KR20190056307A - Silsesquioxane polymer and coating composition including the same - Google Patents

Abstract

Disclosed are: a silsesquioxane polymer coated on a glass substrate to improve the strength of the glass substrate; and a coating composition comprising the same. The silsesquioxane polymer comprises repeating units represented by chemical formula 1 and chemical formula 2. The coating composition according to the present invention can be applied to various types of glass substrates and has an advantage of excellent adhesion to glass substrates.

Description

[0001] Silsesquioxane polymer and coating composition including the same [0002]

The present invention relates to a silsesquioxane polymer and a coating composition comprising the same, and more particularly, to a silsesquioxane polymer which is coated on a glass base material to improve the strength of the glass base material and a coating ≪ / RTI >

Generally, glass products are used not only for buildings or structures such as walls, floors, tiles, roofing materials, windows, but also used for housewares such as cups, dishes and bowls. They are also used for industrial purposes such as semiconductor manufacturing devices. , Glasses, and electronic products. Particularly, glass products are widely applied to electronic products such as touch screen panels because they can be manufactured to be more resistant to heat and scratch than acrylic resin, have a high visible light transmittance, and have a curved shape.

However, when the glass is touched with a finger, the glass can be contaminated with fingerprints and the like, and the flexibility and strength are weak, so that the glass is easily broken upon impact, and the glass fragments can be scattered. Particularly, in the case of a glass having a curved shape rather than a plate shape, there is a problem that the stress is concentrated on the bent portion and is more easily broken when an impact is received. This is due not only to the properties of the glass itself, but also to the microcracks generated on the glass surface. Glass has small scratches on its surface that are invisible to the naked eye during the manufacturing process, and these scratches significantly degrade the strength of the glass. In order to solve such a problem, strength improvement work using a chemical reaction is generally performed.

In the glass strength improvement work using the chemical reaction, an ion exchange reaction is performed in a salt bath (potassium nitrate solution) at about 400 to 500 ° C for 4 to 8 hours to remove sodium ions (Na ⁺ ) from the glass surface Potassium ions (K ⁺ ) to increase the surface strength of glass. The method using such a chemical reaction has a problem of low productivity because a long time of several hours to several tens of hours is required to obtain practical strength. In addition, when the glass is etched with a chemical during the chemical reaction, there arises a problem of appearance unevenness, and therefore there is a disadvantage that mechanical polishing is required. Mechanical grinding work is low in productivity due to manual work by manpower, low production rate due to high defect rate, and limit of strength improvement. For example, a glass that has undergone general mechanical polishing has a low ball drop breaking strength, and when dropped from a height of about 30 cm, a ball of 130 g is destroyed by more than 80%.

An object of the present invention is to provide a silsesquioxane polymer and a coating composition containing the same, which can improve the mechanical strength of glass through a simple coating process without directly reforming the glass using a chemical reaction.

Another object of the present invention is to provide a silsesquioxane polymer excellent in adhesion to glass and a coating composition containing the same.

It is still another object of the present invention to provide a tempered glass panel having improved mechanical strength, frictional resistance and contamination resistance properties such as surface hardness of glass while maintaining the optical properties of the glass.

In order to achieve the above object, the present invention provides a silsesquioxane polymer comprising a repeating unit represented by the following general formulas (1) and (2).

[Chemical Formula 1]

(2)

Wherein R1 is independently selected from the group consisting of hydrogen, deuterium, halogen, an amine group, an epoxy group, a cyclohexyl epoxy group, a (meth) acryl group, a hydroxyl group, a silyl group, an isocyanate group, a nitrile group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryl group having 3 to 40 carbon atoms, or an arylcyclic group having 3 to 40 carbon atoms, and each of R 2 is independently selected from the group consisting of hydrogen, deuterium, halogen, isocyanate group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aralkyl group having 3 to 40 carbon atoms or an epoxy group having 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n: m is 1: 1 to 100: 1 to be.

The present invention also relates to the above silsesquioxane polymer; And a solvent.

The present invention also relates to a glass substrate; And a cured coating layer on which the coating composition is coated.

The silsesquioxane polymer according to the present invention and the coating composition containing the silsesquioxane polymer according to the present invention can form a coating layer on one side or both sides of a glass substrate through a simple coating process so that the mechanical strength, It is possible to improve the friction characteristics and the pollution characteristics. The coating composition according to the present invention can be applied to various types of glass substrates and has an advantage of excellent adhesion to glass substrates.

1 is a sectional view showing the structure of a flat glass panel according to an embodiment of the present invention;
2 is a cross-sectional view showing the structure of a curved glass panel according to another embodiment of the present invention;

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

The present invention provides a silsesquioxane polymer comprising a repeating unit represented by the following general formulas (1) and (2), which is coated on a glass base material to improve the strength of the glass base material.

[Chemical Formula 1]

(2)

Wherein R1 is independently selected from the group consisting of hydrogen, deuterium, halogen, an amine group, an epoxy group, a cyclohexyl epoxy group, a (meth) acryl group, a hydroxyl group, a silyl group, an isocyanate group, a nitrile group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryl group having 3 to 40 carbon atoms, or an arylcyclic group having 3 to 40 carbon atoms, and each of R 2 is independently selected from the group consisting of hydrogen, deuterium, halogen, isocyanate group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, A heteroaryl group having 3 to 40 carbon atoms, an aralkyl group having 3 to 40 carbon atoms, or an epoxy group having 2 to 40 carbon atoms (e.g., a cyclohexyl epoxy group). N and m are each independently an integer of 1 to 100,000, preferably 2 to 1000, more preferably 2 to 50, and the ratio of n and m may be 1: 1 to 100: 1.

In the general formulas 1 and 2, the alkyl group may specifically be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group or a hexyl group, have. In the general formula (2), R 2 may be hydrogen, a methyl group, an ethyl group or a propyl group, and -OR 2 includes oxygen to control the solubility, dispersibility and compatibility of the silsesquioxane polymer.

If necessary, R 1 and R 2 may be substituted with substituents such as deuterium, halogen, amino, vinyl, (meth) acryl, silyl, isocyanate, nitrile or nitro. Specifically, R 1 may have a reactive substituent such as an amino group, a (meth) acrylic group, a hydroxyl group or a silyl group, or a reactive functional group such as a vinyl group or an epoxy group, and may be an alkyl group having a reactive substituent or a functional group , The silsesquioxane polymer of the present invention can be crosslinked by such a reactive substituent or functional group. Examples of R 1 having a reactive substituent or a functional group include a (meth) acryloxypropyl group and a 2- (3,4-epoxycyclohexyl) ethyl group. When the silsesquioxane polymer of the present invention has a reactive substituent or a reactive functional group, the proportion of R1 having a reactive substituent or reactive functional group relative to the entire R1 is, for example, 10 to 100%, specifically 50 to 100% to be. When the content of the reactive substituent or functional group is too small, the silsesquioxane polymer has a low crosslinking ability, and the hardness of the coating film to be finally formed is lowered, and crosslinking of the silsesquioxane polymer takes a long time.

The silsesquioxane polymer may be represented by the following general formula (3).

(3)

In the general formula (3), R 1, R 2, n and m are as defined in the general formulas (1) and (2). The silsesquioxane polymer represented by Formula 3 is a random or block copolymer of a repeating unit represented by n and a repeating unit represented by m and can control the adhesion property with a glass substrate by adjusting the ratio of n: m have. In the silsesquioxane polymer, the repeating unit represented by n serves to strengthen the strength of the silsesquioxane polymer, and the repeating unit represented by m improves the adhesion between the silsesquioxane polymer and the glass substrate And the ratio of n: m may have a ratio of 1: 1 to 100: 1, and more specifically, a ratio of 5: 1 to 30: 1. Here, if the content of the repeating unit represented by n is too small, the alkoxy (-OR2) ratio excessively increases, and the slip property of the silsesquioxane polymer solution increases, and there is a fear that the adhesion force during coating decreases . On the other hand, if the content of the repeating unit represented by n is too large, the alkoxy (-OR2) ratio is too small, which may lower the adhesive force with the glass substrate.

The weight average molecular weight of the silsesquioxane polymer containing the repeating units represented by the above formulas (1) and (2), specifically, the silsesquioxane polymer containing the above formula (3) may vary within a wide range as necessary, It may have a weight average molecular weight of 1,000 to 1,000,000, a weight average molecular weight of 1,000 to 500,000, and a weight average molecular weight of 1,000 to 100,000. When the weight average molecular weight of the silsesquioxane polymer is less than 1,000, the silsesquioxane polymer has the same physical properties as silicone oil, resulting in poor physical properties such as coatability, elasticity and hardness. When the silsesquioxane polymer has a weight average molecular weight exceeding 1,000,000, there is a problem.

The silsesquioxane polymer containing the repeating units represented by the above formulas (1) and (2), specifically, the silsesquioxane polymer containing the above formula (3) may be a ladder type structure or a linear- As an inorganic hybridization (composite) polymer, it is excellent in elasticity and tensile strength when coated on a glass substrate, and has high solubility in solvents and excellent in fairness. Since the silsesquioxane polymer contains an -OR2 group in the middle of the molecule, the silsesquioxane polymer is covalently bonded to Si-OH and Si-O on the surface of the glass substrate and is excellent in bonding force and adhesive force with the glass substrate, The surface hardness and scratch characteristics of the glass substrate can be improved without damaging the properties of the glass substrate.

The silsesquioxane polymer may be prepared by adjusting the degree of condensation in a conventional ladder-type silsesquioxane polymer production process (see Korean Patent Laid-open Publication No. 10-2013- 0110018) in which a trialkoxysilane is hydrolyzed and then condensed, The resulting ladder-type silsesquioxane polymer may be reacted with an alcohol (R2-OH) to partially form Si-O-Si bonds. For example, as described in the following examples, a mixture of distilled water and an alcohol solvent is mixed with a chlorosilane monomer to prepare a precursor, and the precursor is partially condensed to obtain a mixture of repeating units represented by n and m The silsesquioxane polymer having the repeating units represented by the above formulas (1) and (2) having repeating units, specifically, the silsesquioxane polymer containing the above formula (3) Silsesquioxane polymer can be produced by randomly cleaving Si-O-Si bonds by reacting -O- between silane (-Si-) and alcohol.

The coating composition according to the present invention comprises a silsesquioxane polymer containing repeating units represented by the above formulas (1) and (2), specifically a silsesquioxane polymer containing the above formula (3) and a solvent. The silsesquioxane polymer containing the repeating units represented by the formulas (1) and (2), specifically, the silsesquioxane polymer containing the formula (3) may exist in a liquid state depending on the molecular weight, In this case, there is no need to use a separate solvent. However, when the silsesquioxane polymer is present in a solid state or it is necessary to improve the coating property, the silsesquioxane polymer may be dissolved in a solvent to form a composition. As the solvent, a silsesquioxane polymer can be dissolved, and a solvent which can be easily removed by heating or the like can be used without any particular limitation. Examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, , Ketones such as acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furans such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2 But are not limited to, polar solvents such as hexane, hexane, heptane, heptane, octane, heptane, octane, heptane, octane, heptane, Chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol, and the like, but the present invention is not limited thereto. In the coating composition according to the present invention, the content of the silsesquioxane polymer is 30 to 90% by weight, preferably 40 to 70% by weight, more preferably 50 to 65% by weight, 10 to 70% by weight, preferably 30 to 60% by weight, and more preferably 35 to 50% by weight. Here, if the content of the silsesquioxane polymer is too small or too large, there is a fear that the viscosity of the coating composition is too low or high, and the coating film may not be formed smoothly.

The coating composition according to the present invention may further contain additives such as initiators, defoaming agents, leveling agents and the like, if necessary. When the silsesquioxane polymer has reactive substituents or functional groups such as (meth) acryl, vinyl, and epoxy groups, the initiator reacts with the silsesquioxane polymer to crosslink the silsesquioxane polymer do. As the initiator, for example, chloroacetophenone, trichloro acetophenone, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methylpropan- (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexyl phenyl ketone, Trimethyl benzoyldiphenylphosphine oxide, camphor quinine, 2-methyl-2-morpholinopropane-1-one, Azobis (2-methylbutylate), 3,3-dimethyl-4-methoxy-benzophenone, p-methoxy Benzophenone, 2,2-diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenylethan-1-one, t-butylpoxomaleic acid, t-butylhydroperoxide, 4-dichlorobenzoyl peroxide, 1,1-di (t-butylperoxy 3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butylperoxy) valerate and the like can be used. Examples of the antifoaming agent include silicon-based products (e.g., BYK-063, BYK-065, BYK-072, BYK-085 and BYK-141, BYK-1752, BYK- Examples of the leveling agent include polyether-modified polydimethylsiloxane (BYK-300, BYK, BYK-0594, BYK-054, BYK- -301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333 and BYK-310), polyether hydroxypoly (E.g., BYK-308, BYK-373, and the like), polymethylalkylpolysiloxane (e.g., BYK-077, BYK-085, etc.) , Polyether modified methylalkylpolysiloxane (e.g., BYK-320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (E.g., BYK-315, etc.), Aralkyl modified methylalkyl polysiloxane (e.g., BYK-322 and BYK-323), polyester hydroxy functional polydimethylsiloxane BYK-370, etc.), polyester acryl-modified polydimethylsiloxane (e.g., BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxypolydimethylsiloxane-based (E.g., BYK-345, BYK-348, BYK-346, BYK-UV3510, and BYK-375), polyether-modified polydimethylsiloxane (e.g., BYK-332, BYK-337, etc.), non-ionic acrylic copolymer (e.g. BYK-380), ionic acrylic copolymer (e.g. BYK-381) Polyacrylate (E.g., Polyacrylate, e.g., BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK- (E.g., BYK-UV 3530, BYK-UV3530, etc.), polyether siloxane-based (Polyether siloxane-based, polyetheretherketone- modified siloxane such as BYK-347), alcohol alkoxylates (e.g., BYK-DYNWET 800), acrylates (e.g., BYK-392) Silicone modified polyacrylate (OH-functional) (e.g., BYK-Silclean 3700, etc.) may be used. The amount of the additive to be used may vary depending on the intended use of the additive, but is 0.1 to 10 parts by weight, specifically 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the silsesquioxane polymer and the solvent.

When the coating composition according to the present invention is coated on a glass base material and dried or cured to form a coating layer, the mechanical strength, friction resistance, and contamination resistance characteristics such as the surface hardness of the glass An improved tempered glass panel can be manufactured. The curing of the coating composition may be performed by a conventional method such as heating, light irradiation, room temperature disposition, water injection, or catalyst injection. FIG. 1 and FIG. 2 are cross-sectional views illustrating structures of a planar and bendable tempered glass panel according to an embodiment of the present invention, respectively. 1 and 2, a tempered glass panel according to the present invention comprises a planar or bendable glass substrate 10, 12 and a surface (front and / or rear) of the glass substrate 10, And a silsesquioxane polymer coating layer 20 formed of a silsesquioxane polymer having the formula (3). 1, the silsesquioxane polymer coating layer 20 formed by the coating composition according to the present invention comprises a front surface (A in Fig. 1), both surfaces (in Fig. 1 B) or the rear surface (C in Fig. 1). 2, the silsesquioxane polymer coating layer 20 is formed on the front surface (A in FIG. 2), both surfaces (FIG. 2B), or the rear surface Of C). The thickness of the silsesquioxane polymer coating layer 20 is 50 nm to 100 탆, specifically 0.1 to 50 탆, more specifically 1 to 30 탆. If the thickness of the coating layer 20 is 50 nm or less, the friction resistance and the contamination resistance (fingerprint resistance) can be maintained, but the impact strength improvement may be insufficient. On the other hand, when the thickness of the coating layer 20 is more than 100 탆, the impact strength of the tempered glass panel is increased, but the coating layer 20 may be scratched or the coating layer 20 may be damaged when an impact is applied. In addition, it is preferable that the glass panel does not cause damage to the balls of 500 g or less in the ball drop evaluation. The ball drop evaluation is a method of determining the fracture strength by descending a steel ball at a certain height.

The glass substrates 10 and 12 may include a wall material (including a cement wall material) of a building or a structure, a floor material (including a cement floor material), a brick, a tile, a roof, a window; Cups, plates, bowls; A semiconductor manufacturing apparatus; But are not limited to, glass for automobiles, optical products, glasses, electronic products, solar cells themselves, and glass for protection. In particular, the coating composition according to the present invention can be applied to a building or structure such as a wall (including cement wall), a flooring (including cement flooring), a brick, a tile, a roof or a window; Housewares such as cups, plates, bowls; A semiconductor manufacturing apparatus; An automobile glass, an optical product, an eyeglass, an electronic product such as a mobile phone, a solar cell itself, and a glass used for protection. Here, glass is collectively referred to as a solid material including Si.

Since the silsesquioxane polymer coating layer 20 formed according to the present invention is made of a silicone material having optical properties (refractive index and the like) similar to those of glass, the silsesquioxane polymer coating layer 20 is excellent in surface hardness, mechanical strength, It is possible to improve physical properties such as prevention of contamination and fingerprinting performance. In addition, according to the present invention, the coating composition is simply coated on various types of glass surfaces, thus facilitating the coating process.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.

[Production Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-4] Synthesis of silsesquioxane polymer

32 g of distilled water and 100 g of methanol were fed into a flask equipped with a cooling tube and a stirrer and 261.61 g of 3- (trichlorosilyl) propylmethacrylate (trade name) was added while maintaining the temperature at -4 ° C. Was slowly added dropwise over 10 minutes. Further stirring was carried out for 20 minutes, 500 g of toluene was added dropwise, the temperature was raised to room temperature and stirring was further carried out for 10 minutes (simultaneous Si-OH and Si-alkoxy (OR ₂ )). Thereafter, 24.64 g of 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane (2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane) was added dropwise and the mixture was stirred for 10 minutes. 10 g of a 20 wt% aqueous solution of Na ₂ CO ₃ was added dropwise to the reaction solution at once, and the temperature was raised to 100 ° C to conduct a condensation reaction for one day. The reaction solution was separated into a water layer and a toluene layer and purified. After confirming that the pH was neutral, the toluene layer was decompressed in vacuo to remove all the toluene to obtain a silsesquioxane polymer.

The obtained silsesquioxane polymer had a linear structure as shown in Formula 3, and had a weight average molecular weight of 10,000, and no unreacted monomer was present. The weight average molecular weight is the polystyrene reduced average molecular weight measured by gel permeation chromatography. Analysis of the obtained silsesquioxane polymer by decomposition temperature measurement using a TGA (Thermo Gravimetric Analyzer) revealed that the residual ratio of alkoxy (methoxy) was 3% by weight. As a result of analysis by 1 H-NMR, The ratio was about 2: 1. Then, in the same manner, in Production Examples 1-2 to 1-7 and Comparative Examples 1-1 to 1-4, only the ratio of n: m was changed as shown in Table 1 below to prepare each silsesquioxane polymer Respectively.

The remaining ratio of the alkoxy was measured by confirming the decomposition amount of the alkoxy group canceled by condensation at 150 ° C to 250 ° C using TGA. The ratio of n: m was determined by measuring the Si- C and the partial amount of Si-OCH _{3 in} the repeating unit m was calculated.

division Production Example 1-2 Manufacturing example
1-3 Manufacturing example
1-4 Manufacturing example
1-5 Manufacturing example
1-6 Manufacturing example
1-7 Comparative Example
1-1 Comparative Example
1-2 Comparative Example
1-3 Comparative Example
1-4 n: m 1: 1 5: 1 30: 1 50: 1 75: 1 100: 1 105: 1 1: 2 1: 0 0: 1

[Production Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-4] Preparation of coating composition

30 g of the silsesquioxane polymer obtained in Production Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-4 was dissolved in 70 g of methyl isobutyl ketone to prepare 100 g of a coating composition. 3 parts by weight of chloroacetophenone, 1 part by weight of BYK-347 and 1 part by weight of BYK-UV 3500 as photoinitiators were added to 100 parts by weight of the coating composition, and the mixture was stirred for 10 minutes to prepare respective photosetting coating compositions.

[Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-4] Production of Tempered Glass Panel

The coating compositions obtained in Production Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-4 were respectively applied to a plate type glass substrate (gorilla glass substrate) having a thickness of 80 탆 by dip coating, Heat treatment was carried out for 10 minutes under a hot air condition of 85 캜, followed by UV curing. Thereafter, the glass substrate was aged for 1.5 hours under the hot air condition of 200 占 폚 to form a 10 占 퐉 -thick coating film on the organic substrate to prepare a tempered glass panel.

The properties of the tempered glass panels prepared in Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-4 were evaluated by the following methods, and the results are shown in Table 2.

(1) Pencil hardness: Evaluated according to JIS 5600-5-4 with a load of 1000 g. The pencil was made using Mitsubishi products, and five times per pencil hardness, and when two or more scratches occurred, it was judged to be defective. (For example, the number of occurrences of less than 2 scratches / expressed as 5, or less than 2 scratches for 5 occurrences as 5/5)

(2) Evaluation of adhesive strength: According to JIS K5600-5-6, scratches were made with a cutter at intervals of 1 mm and 100 scratches were formed in a lattice pattern. An adhesive tape was applied and peeled off in a direction of 90 degrees, It was visually confirmed whether it was attached or dropped. Table 1 shows the number of scratches that were not dropped in 100 pieces. (Eg number not falling / 100, 100 if not falling).

(3) Evaluation of friction in the inside: It was evaluated according to JIS 5600-5-4 with a load of 1000 g. Steel wool was used to determine the number of times scratches occurred.

(4) Evaluation of fouling resistance (fingerprint): The contact angle before and after coating was checked using a contact angle meter.

Evaluation items n: m Coating thickness Pencil hardness
(500 gf) Adhesion Transmittance (%) My friction Haze (%) Contact angle Before coating - - 8H (5/5) - 93.4 1000 times 0.31 55-70 ° Example 3-1 2: 1 10 탆 9H (5/5) Pass
100/100 92.8 3000 times 0.29 <105 ° Example 3-2 1: 1 10 탆 9H (5/5) Pass
100/100 91.5 3000 times 0.23 <105 ° Example 3-3 5: 1 10 탆 9H (5/5) Pass
100/100 92.5 3000 times 0.28 <105 ° Example 3-4 30: 1 10 탆 9H (5/5) Pass
100/100 91.3 3000 times 0.21 <105 ° Example 3-5 50: 1 10 탆 9H (4/5) Pass
100/100 92.1 3000 times 0.19 <105 ° Examples 3-6 75: 1 10 탆 9H (4/5) Pass
100/100 92.8 3000 times 0.21 <105 ° Examples 3-7 100: 1 10 탆 9H (4/5) Pass
100/100 91.1 3000 times 0.20 <105 ° Comparative Example 3-1 105: 1 10 탆 8H (4/5) Fail
30/100 91.7 1000 times 0.32 <105 ° Comparative Example 3-2 1: 2 10 탆 8H (4/5) Fail
35/100 93.1 1000 times 0.33 <105 ° Comparative Example 3-3 1: 0 10 탆 8H (4/5) Fail
20/100 92.2 500 times 0.26 <105 ° Comparative Example 3-4 0: 1 10 탆 8H (5/5) Fail
50/100 91.3 500 times 0.30 <105 °

[Example 4] Production of tempered glass panel

 A tempered glass panel was produced in the same manner as in Example 3-1, except that a curved glass substrate was used instead of the flat glass substrate.

[Example 5] Production of tempered glass panel

A tempered glass panel was prepared in the same manner as in Example 3-2, except that the coating composition was applied using a spray gun instead of the dipping method.

[Example 6] Production of tempered glass panel

A tempered glass panel was prepared in the same manner as in Example 3-2, except that the coating composition was applied at a rate of 5 mm / sec using Slot Die Coating instead of the dipping method.

The properties of the tempered glass panel prepared in Examples 4 to 6 were evaluated in the same manner as in Example 3-1, and the results are shown in Table 3.

Evaluation items n: m Coating thickness Pencil Hardness (500gf) Adhesion Transmittance (%) My friction Haze (%) Contact angle Example 4 2: 1 10 탆 9H (4/5) Pass
100/100 92.8 3000 times 0.29 <105 ° Example 5 2: 1 10 탆 9H (4/5) Pass
100/100 91.8 3000 times 0.18 <105 ° Example 6 2: 1 10 탆 9H (4/5) Pass
100/100 91.3 3000 times 0.22 <105 °

[Example 7] Production of tempered glass panel

A tempered glass panel was prepared in the same manner as in Example 3-2, except that a coating film having a thickness of 10 mu m was formed on the front, back, front, and rear surfaces of a plate glass substrate having a thickness of 80 mu m.

Thereafter, ball-drop evaluation was performed on the tempered glass panel manufactured in Example 7, and the results are shown in Table 4. [

The ball drop evaluation was carried out by fixing a tempered glass panel specimen and lowering the steel ball (20-2000 g) at a predetermined height (1 m) to evaluate the destruction. Five defects were evaluated per one ball drop evaluation, and when two or more cracks occurred, it was judged as defective (broken: O, no broken: X).

Ball weight (g) Before coating Front Coating
(Example 3-2) Back coat
(Example 3-2) Double-sided coating
(Example 7) 20 X X X X 30 X X X X 50 O X X X 100 O X X X 250 O X X X 500 O X X X 1000 O O X X 2000 O O O X

From the above Examples and Comparative Examples, the silsesquioxane polymer according to the present invention and the coating composition containing the silsesquioxane polymer according to the present invention can be obtained by forming a coating layer on the surface of a glass substrate through a simple coating process, Strength, surface hardness, abrasion resistance, and resistance to contamination.

Claims (11)

A silsesquioxane polymer comprising a repeating unit represented by the following general formula (1) and general formula (2).
[Chemical Formula 1]

(2)

Wherein R1 is independently selected from the group consisting of hydrogen, deuterium, halogen, an amine group, an epoxy group, a cyclohexyl epoxy group, a (meth) acryl group, a hydroxyl group, a silyl group, an isocyanate group, a nitrile group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryl group having 3 to 40 carbon atoms, or an arylcyclic group having 3 to 40 carbon atoms, and each of R 2 is independently selected from the group consisting of hydrogen, deuterium, halogen, isocyanate group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, A heteroaryl group having 3 to 40 carbon atoms, an aralkyl group having 3 to 40 carbon atoms or an epoxy group having 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000,
n: m is 1: 1 to 100: 1. The silsesquioxane polymer according to claim 1, wherein the silsesquioxane polymer comprises a silsesquioxane polymer represented by the following formula (3).
(3)

R 1, R 2, n and m in the general formula (3) are the same as defined in the general formulas (1) and (2). Is a hydrogen atom, a methyl group, an ethyl group or an ethyl group, and R &lt; 2 &gt; is a hydrogen atom, a methyl group, an ethyl group or a propyl group. 3. A compound according to claim 1 or 2, wherein R1 is a reactive substituent or a functional group selected from the group consisting of amino group, (meth) acryl group, hydroxyl group, Lt; / RTI &gt; polymer. A silsesquioxane polymer containing a repeating unit represented by the following formula (1) and (2); And
And a solvent.
[Chemical Formula 1]

(2)

Wherein R1 is independently selected from the group consisting of hydrogen, deuterium, halogen, an amine group, an epoxy group, a cyclohexyl epoxy group, a (meth) acryl group, a hydroxyl group, a silyl group, an isocyanate group, a nitrile group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryl group having 3 to 40 carbon atoms, or an arylcyclic group having 3 to 40 carbon atoms, and each of R 2 is independently selected from the group consisting of hydrogen, deuterium, halogen, isocyanate group, An alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, A heteroaryl group having 3 to 40 carbon atoms, an aralkyl group having 3 to 40 carbon atoms or an epoxy group having 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000,
n: m is 1: 1 to 100: 1. The coating composition according to claim 4, wherein the silsesquioxane polymer comprises the following formula (3).
(3)

R 1, R 2, n and m in the general formula (3) are the same as defined in the general formulas (1) and (2). Is a hydrogen atom, a methyl group, an ethyl group or a propyl group; R &lt; 2 &gt; is a hydrogen atom, a methyl group, an ethyl group or an ethyl group; Propyl group. The coating composition according to claim 4 or 5, wherein the content of the silsesquioxane polymer is 50 to 99% by weight and the content of the solvent is 1 to 50% by weight. Glass substrates; And
A glass panel comprising a cured coating layer coated with the coating composition of claim 4 or claim 5. The glass panel according to claim 8, wherein the silsesquioxane polymer coating layer has a thickness of 50 nm to 100 탆. The glass panel according to claim 8, wherein the silsesquioxane polymer coating layer is coated on one or both surfaces of the glass substrate. 9. The method of claim 8,
Wherein the glass panel does not cause damage to balls less than 500 g in the ball drop evaluation.

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