness Example 5 8H 115 A fitness Example 6 8H 110 A fitness Example 7 7H 105 B fitness Example 8 8H 109 A fitness Example 9 8H 111 A fitness Example 10 8H 105 B fitness Example 11 9H 116 A fitness Comparative Example 1 3H 99 C incongruity Comparative Example 2 4H 98 C incongruity Comparative Example 3 3H 95 D incongruity Comparative Example 4 4H 97 D incongruity Comparative Example 5 6H 110 B incongruity Comparative Example 6 6H 96 C fitness Comparative Example 7 7H 107 B fitness Reference Example 1 4H 95 D incongruity Reference Example 2 7H 98 C fitness Reference Example 3 7H 100 C fitness

Referring to Table 2, the abrasion resistance (pencil hardness), the water repellency (water contact angle), the antifouling property and the durability were significantly different depending on the composition and structure according to each experimental example. In particular, the cage type oligomeric silsesquioxane In the case of the embodiment using the quinoxane, the water repellency of the water contact angle of 100 degrees or more with the excellent abrasion resistance of the pencil hardness 7H or more could be provided, and the water repellency of 115 degrees was also provided depending on the composition and structure of the examples. Both antifouling and durability provided improved results over comparative examples.

It is possible to provide a composition for coating a glass film having various physical properties by various combinations and structure control of the raw materials.

Claims (15)

A composition for coating a glass film, comprising silica particles as a glass coating film forming material and bonding sites thereof, wherein the silica particles are polyhedral oligomeric silsesquioxane. The method according to claim 1,
The room temperature-curable oligomeric silsesquioxane of the formula (RSiO _{1. 5)} and the cage nanoparticles represented by m, in which R is hydroxy, alkoxy, amino, mercapto, vinyl, halogen having 1 to 3 carbon atoms, Is an alkyl having 1 to 20 carbon atoms substituted with a functional group independently selected from the group consisting of an isocyanate group or an (meth) acrylate group, or an aryl group having 6 to 20 carbon atoms, and the repeating unit (m) is an integer of 20 or less. 3. The method of claim 2,
The room temperature curable oligomeric silsesquioxane is a mixture of repeating units (m) of the above formula in an integer of 8 to 16,
The functional group

,

,

,

,

,

,

or

(n is an integer of 0 to 20). The method according to claim 1,
Wherein the glass coating film forming material is at least one selected from the group consisting of a siloxane glass coating film forming material, a silazane glass coating film forming material, a silane glass coating film forming material, a silica glass coating film forming material and a fluorine glass coating film forming material Composition. The method according to claim 1,
A silane-based glass coating film forming material as the glass coating film forming material, and the formula as its binding site material (RSiO _{1. 5)} m (wherein R is hydroxy, alkoxy, amino, mercapto, vinyl, halogen-C 1 -C 3 , An isocyanate or a (meth) acrylate group, and the repeating unit (m) is an integer of 20 or less) substituted with a functional group independently selected from the group consisting of Curable oligomeric silsesquioxane,
In the curing process of the silane-based glass coating film-forming material, the room temperature curable oligomeric silsesquioxane is used as a crosslinking site to form the silane starting material compound or the room temperature curing oligomeric silane Wherein the sesquioxane is linked to the cross-linking site by -Si-O- linkages to form a skeleton. 6. The method of claim 5,
The silane-based glass coating film-
a) at least one member selected from the group consisting of octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetraphenylcyclotetrasiloxane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. At least one silane starting compound for condensation selected from the group consisting of:
b) methacryloxypropyl trimethoxy silane (MATS), acryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and allyl trimethoxysilane. At least one reactive silane coupling agent selected from the group consisting of allyltrimethoxysilane;
c) a mixture of monoglyme, diglyme, butyl carbitol, alpha-terpineol, glycerine, ethyl acetate, butyl acetate, ethyl lactate, carbitol acetate, acetone, methyl ethyl ketone, cyclohexanone Methylene chloride, diethyl ether, tetrahydrofuran, dioxane, hexane, cyclohexane, heptane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, benzene, toluene, xylene, At least one hydrocarbon solvent selected from the group consisting of terpine, white spirit, petroleum and ligroin; And
d) a solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, benzyl alcohol, diacetone alcohol, methoxyethanol, ethoxyethanol, butoxyethanol, ethylene glycol, butylene glycol, diethylene glycol and propylene glycol monomethyl ether And at least one alcohol solvent. The method according to claim 1,
The siloxane-based glass coating film forming material as the glass coating film forming material, and the formula as its binding site material (RSiO _{1. 5)} m (wherein R is hydroxy, alkoxy, amino, mercapto, vinyl, halogen-C 1 -C 3 , An isocyanate or a (meth) acrylate group, and the repeating unit (m) is an integer of 20 or less) substituted with a functional group independently selected from the group consisting of Curable oligomeric silsesquioxane,
Wherein the room temperature curable oligomeric silsesquioxane is used as a dispersion site in the drying process of the siloxane-based glass coating film-forming material. 8. The method of claim 7,
The siloxane-based glass coating film-
(a) polyorganosiloxanes including alkoxy-terminated dimethylpolysiloxanes and aminoalkoxy-terminated dimethylpolysiloxanes;
(b) at least one compound selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, triisopropanolamine, dibutylamine, tributylamine, diisopropanolamine, methylmonoethanolamine, methyldiethanolamine, ethylenediamine, diethylene tri At least one water-soluble aliphatic amine compound selected from the group consisting of amine, triethylenetetraamine, tetraethylenepentamine, dimethylethanolamine, isopropylamine, cyclopentylamine, cyclohexylamine and diamylamine;
(c) at least one compound selected from the group consisting of malonic acid, itaconic acid, naphthenic acid, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 5-norbornene 2-carboxylic acid, 5-norbornene 2,3-dicarboxylic acid, Acetic acid, acetic acid, 2-methyl-acetoacetic acid, oxalic acid, pivalic acid, 2-ethylhexanoic acid, malic acid, malic acid, maleic acid, But are not limited to, acid, maleic acid, fumaric acid, glyoxylic acid, pyruvic acid, succinic acid, glutaric acid, gluconic acid, picric acid, citric acid, benzoic acid, neodecanoic acid, stearic acid, oleic acid, linoleic acid, abietic acid, Alkyl sulfosuccinates, alkyl sulfosuccinates, alkyl ethoxylated caprosinates, alpha-sulfonated fatty acids, alpha olefin sulfonates and alkyl sulfates such as alkyl sulfosuccinates, Alkoxy &lt; / RTI &gt; A surfactant one or more of;
(d) monoglyme, diglyme, butyl carbitol, alpha-terpineol, glycerin, ethyl acetate, butyl acetate, ethyl lactate, carbitol acetate, acetone, methyl ethyl ketone, cyclohexane A solvent such as methanol, ethanol, propanol, isopropanol, butanol, isopropanol, butanol, isopropanol, butanol, isopropanol, , At least one hydrocarbon solvent selected from the group consisting of terpine, white spirit, petroleum and ligroin; And (e) water. The method according to claim 1,
Wherein the molar ratio of the room temperature curable oligomeric silsesquioxane to the glass coating film forming material is 1: 0.1 to 0.5. Coating a substrate with a mixed solution of the glass coating film forming material of claim 1 and room temperature curable oligomeric silsesquioxane on a substrate; And
Wherein the room temperature curable oligomeric silsesquioxane is incorporated in the glass coating film forming material as a crosslinking site or dispersing site and is bonded to each other by -Si-O- linkage Of the total thickness of the glass substrate. 11. The method of claim 10,
The mixed solution of the glass-coating film-forming material and the room-temperature-curable oligomeric silsesquioxane is a solvent-dispersed coating solution, and the room temperature curable oligomeric silsesquioxane is used as a crosslinking site to form silane raw material Compound, or another room-temperature-curable oligomeric silsesquioxane is bonded to each other at the cross-linking site to form a skeleton. 11. The method of claim 10,
The mixed solution of the glass-coating film-forming material and the room temperature-curable oligomeric silsesquioxane is a microemulsion, and the room temperature curable oligomeric silsesquioxane is used as a dispersion bond to form the polyorgano Siloxane is bonded or the room temperature curable oligomeric silsesquioxane is dispersed. A film having water repellency, abrasion resistance, antifouling property and durability produced by the method of claim 10. A coating material having water repellency, abrasion resistance, antifouling property and durability, which is produced by the method of claim 10. Coating a substrate with a composition for coating a glass film based on a silane-based glass-coating-film forming material, and curing the coating at room temperature to prepare a room-temperature-curable oligomeric silsesquioxane contained in the composition for coating a glass- A silane starting compound constituting the silane-based glass coating film-forming material, or another stereoscopic structure in which another room-temperature-curable oligomeric silsesquioxane is linked with the -Si-O- linkage at the crosslinking site to form a skeleton A first step of forming a glass film to be provided; And
The glass-film coating composition based on the siloxane-based glass-coating-film-forming material different from the glass-film-coating composition used in the first step is coated on the glass-film layer connected to each other by the -Si-O- And curing the coating at room temperature to prepare a room temperature curable oligomeric silsesquioxane contained in the glass coating composition as a dispersion binding site to bind the polyorganosiloxane constituting the salicylic acid glass coating film forming material, And a second step of forming a second glass film that provides a stereoscopic structure in which the room temperature curable oligomeric silsesquioxane is dispersed.

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