CN111344334A - Silsesquioxane polymer and coating composition comprising same - Google Patents
Silsesquioxane polymer and coating composition comprising same Download PDFInfo
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- CN111344334A CN111344334A CN201880073725.XA CN201880073725A CN111344334A CN 111344334 A CN111344334 A CN 111344334A CN 201880073725 A CN201880073725 A CN 201880073725A CN 111344334 A CN111344334 A CN 111344334A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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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 includes repeating units of chemical formula 1 and chemical formula 2.
Description
Technical Field
The present invention relates to a silsesquioxane polymer and a coating composition comprising the same, and more particularly, to a silsesquioxane polymer coated on a glass substrate (glass base material) to improve the strength of the glass substrate and a coating composition comprising the same.
Background
Generally, glass products are widely used for buildings and structures such as wall materials, floor materials, tiles, roof materials, and windows; household articles such as cups, dishes, bowls and the like; industries such as semiconductor manufacturing equipment; automobile parts, optical products, glasses, electronic products, and the like. In particular, glass products can be made more resistant to heat and scratch than acryl resins, have high visible light transmittance, and can realize a curved (bent) form, and thus, are widely used in electronic products such as touch screen panels.
However, the glass has the following problems: when touched with a finger (touch), the glass sheet may be contaminated with fingerprints and the like, and may be easily broken and scattered when subjected to an impact because of its low flexibility and hardness. Particularly, in the case of glass having a bent form rather than a plate form, there is a problem that it is more easily broken when an impact is applied due to stress concentration at a bent portion. This is not only the property of the glass itself but also because of micro cracks (micro cracks) generated on the surface of the glass. During the manufacturing process, small cracks invisible to the naked eye appear on the surface of the glass, and the cracks can greatly reduce the strength of the glass. To solve these problems, strength improvement work using chemical reaction is generally performed.
The work for improving the strength of glass by chemical reaction is to perform an ion exchange reaction in a salt bath (molten potassium nitrate) at about 400 to 500 ℃ for 4 to 8 hours to remove sodium ions (Na) from the surface of the glass+) Replacement with potassium ion (K) having a large ionic radius+) To increase the surface strength of the glass. The method using such a chemical reaction requires a long time of several hours or even several tens of hours to obtain practical strength, resulting in a problem of low productivity. In addition, in the chemical reaction, when the glass is etched with chemicals (Etching), the problem of the appearance unevenness occurs, and thus, there is a disadvantage that the mechanical Polishing (polising) work is required. Since the mechanical polishing work is manually performed by manpower, productivity is low, a defective rate is high, production yield is low, and improvement of strength is limited. For example, since glass subjected to general mechanical grinding has low breaking strength by Ball drop (Ball drop), 130g of steel balls are broken by 80% or more when dropped from a height of about 30 cm.
Disclosure of Invention
Technical subject
The purpose of the present invention is to provide a silsesquioxane polymer that can improve the mechanical strength of glass by a simple coating process without directly modifying the glass by a chemical reaction, and a coating composition containing the silsesquioxane polymer.
Another object of the present invention is to provide a silsesquioxane polymer having excellent adhesion to glass, and a coating composition containing the silsesquioxane polymer.
It is still another object of the present invention to provide a tempered glass panel having improved mechanical strength such as surface hardness, abrasion resistance and stain resistance while maintaining optical characteristics of glass.
Means for solving the problems
To achieve the object, the present invention provides a silsesquioxane polymer comprising repeating units of the following chemical formula 1 and chemical formula 2:
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulas 1 and 2, R1 are each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth) acrylic group, hydroxyl group, thiol group, isocyanate group, nitrile group, nitro group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, aralkyl group having 3 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms or arylthiol group having 3 to 40 carbon atoms, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, 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 100000, and n: m is 1:1 to 100: 1.
In addition, the present invention provides a coating composition comprising: the silsesquioxane polymer and a solvent.
In addition, the present invention provides a glass panel comprising: a glass substrate; and a coating layer formed by coating and curing the coating composition.
Effects of the invention
According to the silsesquioxane polymer and the coating composition containing the silsesquioxane polymer of the present invention, a coating layer is formed on one or both surfaces of a glass substrate through a simple coating process, so that the mechanical strength, surface hardness, abrasion resistance, stain resistance, and the like of glass can be improved while maintaining the optical properties of glass. The coating composition according to the present invention has advantages that it can be applied to various forms of glass substrates and has excellent adhesion to the glass substrates.
Drawings
Fig. 1 is a sectional view illustrating a structure of a flat plate type glass panel according to an embodiment of the present invention.
Fig. 2 is a sectional view illustrating the structure of a bent type glass panel according to another embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
The present invention provides a silsesquioxane polymer that is a substance coated on a glass substrate (glass base material) to improve the strength of the glass substrate, and includes repeating units of the following chemical formulae 1 and 2.
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulas 1 and 2, R1 are each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth) acrylic group, hydroxyl group, thiol group, isocyanate group, nitrile group, nitro group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, aralkyl group having 3 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms or arylthiol group having 3 to 40 carbon atoms, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, 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 (for example, a cyclohexylepoxy group). Each of n and m is independently an integer of 1 to 100000, preferably 2 to 1000, more preferably 2 to 50, and the ratio of n to m may be 1:1 to 100: 1.
In the chemical formula 1 and the chemical formula 2, the alkyl group may be specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, etc., and the aryl group may be phenyl, etc. In the chemical formula 2, R2 may be hydrogen, methyl, ethyl, OR propyl, -OR2 adjusts solubility, dispersibility, and compatibility of the silsesquioxane polymer by including oxygen.
The above-mentioned R1 and R2 may be substituted with a substituent such as deuterium, halogen, amino group, vinyl group, (meth) acrylic group, thiol group, isocyanate group, nitrile group, nitro group or the like, as required. Specifically, R1 may have a reactive substituent such as an amino group, a (meth) acrylic group, a hydroxyl group, or a thiol group, or a reactive functional group such as a vinyl group or an epoxy group, and may be, for example, an alkyl group having the reactive substituent or functional group, and the silsesquioxane polymer of the present invention may be crosslinked and bonded based on the reactive substituent or functional group. Examples of R1 having the reactive substituent or functional group include methacryloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like. When the silsesquioxane polymer of the present invention has a reactive substituent or a reactive functional group, the ratio of R1 having a reactive substituent or a reactive functional group to R1 as a whole is, for example, 10 to 100%, specifically 50 to 100%. If the content of the reactive substituent or functional group is too small, the silsesquioxane polymer has a low degree of crosslinking, and the hardness of the finally formed coating film decreases or the time required for crosslinking and bonding of the silsesquioxane polymer increases.
The silsesquioxane polymer may be represented by the following chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, R1, R2, n, and m are the same as defined in chemical formula 1 and chemical formula 2. The silsesquioxane polymer represented by chemical formula 3 is a random copolymer or a block copolymer of a repeating unit represented by n and a repeating unit represented by m, and the ratio of n to m can be adjusted to adjust the adhesion characteristics to the glass substrate. In the silsesquioxane polymer, the repeating unit represented by n plays a role of reinforcing the strength of the silsesquioxane polymer, the repeating unit represented by m plays a role of improving the adhesion of the silsesquioxane polymer to the glass substrate, and the ratio of n: m may have a ratio of 1:1 to 100:1, specifically, may have a ratio of 5:1 to 30: 1. When the content of the repeating unit represented by n is too small, the ratio of the alkoxy group (-OR2) is excessively increased, and the oil-slip (oil) property of the silsesquioxane polymer solution is increased, thereby decreasing the adhesion force at the time of coating. Conversely, if the content of the repeating unit represented by n is too high, the ratio of alkoxy groups (-OR2) is too small, and the adhesion to the glass substrate is lowered.
The silsesquioxane polymer including the repeating units of chemical formula 1 and chemical formula 2, specifically, the silsesquioxane polymer including chemical formula 3 may have a weight average molecular weight in a wide range as needed, but, in general, may have a weight average molecular weight of 1000 to 1000000, may have a weight average molecular weight of 1000 to 500000, and may have a weight average molecular weight of 1000 to 100000. However, when the weight average molecular weight of the silsesquioxane polymer is less than 1000, physical properties similar to those of Silicone oil (Silicone oil) are exhibited, and thus there is a problem that physical properties such as coatability, elasticity, and hardness are deteriorated, and when it exceeds 1000000, processability is deteriorated.
The silsesquioxane polymer including the repeating units of chemical formulas 1 and 2, specifically, the silsesquioxane polymer of chemical formula 3 is an organic-inorganic hybrid (composite) polymer having a ladder type structure or a linear structure, and has advantages of excellent elasticity and tension, high solubility in a solvent, and excellent workability when coated on a glass substrate. Further, the silsesquioxane polymer includes a group of-OR 2 in the middle of the molecule, and therefore is covalently bonded to Si — OH, Si — O, OR the like on the surface of the glass substrate, and has excellent bonding force and adhesion to the glass substrate, and improves the surface hardness, scratch property, and the like of the glass substrate without deteriorating the optical properties of the glass substrate.
The silsesquioxane polymer can be made as follows: in a general process for producing a ladder-type silsesquioxane polymer in which trialkoxysilane is hydrolyzed and condensed (see Korean patent laid-open publication No. 10-2013-0110018), the ladder-type silsesquioxane polymer produced by the condensation reaction is reacted with an alcohol (R2-OH) to partially cleave Si-O-Si bonds. For example, as described in the following examples, a silsesquioxane polymer including repeating units of the chemical formulae 1 and 2 having repeating units represented by n and m, specifically a silsesquioxane polymer including the chemical formula 3 (that is, a silsesquioxane polymer including the chemical formula 3 can be produced by reacting-O-in silane (-Si-) with an alcohol to randomly cleave Si-O-Si bonds) by mixing distilled water and an alcohol solvent, adding a chlorosilane monomer to produce a precursor, and partially condensing the precursor
The coating composition according to the present invention includes a silsesquioxane polymer including the repeating units of chemical formula 1 and chemical formula 2, specifically chemical formula 3, and a solvent. The silsesquioxane polymer including the repeating units of chemical formula 1 and chemical formula 2, specifically the silsesquioxane polymer of chemical formula 3, may exist in a liquid state according to the molecular weight and the kinds of R1 and R2, and in this case, it is not necessary to use another solvent. However, when the silsesquioxane polymer is present in a solid state or when it is necessary to improve coatability, the silsesquioxane polymer may be dissolved in a solvent to form a composition. The solvent may be any solvent that dissolves the silsesquioxane polymer and is easily removed by heating, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, and cellosolve, lactic acid esters, ketones such as acetone and methyl (isobutyl) ethanone, glycols such as ethylene glycol, furans such as tetrahydrofuran, polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, and various solvents such as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, xylene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, dichloromethane, octadecylamine, aniline, dimethylsulfoxide, and benzyl alcohol. In the coating composition according to the present invention, the silsesquioxane polymer is contained in an amount of 30 to 90 wt%, preferably 40 to 70 wt%, and more preferably 50 to 65 wt%, and the solvent is contained in an amount of 10 to 70 wt%, preferably 30 to 60 wt%, and more preferably 35 to 50 wt%. If the content of the silsesquioxane polymer is too small or too large, the viscosity of the coating composition may be too low or too high, and a coating film may not be formed smoothly.
The coating composition of the present invention may further contain additives such as an initiator, a defoaming agent, and a leveling agent, if necessary. When the silsesquioxane polymer has reactive substituents or functional groups such as (meth) acrylic groups, vinyl groups, and epoxy groups, the initiator reacts with them to function to crosslink the silsesquioxane polymer. Examples of the initiator include chloroacetophenone (chloroacetophenone), trichloroacetophenone (trichloroacetophenone), diethoxyacetophenone (diethoxy acetophenone), 1-phenyl-2-hydroxy-2-methylpropan-1-one (1-phenyl-2-hydroxy-2-methylpropan-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylphenylsulfanyl) -2-morpholinopropan-1-one (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (trimethyzoylphenyldiphenylphosphine oxide), quinine camphorate (campholquinone), 2' -azobis (2-methylbutyronitrile) (2, photoinitiators such as 2 '-Azobis (2-methylbutyronitrile), dimethyl-2, 2' -Azobis (2-methylbutyrate), 3-dimethyl-4-methoxybenzophenone, p-methoxybenzophenone, 2-diethoxyacetophenone, 2-dimethoxy-1, 2-diphenylethan-1-one and the like; thermal initiators such as t-butyl peroxymaleate, t-butyl hydroperoxide, 2, 4-dichlorobenzoyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, and N-butyl-4, 4-bis (t-butylperoxy) valerate.
As the defoaming agent, silicon-based (for example, BYK-063, BYK-065, BYK-072, BYK-085, BYK-141, etc. from Pico) and non-silicon-based (for example, BYK-1752, BYK-1790, BYK-1794, BYK-054, BYK-055, BYK-057, etc.) may be used, and as the leveling agent, Polyether-modified polydimethylsiloxanes (for example, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc. from Pico), Polyether-modified hydroxy-functional polydimethylsiloxanes (for example, Polyether byK-hydroxy-308, BYK-310, etc. from Pico, Inc, BYK-373, etc.), methylalkylpolysiloxanes (e.g., BYK-077, BYK-085, etc.), Polyether modified methylalkylpolysiloxanes (e.g., BYK-320, BYK-325, etc.), Polyester modified polymethylalkylsiloxanes (e.g., BYK-315, etc.), Aralkyl modified methylalkylpolysiloxanes (e.g., BYK-322, BYK-323, etc.), Polyester modified hydroxy functional polydimethylsiloxanes (e.g., BYK-370, etc.), Acrylic functional Polyester modified polydimethylsiloxanes (e.g., Acrylic Polyester modified polydimethylsiloxanes, Polyether modified polyesters such as BYK-3570, etc.), for example, BYK-375, etc.), Polyether modified dimethylpolysiloxanes (Polyether modified dimethylpolysiloxanes, for example, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), Non-Ionic acrylic copolymers (Non-Ionic acrylic copolymers, for example, BYK-380, etc.), Ionic acrylic copolymers (Ionic acrylic polymers, for example, BYK-381, etc.), polyacrylates (polyacrylates, for example, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-36IN, BYK-357, BYK-358, 358N, BYK-352, etc.), polymethacrylates (polymethacrylates, for example, BYK-390, etc.), Polyether modified acrylic functional polydimethylsiloxanes (Polyether modified acrylic copolymers, for example, UV-3500, ultraviolet copolymers, etc.), polyvinyl alcohol copolymers (polyvinyl alcohol, etc.), and the like, BYK-UV3530, etc.), Polyether modified siloxanes (e.g., BYK-347, etc.), Alcohol alkoxylates (e.g., BYK-DYNFET 800, etc.), acrylates (e.g., BYK-392, etc.), Silicone modified polyacrylates (e.g., hydroxy functional (OH-functional)) such as BYK-Silclean 3700, etc. The amount of the additive to be used may vary depending on the purpose of 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 of the silsesquioxane polymer and the solvent.
When the coating composition according to the present invention is applied to a glass substrate (glass base material) and dried or cured to form a coating layer, a tempered glass panel which can maintain the optical characteristics of glass and can improve the mechanical hardness such as the surface hardness of glass, the abrasion resistance and the contamination resistance can be manufactured. The curing of the coating composition may be carried out by a conventional method such as heating, light irradiation, normal temperature arrangement, moisture injection, catalyst injection, etc. Fig. 1 and 2 are sectional views illustrating the structure of a flat-type and curved-type tempered glass panel according to an embodiment of the present invention, respectively. As shown in fig. 1 and 2, a tempered glass panel according to the present invention includes: a flat glass substrate 10 and a curved glass substrate 12, and a silsesquioxane polymer coating layer 20 formed of a silsesquioxane polymer of the chemical formula 3, which is coated on the surface (front surface and/or rear surface) of the glass substrates (10, 12). The silsesquioxane polymer coating layer 20 formed from the coating composition according to the present invention may be formed on the front surface (a of fig. 1), both surfaces (B of fig. 1), or the rear surface (C of fig. 1) of the flat plate-type glass substrate 10 as shown in fig. 1. As shown in fig. 2, the silsesquioxane polymer coating layer 20 may be formed on the front surface (a in fig. 2), both surfaces (B in fig. 2), or the rear surface (C in fig. 2) of the curved glass substrate 12. The silsesquioxane polymer coating 20 has a thickness of 50nm to 100 μm, specifically 0.1 to 50 μm, more specifically 1 to 30 μm. However, when the thickness of the coating layer 20 is 50nm or less, the abrasion resistance and the stain resistance (fingerprint resistance) may be maintained, but the impact strength improvement effect may be insufficient. On the contrary, when the thickness of the coating layer 20 exceeds 100 μm, although the impact strength of the tempered glass panel increases, cracks may be generated in the coating layer 20 or the coating layer 20 may be damaged when an impact is applied. In addition, the glass panel is preferably free from damage to a ball of 500g or less in the ball drop evaluation. The ball drop evaluation is a method of obtaining the breaking strength by dropping a steel ball (steel ball) from a certain height.
The glass substrates (10, 12) may be wall materials (including cement wall materials), floor materials (including cement floor materials), bricks, tiles, roofs, windows; cups, dishes, bowls; a semiconductor manufacturing apparatus; glass for automobiles, optical products, glasses, electronic products, solar cell bodies, and protective glass, but not limited thereto. In particular, the coating composition according to the present invention can be effectively used for wall materials (including cement wall materials), flooring materials (including cement flooring materials), buildings or structures such as bricks, tiles, roofs, and windows; household articles such as cups, dishes, bowls and the like; a semiconductor manufacturing apparatus; glass for automobiles, optical products, glasses, electronic products such as mobile phones, solar cell bodies, glass for protection, and the like. Among them, glass is a generic term for solid substances including Si.
The silsesquioxane polymer coating layer 20 formed according to the present invention is formed of a silicon-based material having optical characteristics (refractive index) similar to those of glass, and therefore, while maintaining excellent optical characteristics of glass, physical characteristics such as surface hardness, mechanical strength, prevention of abrasion and stain resistance, and fingerprint resistance can be improved. In addition, according to the present invention, since the coating composition is simply applied to the surfaces of various types of glass, there is an advantage that the coating process is easy.
Detailed description of the preferred embodiments
The present invention will be described in more detail below with reference to specific examples. The following examples are illustrative of the present invention, and the present invention is not limited to the examples described below.
Production examples 1-1 to 1-7 and comparative examples 1-1 to 1-4 Synthesis of silsesquioxane polymers
In a flask equipped with a cooling tube and a stirrer, 32g of distilled water and 100g of methanol were charged, and 261.61g of 2-methyl-2-propenoic acid-3- (trichlorosilyl) propyl ester (3- (trichlorosilyl) propionate) was slowly dropped for 10 minutes while maintaining the temperature at-4 ℃. After further stirring for 20 minutes, 500g of toluene was added dropwise, the temperature was raised to room temperature, and then stirring was carried out for 10 minutes (Si-OH and Si-alkoxy (OR) were obtained simultaneously)2)). Then, 24.64g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) was added dropwise thereto and stirred for 10 minutes. 10g of Na was added dropwise to the reaction solution at one time2CO320% by weight aqueous solution, the temperature was raised to 100 ℃ and condensation was carried out for one day. The reaction mixture was separated into an aqueous layer and a toluene layer, and purified, and after confirming that the pH was neutral, the toluene layer was subjected to vacuum pressure reduction to remove all toluene, thereby obtaining a silsesquioxane polymer.
The obtained silsesquioxane polymer had a linear structure as shown in chemical formula 3, a weight average molecular weight of 10000, and no unreacted monomer was present. The weight average molecular weight is a polystyrene-reduced weight average molecular weight measured using gel permeation chromatography. The silsesquioxane polymer obtained was analyzed by a thermogravimetric Analyzer (TGA) using a decomposition temperature measurement method, and the residual ratio of alkoxy groups (methoxy groups) was 3 wt%, and the ratio of n: m was about 2:1 as a result of 1H-NMR analysis. Then, using the same method, for 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 the following table 1, respectively, and silsesquioxane polymers were produced, respectively.
The residual ratio of the alkoxy group is measured by confirming the decomposition amount of the alkoxy group by condensation at a temperature ranging from 150 ℃ to 250 ℃ by TGA, and the ratio of n: m is obtained by calculating the area integral amount of Si-C derived from the functional groups of the repeating units n and m and Si-OCH appearing only in the repeating unit m3Amount of C portion integration ofTo measure.
[ Table 1]
Production examples 2-1 to 2-7 and comparative examples 2-1 to 2-4 production of coating compositions
30g of the silsesquioxane polymers obtained in production examples 1-1 to 1-7 and comparative examples 1-1 to 1-4 were dissolved in 70g of methyl isobutyl ketone, respectively, to prepare 100g of a coating composition. To 100 parts by weight of the obtained coating composition, 3 parts by weight of chloroacetophenone as a photoinitiator, 1 part by weight of BYK-347 and 1 part by weight of BYK-UV3500 were added and the mixture was stirred for 10 minutes to prepare a photocurable coating composition.
Production examples 3-1 to 3-7 and comparative examples 3-1 to 3-4 production of tempered glass panels
The coating compositions obtained from production examples 2-1 to 2-7 and comparative examples 2-1 to 2-4 were coated on plate-type glass substrates (gorilla glass substrates) having a thickness of 80 μm by dipping (dip coating), heat-treated at 85 ℃ for 10 minutes in hot air, and then irradiated with UV for curing. Then, the glass plate was subjected to firing (bonding) treatment at 200 ℃ for 1.5 hours to form a coating film having a thickness of 10 μm on the glass substrate, thereby producing a tempered glass panel.
The physical properties of the tempered glass panels produced 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: evaluation was carried out according to JIS 5600-5-4 with a load of 1000 g. The pencil is made of Mitsubishi product, hardness of each pencil is implemented for 5 times, and if more than 2 scratches occur, the pencil is judged to be bad. (e.g., labeled as number of scratches occurring less than 2/5, and labeled 5/5 when less than 2 scratches occurred in 5).
(2) Evaluation of adhesion: the adhesive tape was peeled off at 90 degrees by scratching every 1mm with a spatula (cutter) according to JIS K5600-5-6, making 100 cracks in a lattice pattern, and the coated surface was visually checked to see whether or not the adhesive tape was stuck and peeled off. The number of cracks that did not break off among 100 cracks is shown in table 1. (e.g., labeled as number not dropped/100, and when 100 are not dropped, labeled as 100/100).
(3) Evaluation of abrasion resistance: evaluation was carried out according to JIS 5600-5-4 with a load of 1000 g. The number of scratches was confirmed using steel wool (steelwool).
(4) Evaluation of stain resistance (fingerprint resistance): contact angles before and after coating were confirmed by using a contact angle measuring instrument.
[ Table 2]
EXAMPLE 4 production of tempered glass Panel
A tempered glass panel was manufactured in the same manner as in example 3-1, except that a bent type glass substrate was used instead of the plate type glass substrate.
EXAMPLE 5 production of tempered glass Panel
A tempered glass panel was manufactured in the same manner as in example 3-2, except that the coating composition was applied using a paint spray gun instead of the dipping method.
EXAMPLE 6 production of tempered glass Panel
A tempered glass panel was produced in the same manner as in example 3-2, except that the Coating composition was applied at a speed of 5mm/sec in the manner of Slot Die Coating (Slot Die Coating) instead of the dipping method.
The tempered glass panels produced in examples 4 to 6 were subjected to physical property evaluation in the same manner as in example 3-1, and the results are shown in table 3.
[ Table 3]
EXAMPLE 7 production of tempered glass Panel
A tempered glass panel was produced in the same manner as in example 3-2, except that a coating film having a thickness of 10 μm was formed on the front, rear or both of a plate-type glass substrate having a thickness of 80 μm.
Then, the tempered glass panel produced in example 7 was evaluated for falling ball (ball drop), and the results are shown in table 4.
The ball drop evaluation was carried out by dropping a steel ball (steelball, 20-2000g) from a predetermined height (1m) after fixing the tempered glass panel test piece, and the presence or absence of breakage was evaluated. Evaluation was performed 5 times per ball drop, and when 2 or more cracks occurred, it was judged to be defective. (with breakage: O, without breakage: X).
[ Table 4]
As is apparent from the examples and comparative examples, the silsesquioxane polymer and the coating composition containing the silsesquioxane polymer according to the present invention form a coating layer on the surface of a glass substrate through a simple coating process, thereby improving the mechanical strength, surface hardness, abrasion resistance, and stain resistance of the glass while maintaining the optical properties of the glass.
Claims (11)
1. A silsesquioxane polymer wherein the silsesquioxane polymer comprises repeating units of the following chemical formula 1 and chemical formula 2:
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulas 1 and 2, R1 are each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth) acrylic group, hydroxyl group, thiol group, isocyanate group, nitrile group, nitro group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, aralkyl group having 3 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms or arylthiol group having 3 to 40 carbon atoms, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, 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 100000,
n: m is 1:1 to 100: 1.
2. A silsesquioxane polymer according to claim 1 wherein the silsesquioxane polymer comprises the following formula 3:
[ chemical formula 3]
R1, R2, n and m of the chemical formula 3 are the same as defined in the above chemical formula 1 and chemical formula 2.
3. A silsesquioxane polymer according to claim 1 or2, wherein R1 has a reactive substituent or functional group selected from the group consisting of an amino group, a (meth) acrylic group, a hydroxyl group, a thiol group, a vinyl group, and an epoxy group, and R2 is hydrogen, a methyl group, an ethyl group, or a propyl group.
4. A coating composition, comprising:
a silsesquioxane polymer comprising repeating units of the following chemical formula 1 and chemical formula 2: and a solvent, wherein the solvent is a mixture of,
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulas 1 and 2, R1 are each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth) acrylic group, hydroxyl group, thiol group, isocyanate group, nitrile group, nitro group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, aralkyl group having 3 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms or arylthiol group having 3 to 40 carbon atoms, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, 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 100000,
n: m is 1:1 to 100: 1.
5. The coating composition of claim 4, wherein the silsesquioxane polymer comprises the following chemical formula 3,
[ chemical formula 3]
R1, R2, n and m of the chemical formula 3 are the same as defined in the above chemical formula 1 and chemical formula 2.
6. The coating composition of claim 4 or 5, wherein R1 has a reactive substituent or functional group selected from the group consisting of amino, (meth) acrylic, hydroxyl, thiol, vinyl, and epoxy groups, and R2 is hydrogen, methyl, ethyl, or propyl.
7. A coating composition according to claim 4 or 5, wherein the silsesquioxane polymer is present in an amount of 50 to 99 wt.% and the solvent is present in an amount of 1 to 50 wt.%.
8. A glass panel, comprising:
a glass substrate; and
a coating layer obtained by applying and curing the coating composition according to claim 4 or 5.
9. The glass panel of claim 8, wherein the silsesquioxane polymer coating has a thickness of 50nm to 100 μ ι η.
10. The glass panel of claim 8, wherein the silsesquioxane polymer coating is applied to one or both sides of the glass substrate.
11. The glass panel of claim 8, wherein the glass panel does not damage balls below 500g in a ball drop evaluation.
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| KR20170153244 | 2017-11-16 | ||
| KR10-2017-0153244 | 2017-11-16 | ||
| PCT/KR2018/013712 WO2019098622A1 (en) | 2017-11-16 | 2018-11-12 | Silsesquioxane polymer and coating composition comprising same |
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| CN113260686A (en) * | 2018-12-31 | 2021-08-13 | 株式会社东进世美肯 | Synthetic resin coating composition and method for producing synthetic resin substrate using same |
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| CN114867794B (en) * | 2019-12-31 | 2023-10-27 | 株式会社东进世美肯 | Water-repellent coating composition for wet coating comprising silsesquioxane oligomer |
| KR20210111946A (en) * | 2020-03-03 | 2021-09-14 | 삼성디스플레이 주식회사 | Light emitting device |
| KR20220096987A (en) * | 2020-12-31 | 2022-07-07 | 주식회사 동진쎄미켐 | Silsesquioxane resin and antireflection composition comprising the same and having anti-fingerprint properties |
| KR20240103797A (en) * | 2022-12-27 | 2024-07-04 | 주식회사 동진쎄미켐 | Coating Composition Comprising Silsesquioxane Polymer and Reactive Linear Polymer, and Flexible Display Film |
| WO2024157637A1 (en) * | 2023-01-26 | 2024-08-02 | 株式会社ダイセル | Laminate and image display device |
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| KR20190056307A (en) | 2019-05-24 |
| CN111344334B (en) | 2022-09-16 |
| JP2024129013A (en) | 2024-09-26 |
| JP2021503540A (en) | 2021-02-12 |
| WO2019098622A1 (en) | 2019-05-23 |
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