KR20220039575A - Compound for ultra-thin reinforced coating agent and reinforced coating agent comprising the same - Google Patents

Abstract

The present invention relates to a compound for a coating agent that reinforces strength with ultra-thin coatings, and a coating agent for strength reinforcement comprising the same. More specifically, the present invention relates to a compound for a coating agent that can improve the strength of an object to be coated, such as preventing breakage due to external impact and force, and to a coating agent for strength reinforcement comprising the same. To this end, the present invention is configured such that an object is coated with ultra-thin coatings of about 1 micrometer or less thickness by dry or wet methods, thereby reinforcing the fragile properties of regular glass and tempered glass.

Description

COMPOUND FOR ULTRA-THIN REINFORCED COATING AGENT AND REINFORCED COATING AGENT COMPRISING THE SAME}

The present invention relates to a compound for an ultra-thin strength reinforcing coating agent and a strength reinforcing coating agent comprising the same, and more particularly, by coating it in an ultra-thin (thickness of 1 micrometer or less) through a dry or wet method to easily break tempered glass and ultra-thin glass It relates to a compound for a useful strength-reinforcing coating agent capable of providing an anti-breaking function due to impact and pressure by reinforcing it, and a strength-reinforcing coating agent comprising the same.

Recently, with the rapid development of touch-type displays such as IT-based smart phones, consumers' expectations for quality are getting higher and higher. Tempered glass used for glass is getting thinner and thinner. In order to provide optical properties such as anti-reflection or color sense, laminated coating using metal oxide (SiO ₂ , TiO ₂ , etc.), which is a high refractive and low refractive material, is required. There is an increasing tendency to break easily by pressure, so there is an urgent need for prevention of cracking due to the strength-reinforcing coating.

In addition, with the advent of variously curved or foldable displays, ultra-thin glass (100 micrometers or less) in the form of a thinner film has begun to be used in order to impart flexible bending properties. In order to cope with such flexible materials, it is essential to develop a coating material that overcomes difficulties such as the ability to coat the strength reinforcing coating as an ultra-thin film, and the excellent anti-break function.

However, the coating thickness itself is several micrometers, such as using silicone resin in combination with other additives (Korean Patent No. 10-1836802) or using it directly on a glass substrate (Korean Patent Publication No. 10-2004-0017552). It is limited to a composition for hard coating that is thick in the order of several tens of micrometers or is applied to a polymer film by mixing an acrylate and a silane structure (Korean Patent Publication Nos. 10-2016-0013402, 10-2018-0074544). The ultra-thin film strength-reinforcing coating agent has a disadvantage in that it is not suitable for application.

Therefore, it is coated with an ultra-thin film of 1 micrometer or less to maintain optical properties, while having the flexibility required for thin tempered glass and ultra-thin glass (UTG; Ultra Thin Glass, 0.1 mm or less) with a thickness of less than 0.5 mm and preventing breakage The development of a strength-reinforcing coating agent with

In order to solve this problem, in the present invention, it is coated with an ultra-thin (thickness of 1 micrometer or less) through a dry or wet method to reinforce the properties of tempered glass and ultra-thin glass that are easily broken to provide a function to prevent breakage due to external impact and pressure. An object of the present invention is to provide a useful strength-reinforcing coating compound and a strength-reinforcing coating agent comprising the same.

According to the first aspect of the present invention, there is provided a compound for a strength-reinforcing coating agent comprising a structure represented by the following Chemical Formula 1 or 2:

[Formula 1]

A-[BR ¹ -Si(OR ² ) _3-n ] _m

[Formula 2]

(E) _k -[BR ¹ -Si(OR ² ) _3-n ] _m

In Formulas 1 and 2, R ¹ is a direct bond or a substituted or unsubstituted aliphatic group having 1 to 10 carbon atoms (more specifically, 1 to 9, 2 to 10, or 2 to 9);

R ² is a substituted or unsubstituted aliphatic group having 1 to 5 carbon atoms;

each B is independently a linker connecting the siloxane group, which is a terminal functional group, to the main chain;

A is a substituted or unsubstituted straight-chain and branched aliphatic or aromatic group having 1 to 40 carbon atoms;

E is C _1-3 alkyleneoxyC _1-3 alkylene, provided that the terminal E is C _1-3 alkyloxyC _1-3 alkylene;

n is an integer from 0 to 2;

m is an integer from 1 to 6;

k is an integer from 1 to 20;

In one embodiment, B is -NH-, -O-, -C(=O)O-, -CH ₂ O-, -CH ₂ SRO-, -CH ₂ SROC(=O)-, -CH ₂ SRC(=O)O-, -CH ₂ SRNHC(=O)-, -CH ₂ SROC(=O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SRC(=O)-, -CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROC(=O)-, -CH ₂ SO ₂ RC(=O)O-, -CH ₂ SO ₂ RNHC(=O)-, -CH ₂ SO ₂ ROC( =O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SO ₂ RC(=O)-, CH ₂ O(CH ₂ ) ₃ S(CH ₂ ) ₂ NH-, -OC(=O) RO-, -OC(=O)ROC(=O)-, -OC(=O)RC(=O)O-, -OC(=O)RNHC(=O)-, -OC(=O)ROC (=O)(CH ₂ ) ₂ OC(=O)-, -OC(=O)RC(=O)-, -C(=O)ORO-, -C(=O)OROC(=O)- , -C(=O)ORC(=O)O-, -C(=O)ORNHC(=O)-, -C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O)- , -C(=O)ORC(=O)-, -ORO-, -OROC(=O)-, -ORC(=O)O-, -ORNHC(=O)-, -OROC(=O)( CH ₂ ) ₂ OC(=O)-, -ORC(=O)-, -NHRO-, -NHC(=O)O-, -NHROC(=O)-, -NHRC(=O)O-, - NHRNHC(=O)-, -NHROC(=O)(CH ₂ ) ₂ OC(=O)-, -NHRC(=O)-, -CH ₂ RO-, -CH ₂ ROC(=O)-, - CH ₂ RC(=O)O-, -CH ₂ RNHC(=O)-, -OCH ₂ CHOHCH ₂ -, -OCH ₂ CHOHCH ₂ O-, -CH ₂ ROC(=O)(CH ₂ ) ₂ OC( =O)-, -OC ₆ H ₄ RO-, -OC ₆ H ₄ ROC(=O)-, -OC ₆ H ₄ RC(=O)O-, -OC ₆ H ₄ RNHC(=O)-, -OC ₆ H ₄ ROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ RC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)-, -OC ₆ H ₄ C(=O)ORC(=O)O-, -OC ₆ H ₄ C(=O)ORO-, -OC ₆ H ₄ C(=O)ORNHC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ C(= O)ORC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)-, -OC ₆ H ₄ C(=O)NHRC(=O)O-, -OC ₆ H ₄ C (=O)NHRO-, -OC ₆ H ₄ C(=O)NHRNHC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)(CH ₂ ) ₂ OC(=O)- and -OC ₆ H ₄ C(=O)NHRC(=O)-, wherein R is hydrogen or a substituted or unsubstituted C 1 to C 10 alkylene group.

According to a second aspect of the present invention, there is provided a compound for a strength-reinforcing coating agent comprising a structure represented by the following Chemical Formula 3 or 4:

[Formula 3]

X-{A-[BR ¹ -Si(OR ² ) _3-n ] _m } _l

[Formula 4]

X-{(E) _k -[BR ¹ -Si(OR ² ) _3-n ] _m } _l

In Formulas 3 and 4, R ¹ , R ² , B, A, E, n, m and k are as defined in Formulas 1 and 2,

X is one of O, S, N, C and P;

l is a valency of X, and is an integer selected from 2 to 6.

In one embodiment, the total molecular weight of the compound for a strength-reinforcing coating agent comprising any one of the structures of Formulas 1 to 4 according to the present invention is 200 to 4,000 g/mol.

According to a third aspect of the present invention, at least one compound for a strength-reinforcing coating agent of the present invention; and a solvent; including, a strength-reinforcing coating agent is provided.

According to a fourth aspect of the present invention, there is provided a method for manufacturing tempered glass, comprising wet coating a glass substrate using the strength reinforcing coating agent of the present invention.

According to a fifth aspect of the present invention, there is provided a method for manufacturing tempered glass, comprising dry coating a glass substrate using the strength reinforcing coating agent of the present invention.

The present invention is possible to provide a compound for a strength-reinforcing coating agent used in a strength-reinforcing coating agent having a function of preventing the glass from breaking due to impact or pressure by coating with an ultra-thin film of 1 micrometer or less.

In addition, it is possible to provide an ultra-thin strength-reinforcing coating agent having excellent flexibility in accordance with the characteristics of a flexible flexible display such as ultra-thin glass.

The present invention can provide an ultra-thin strength-reinforcing coating agent having excellent surface pressure (surface strength) by deposition using a metal oxide in order to impart optical properties to thin tempered glass.

The present invention is an ultra-thin film and has excellent adhesion to metal oxides such as tempered glass, so that it can be applied as a coating agent to prevent breakage due to impact of ceramic semiconductors.

1 is a graph showing transmittance measurement results according to wavelengths of Examples 2-1 and 2-2 of the present invention compared to Comparative Example 1-1.
2 is a graph showing reflectance measurement results according to wavelengths of Examples 2-1 and 2-2 of the present invention compared to Comparative Example 1-1.
3 is a diagram illustrating a measurement state of a GIT (Glass Impact Test) device for measuring the impact strength of specimen glass.
4 is an impact strength measurement (GIT) result of Examples 2-1 and 2-2 of the present invention compared to Comparative Example 1-1.
5 is a diagram for explaining the measurement state of the ROR (Ring on Ring) device for measuring the surface pressure of the glass specimen.
6 is a surface pressure measurement (ROR) result of Examples 2-1 and 2-2 of the present invention compared to Comparative Example 1-1.
7 is a surface pressure measurement (ROR) result of Example 4-1, Example 4-2, Example 4-3, and Example 4-4 in comparison with Comparative Example 1-2.

Hereinafter, the present invention will be described in more detail.

According to the first aspect of the present invention, there is provided a compound for a strength-reinforcing coating agent comprising a structure represented by the following Chemical Formula 1 or 2:

[Formula 1]

A-[BR ¹ -Si(OR ² ) _3-n ] _m

[Formula 2]

(E) _k -[BR ¹ -Si(OR ² ) _3-n ] _m

In Formulas 1 and 2, R ¹ is a direct bond or a substituted or unsubstituted aliphatic group having 1 to 10 carbon atoms (more specifically, 1 to 9, 2 to 10, or 2 to 9);

R ² is a substituted or unsubstituted aliphatic group having 1 to 5 carbon atoms;

each B is independently a linker connecting the siloxane group, which is a terminal functional group, to the main chain;

A is a substituted or unsubstituted straight-chain and branched aliphatic or aromatic group having 1 to 40 carbon atoms;

E is C _1-3 alkyleneoxyC _1-3 alkylene, provided that the terminal E is C _1-3 alkyloxyC _1-3 alkylene;

n is an integer from 0 to 2;

m is an integer from 1 to 6;

k is an integer from 1 to 20;

In the formula described herein, the structure of XY _n means a state in which n Ys are each independently bonded to X.

In the formulas described herein, the term “substituted or unsubstituted” means that the group is unsubstituted, or one or more substituents (eg, a hydroxy group, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms) , or at least one selected from the group consisting of an aryl group having 6 to 10 carbon atoms).

In one embodiment, B is -NH-, -O-, -C(=O)O-, -CH ₂ O-, -CH ₂ SRO-, -CH ₂ SROC(=O)-, -CH ₂ SRC(=O)O-, -CH ₂ SRNHC(=O)-, -CH ₂ SROC(=O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SRC(=O)-, -CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROC(=O)-, -CH ₂ SO ₂ RC(=O)O-, -CH ₂ SO ₂ RNHC(=O)-, -CH ₂ SO ₂ ROC( =O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SO ₂ RC(=O)-, CH ₂ O(CH ₂ ) ₃ S(CH ₂ ) ₂ NH-, -OC(=O) RO-, -OC(=O)ROC(=O)-, -OC(=O)RC(=O)O-, -OC(=O)RNHC(=O)-, -OC(=O)ROC (=O)(CH ₂ ) ₂ OC(=O)-, -OC(=O)RC(=O)-, -C(=O)ORO-, -C(=O)OROC(=O)- , -C(=O)ORC(=O)O-, -C(=O)ORNHC(=O)-, -C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O)- , -C(=O)ORC(=O)-, -ORO-, -OROC(=O)-, -ORC(=O)O-, -ORNHC(=O)-, -OROC(=O)( CH ₂ ) ₂ OC(=O)-, -ORC(=O)-, -NHRO-, -NHC(=O)O-, -NHROC(=O)-, -NHRC(=O)O-, - NHRNHC(=O)-, -NHROC(=O)(CH ₂ ) ₂ OC(=O)-, -NHRC(=O)-, -CH ₂ RO-, -CH ₂ ROC(=O)-, - CH ₂ RC(=O)O-, -CH ₂ RNHC(=O)-, -OCH ₂ CHOHCH ₂ -, -OCH ₂ CHOHCH ₂ O-, -CH ₂ ROC(=O)(CH ₂ ) ₂ OC( =O)-, -OC ₆ H ₄ RO-, -OC ₆ H ₄ ROC(=O)-, -OC ₆ H ₄ RC(=O)O-, -OC ₆ H ₄ RNHC(=O)-, -OC ₆ H ₄ ROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ RC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)-, -OC ₆ H ₄ C(=O)ORC(=O)O-, -OC ₆ H ₄ C(=O)ORO-, -OC ₆ H ₄ C(=O)ORNHC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ C(= O)ORC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)-, -OC ₆ H ₄ C(=O)NHRC(=O)O-, -OC ₆ H ₄ C (=O)NHRO-, -OC ₆ H ₄ C(=O)NHRNHC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)(CH ₂ ) ₂ OC(=O)- and -OC ₆ H ₄ C(=O)NHRC(=O)-, wherein R is hydrogen or a substituted or unsubstituted C 1 to C 10 alkylene group.

According to the second aspect of the present invention, a compound for a strength-reinforcing coating agent having a function of preventing breakage due to external impact or pressure while capable of ultra-thin coating, including a structure represented by the following Chemical Formula 3 or 4, is provided:

[Formula 3]

X-{A-[BR ¹ -Si(OR ² ) _3-n ] _m } _l

[Formula 4]

X-{(E) _k -[BR ¹ -Si(OR ² ) _3-n ] _m } _l

In Formulas 3 and 4, R ¹ , R ² , B, A, E, n, m and k are as defined in Formulas 1 and 2,

X is one of O, S, N, C and P;

l is a valency of X, and is an integer selected from 2 to 6.

In one embodiment, the total molecular weight of the compound for a strength-reinforcing coating agent including the structure of any one of Chemical Formulas 1 to 4 according to the present invention may be 200 to 4,000 g/mol.

According to a third aspect of the present invention, at least one compound for a strength-reinforcing coating agent of the present invention; and a solvent; including, a strength-reinforcing coating agent is provided.

The solvent that can be included in the strength reinforcing coating agent according to the present invention is not particularly limited, and a solvent known in the art can be used, for example, alcohol-based (methanol, ethanol, isopropanol, butanol, methyl cellosolve, etc.), ketone (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.), hexane (hexane, heptane, octane, etc.), benzene (benzene, toluene, xylene, etc.) ) may be used. These may be used alone or in combination of two or more.

In one embodiment, the strength-reinforcing coating agent of the present invention may further include a catalyst to promote hydrolysis of siloxane. Examples of the usable catalyst include acid catalysts such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, sulfuric acid, chlorosulfonic acid, iodic acid, and pyrophosphoric acid; base catalysts such as ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide, imidazole, n-butylamine, di-n-butylamine, tri-n-butylamine, ammonium perchlorate, and tetramethyl-hydroxide; and ion exchange resins such as Amberite IRA-400 and IRA-67, and may be selected from the group consisting of combinations thereof.

The amount of the catalyst is not particularly limited, but in the case of an acid catalyst and a base catalyst, about 0.0001 to 0.01 parts by weight may be added based on 100 parts by weight of the compound for the strength reinforcing coating agent, and in the case of an ion exchange resin, 100 parts by weight of the compound for the strength reinforcing coating agent 1 to 10 parts by weight may be added, but is not limited thereto.

According to a fourth aspect of the present invention, there is provided a method for manufacturing tempered glass, comprising wet coating a glass substrate using the strength reinforcing coating agent of the present invention.

The method for the wet coating is not particularly limited, and for example, spin coating, spray coating, spindle coating, bar coating, flow coating, slot die coating, gravure printing, etc. may be performed.

According to a fifth aspect of the present invention, there is provided a method for manufacturing tempered glass, comprising dry coating a glass substrate using the strength reinforcing coating agent of the present invention.

The method for the dry coating is not particularly limited, and for example, the coating may be performed by a vacuum deposition method by heating with an e-beam or resistance heating method at a vacuum degree of 1x10 ^-3 torr or more.

In the method for manufacturing tempered glass by dry coating, an anti-reflection coating or color coating may be additionally performed, and this additional coating may be performed by e-beam or resistance heating heating or vacuum deposition of sputtering.

Hereinafter, the present invention will be described in more detail through synthesis examples and examples. However, the scope of the present invention is not limited thereto.

[Example]

1. Synthesis Example 1

Ethylbis(uretanopropyltriethoxysilane) was prepared as follows.

Put 20 g of 3-isocyanate propyltriethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. Into this solution, 2.76 g of ethylene glycol was added, and the temperature was gradually raised to 75° C. while vigorously stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of dibutyltin dilaurate catalyst was added and vigorously stirred. When it is confirmed that the isocyanate peak (2270-2290 cm ^-1 ) disappears from the FTIR spectrum, it is cooled and the solvent and impurities are primarily removed using a rotary evaporator, and a vacuum oven 1 torr, 50 ° C. . The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: -(CH ₂ ) ₂ -; If m: 2]

2. Synthesis Example 2

Ethylbis(uretanopropyltrimethoxysilane) was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. Into this solution, 2.29 g of ethylene glycol was added, and the temperature was gradually raised to 75° C. while strongly stirring under a nitrogen atmosphere with a dehydrator attached, and a drop of dibutyltin dilaurate catalyst was added thereto and vigorously stirred. When it is confirmed that the isocyanate peak (2270-2290 cm ^-1 ) disappears from the FTIR spectrum, it is cooled and the solvent and impurities are primarily removed using a rotary evaporator, and a vacuum oven 1 torr, 50 ° C. . The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: -(CH ₂ ) ₂ -; If m: 2]

3. Synthesis Example 3

1,1,1-tris(uretanopropyltriethoxysilylmethyl)propane was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 5.06 g of 1,1,1-tris (hydroxymethyl) propane was added to this solution, and the temperature was gradually raised to 75° C. while vigorously stirring under a nitrogen atmosphere with a dehydrator attached. A drop of dibutyltin dilaurate catalyst was added and vigorously stirred. . When it was confirmed that the isocyanate peak (2270-2290 cm ^-1 ) disappeared from the FTIR spectrum, the solvent and impurities were primarily removed using a rotary evaporator, and second purification was performed in a vacuum oven at 1 torr, 50 ° C. to obtain a solid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: CH ₃ CH ₂ C(CH ₂ ) ₃ -; If m: 2]

4. Synthesis Example 4

2,2'-oxybis(methylene)bis[2-ethyl-1,3-bis(uretanopropyltriethoxysilane)] was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. To this solution, 2.76 g of di(trimethylolpropane) was added, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of dibutyltindilaurate catalyst was added and vigorously stirred. When it was confirmed that the isocyanate peak (2270-2290 cm ^-1 ) disappeared from the FTIR spectrum, the solvent and impurities were primarily removed using a rotary evaporator, and second purification was performed in a vacuum oven at 1 torr, 50 ° C. to obtain a solid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 3, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: CH ₃ CH ₂ C(CH ₂ ) ₃ -; m: 2; l: 2; If X: O]

5. Synthesis Example 5

2,2',2" nitrilotriethyluretanopropyltriethoxysilane was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. To this solution, 4.02 g of triethanolamine was added, and the temperature was gradually raised to 75° C. while vigorously stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of dibutyltin dilaurate catalyst was added and vigorously stirred. When it is confirmed that the isocyanate peak (2270~2290cm ^-1 ) disappears from the FTIR spectrum, it is cooled, the solvent and impurities are primarily removed using a rotary evaporator, and the liquid compound with high viscosity is purified secondarily at 1torr in a vacuum oven, 50℃ got The NMR and FTIR spectra were consistent with the following structures.

[In Formula 3, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: -(CH ₂ ) ₂ -; m: 1; l: 3; If X: N]

6. Synthesis Example 6

1,2,6-hexanetri(uretanopropyltriethoxysilane) was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. In this solution, 3.61 g of hexanetriol was added, and the temperature was gradually raised to 75° C. while vigorously stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of dibutyltin dilaurate catalyst was added thereto and vigorously stirred. When it is confirmed that the isocyanate peak (2270~2290cm ^-1 ) disappears from the FTIR spectrum, it is cooled, the solvent and impurities are primarily removed using a rotary evaporator, and the liquid compound with high viscosity is purified secondarily at 1torr in a vacuum oven, 50℃ got The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: -(CH ₂ ) ₄ CHCH ₂ -; If m: 3]

7. Synthesis Example 7

1,2-Benzenebis(uretanopropyltriethoxysilane) was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. Into this solution, 4.45 g of pyrocatechol was added, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere equipped with a dehydration device, and a drop of dibutyltin dilaurate catalyst was added thereto, followed by vigorous stirring. When it is confirmed that the isocyanate peak (2270~2290cm ^-1 ) disappears from the FTIR spectrum, it is cooled, the solvent and impurities are primarily removed using a rotary evaporator, and the viscous liquid compound is secondarily purified at 1torr in a vacuum oven, 50℃. got The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: phenyl; If m: 2]

8. Synthesis Example 8

1,3-Benzenebis(uretanopropyltriethoxysilane) was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 4.45 g of resorcinol was added to this solution, and the temperature was gradually raised to 75° C. while vigorously stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of dibutyltin dilaurate catalyst was added and vigorously stirred. When it is confirmed that the isocyanate peak (2270~2290cm ^-1 ) disappears from the FTIR spectrum, it is cooled, the solvent and impurities are primarily removed using a rotary evaporator, and the liquid compound with high viscosity is purified secondarily at 1torr in a vacuum oven, 50℃ got The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: phenyl; If m: 2]

9. Synthesis Example 9

1,4-Benzenebis(uretanopropyltriethoxysilane) was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 4.45 g of hydroquinone was added to this solution, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere equipped with a dehydration device, and a drop of dibutyltin dilaurate catalyst was added and vigorously stirred. When it was confirmed that the isocyanate peak (2270-2290 cm ^-1 ) disappeared from the FTIR spectrum, the solvent and impurities were primarily removed using a rotary evaporator, and second purification was performed in a vacuum oven at 1 torr, 50 ° C. to obtain a solid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NHC(=O)O-; A: phenyl; If m: 2]

10. Synthesis Example 10

1,3,3'-Aminohydroxylethoxybis(propyltriethoxysilane) was prepared as follows.

Put 20 g of 3-glycidoxypropyltriethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 15.9 g of aminopropyltriethoxysilane was added to this solution, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere with a dehydrator attached, and 0.01 g of Novozyme 435 catalyst was added and stirred vigorously. When it is confirmed that the hydroxy peak (3640-3610 cm ^-1 ) is generated in the FTIR spectrum, it is cooled, the solvent and impurities are primarily removed using a rotary evaporator, and the transparent liquid compound is obtained by secondary purification at 1 torr in a vacuum oven and 50 ° C. got it The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -NH-, -O-; A: —CH ₂ COHCH ₂ —; If m: 2]

11. Synthesis Example 11

Bis[3-(triethoxysilylpropoxy)-2-hydropropoxyethoxy]ethane was prepared as follows.

Put 20 g of 3-glycidoxypropyltriethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. Into this solution, 4.45 g of ethylene glycol was added, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere with a dehydrator attached, and a drop of dibutyltin dilaurate catalyst was added thereto and vigorously stirred. When it is confirmed that the hydroxy peak (3640-3610 cm ^-1 ) is generated in the FTIR spectrum, it is cooled, the solvent and impurities are primarily removed using a rotary evaporator, and the transparent liquid compound is obtained by secondary purification at 1 torr in a vacuum oven, 50 ° C. got it The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : -(CH ₂ ) ₃ -; B: -OCH ₂ CHOHCH ₂ O-; A: -(CH ₂ ) ₂ -; If m: 2]

12. Synthesis Example 12

Oxybis(ethane-2,1-diyl)bis(2methyl-1,3-(triethoxysilyl)propanoate was prepared as follows.

Put 20 g of diethylene glycol dimethacrylate and 20 g of toluene in a 100 mL round-bottom flask and stir at room temperature for 30 minutes. 30 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 45° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 2, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : —CH(CH ₃ )CH ₂ —; B: -C(=O)O-; E: —CH ₂ CH ₂ OCH ₂ CH ₂ —; k: 1; If m: 2]

13. Synthesis Example 13

Bis(3-(trimethoxysilyl)propyl)carbonate was prepared as follows.

Put 10 g of diallyl carbonate and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 30 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 60° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₃ ; n: 0; R ¹ : -CH ₂ CH ₂ CH ₂ -; B: -O-; A: -C(=O)-; If m: 2]

14. Synthesis Example 14

Naphthalene-2,3-diylbis(3-(trimethoxysilyl)propanoate was prepared as follows.

Put 12.5 g of 2,3-dihydroxy-naphthalene and 30 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 15 g of acrylic acid was added to this solution, and the temperature was gradually raised to 80° C. with strong stirring, 0.1 ml of sulfuric acid was added, and the mixture was vigorously stirred for 20 hours. After cooling to room temperature, it was transferred to a 250 ml separatory funnel, and washed with purified water several times until the sulfuric acid used as a catalyst was removed. The solution obtained by washing with water was filtered using a membrane filter to obtain a clear solution. The solvent and impurities were removed from this clear solution using a rotary evaporator. Transfer the purified syrupy intermediate to a 100ml round bottom flask, add 30g of toluene, and stir at room temperature for 30 minutes. 30 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 60° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₃ ; n: 0; R ¹ : —CH ₂ CH ₂ —; B: -C(=O)O-; A: naphthyl; If m: 2]

15. Synthesis Example 15

1,2-phenylenebis(3-(trimethoxysilyl)propanoate was prepared as follows.

Put 10 g of 1,2-benzenediol and 30 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 15 g of acrylic acid was added to this solution, and the temperature was gradually raised to 80° C. with strong stirring, 0.1 ml of sulfuric acid was added, and the mixture was vigorously stirred for 20 hours. After cooling to room temperature, it was transferred to a 250 ml separatory funnel, and washed with purified water several times until the sulfuric acid used as a catalyst was removed. The solution obtained by washing with water was filtered using a membrane filter to obtain a clear solution. The solvent and impurities were removed from this clear solution using a rotary evaporator. Transfer the purified syrupy intermediate to a 100ml round bottom flask, add 30g of toluene, and stir at room temperature for 30 minutes. 15 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 60° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₃ ; n: 0; R ¹ : —CH ₂ CH ₂ —; B: -C(=O)O-; A: phenyl; If m: 2]

16. Synthesis Example 16

1,2-bis(3-trimethoxysilyl)propoxy)benzene was prepared as follows.

10 g of 1,2-benzenediol and 30 g of toluene were added to a 100 mL round-bottom flask, and the mixture was stirred at room temperature for 30 minutes. 10 g of sodium hydroxide was added to this solution, and the temperature was gradually raised to 65° C. with strong stirring, followed by vigorous stirring for 4 hours. 20 g of allyl bromide was added to the solution, and the temperature was gradually raised to 60° C. with strong stirring, followed by vigorous stirring for 14 hours. After cooling to room temperature, it was transferred to a 250 ml separatory funnel and washed with water repeatedly until the impurities were removed and clear using hydrochloric acid of 3 normal concentration. 2 g of hydrotalcite was added to the solution obtained by washing with water to remove acid, and a clear solution was obtained while filtration using a membrane filter. The solvent and impurities were removed from this clear solution using a rotary evaporator. Transfer the purified syrupy intermediate to a 100ml round bottom flask, add 30g of toluene, and stir at room temperature for 30 minutes. 15 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 60° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₃ ; n: 0; R ¹ : -CH ₂ CH ₂ CH ₂ -; B: -O-; A: phenyl; If m: 2]

17. Synthesis Example 17

1,3,5-tris(trimethoxysilyl)propoxy)benzene was prepared as follows.

10 g of 1,3,5-trihydroxybenzene dihydrate and 60 g of toluene were added to a 250 mL round-bottom flask, and the mixture was stirred at room temperature for 30 minutes. 15 g of sodium hydroxide was added to this solution, and the temperature was gradually raised to 65° C. with strong stirring, followed by vigorous stirring for 4 hours. 26 g of allyl bromide was added to the solution, and the temperature was gradually raised to 60° C. with strong stirring, followed by vigorous stirring for 14 hours. After cooling to room temperature, it was transferred to a 500 ml separatory funnel, and washed with water repeatedly until the impurities were removed and clear using hydrochloric acid of 3 normal concentration. 2 g of hydrotalcite was added to the solution obtained by washing with water to remove acid, and a clear solution was obtained while filtration using a membrane filter. The solvent and impurities were removed from this clear solution using a rotary evaporator. Transfer the purified syrupy intermediate to a 100ml round bottom flask, add 30g of toluene, and stir at room temperature for 30 minutes. 20 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 60° C. under strong stirring under a nitrogen atmosphere equipped with a dehydration device, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₃ ; n: 0; R ¹ : -CH ₂ CH ₂ CH ₂ -; B: -O-; A: phenyl; If m: 3]

18. Synthesis Example 18

4,4'-bis(3-(trimethoxysilyl)propylurethanoxy)oxydibenzoate was prepared as follows.

Put 20 g of 3-isocyanate propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 12 g of 4,4'-oxybis(benzoic acid) was added to this solution, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere with a dehydrator attached, and a drop of dibutyltin dilaurate catalyst was added and stirred vigorously. When it was confirmed that the isocyanate peak (2270-2290 cm ^-1 ) disappeared from the FTIR spectrum, the solvent and impurities were primarily removed using a rotary evaporator, and second purification was performed in a vacuum oven at 1 torr, 50 ° C. to obtain a solid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 3, R ² : -CH ₃ ; n: 0; R ¹ : -CH ₂ CH ₂ CH ₂ -; B: -NHC(=O)O-; A: -C(=O)-phenyl-; m: 1; l: 2; If X: O]

19. Synthesis Example 19

Trimethoxysilylpropyltriethoxyethylsulfide was prepared as follows.

Put 20 g of 3-mercaptopropyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 19.39 g of vinyltriethoxysilane was added to this solution, and the temperature was gradually increased to 75° C. while vigorously stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 3, R ² : -CH ₃ ; n: 0; R ¹ : -CH ₂ -; B: -CH ₂ -; A: -CH ₂ -; m: 1; l: 2; X: If S]

20. Synthesis Example 20

1,2-bis(triethoxysilyl)ethane was prepared as follows.

Put 20 g of vinyltriethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. 12.84 g of triethoxysilane was added to this solution, and the temperature was gradually raised to 70° C. under strong stirring under a nitrogen atmosphere with a dehydrator attached, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : direct bond; B: -CH ₂ -; A: -CH ₂ CH ₂ -; If m: 2]

21. Synthesis Example 21

1,3-Methacrylomethylpropyl-bis(triethoxysilane) was prepared as follows.

Put 20 g of 3-methacrylic propyltrimethoxysilane and 20 g of toluene in a 100 mL round-bottom flask, and stir at room temperature for 30 minutes. To this solution, 9.83 g of triethoxysilane was added, and the temperature was gradually raised to 75° C. under strong stirring under a nitrogen atmosphere equipped with a dehydrator, and a drop of platinum catalyst was added and vigorously stirred. When it is confirmed that the carbon double bond (-C=C) peak (1680~1640cm ^-1 ) disappears from the FTIR spectrum, the solvent and impurities are primarily removed using a rotary evaporator, and the second is performed in a vacuum oven at 1torr, 50℃. Purification was performed to obtain a transparent liquid compound. The NMR and FTIR spectra were consistent with the following structures.

[In Formula 1, R ² : -CH ₂ CH ₃ ; n: 0; R ¹ : direct bond; B: -CH ₂ -; A: -CH ₂ CH ₂ OC(=O)CH(CH ₃ )-; If m: 2]

Example 1: Preparation of wet coating solution

Example 1-1 : A coating solution was prepared using the compound prepared in Synthesis Example 1 among the above Synthesis Examples.

2 g of synthesized ethylbis (uretanopropyltriethoxysilane) was diluted with 98 g of ethanol, 0.01 g of aqueous ammonia was added thereto, and the solution was sufficiently stirred to prepare a solution.

Example 1-2 : A coating solution was prepared by mixing the compound prepared in Synthesis Example 1 and the compound prepared in Synthesis Example 11 in a ratio of 7 to 3 among the above Synthesis Examples.

After mixing 1.5 g of synthesized ethylbis (uretanopropyltriethoxysilane) and 0.5 g of bis[3-(triethoxysilylpropoxy)-2-hydropropoxyethoxy]ethane, diluted with 98 g of ethanol A solution was prepared by adding 0.01 g of aqueous ammonia and sufficiently stirring.

Example 1-3 : A wet coating solution was prepared using the compounds prepared in Synthesis Example 1 to Synthesis Example 21, respectively.

2 g of each synthesized compound was diluted with 98 g of ethanol, 0.01 g of aqueous ammonia was added thereto, and the solution was sufficiently stirred to prepare a solution.

Example 2: Wet Coating

Example 2-1 : 0.25 mL of the solution prepared in Example 1-1 was injected into Corning's 'Gorilla Glass 5 (GG5)' using a micropipette, and uniformly in a bar coater using the No. 4 (#4) bar. applied generously. The coated glass was cured in an oven at 150°C for 30 minutes and the properties were analyzed. The coating thickness measured using an ellipsometer was 100 nm.

Example 2-2 : 0.250 mL of the solution prepared in Example 1-2 was injected into Corning's 'Gorilla Glass 3 (GG3)' using a micropipette, and uniformly in a bar coater using the No. 4 (#4) bar. applied generously. The coated glass was cured in an oven at 150°C for 30 minutes and the properties were analyzed. The coating thickness measured using an ellipsometer was 100 nm.

Example 2-3 : Using a micropipette, 0.25 mL of the solution prepared in Example 1-3 was injected into LK Lab's 'Micro Cover Glass (borosilicate 3.3 glass, 0.13 to 0.16 mm)', and 4 times (# 4) Using a bar, uniformly applied 5 sheets each in a bar coater. The coated glass was cured in an oven at 150° C. for 30 minutes, prepared 5 sheets each, and labeled as Examples 2-3-1 to 2-3-21, and characteristics were analyzed. The coating thickness measured using an ellipsometer was 100 nm.

Example 3: Preparation of dry coatings

Example 3-1 : A dry coating agent (vacuum deposition) was prepared using the compound prepared in Synthesis Example 1 among the above Synthesis Examples.

A dry coating agent was prepared by diluting 8 g of synthesized ethylbis (uretanopropyltriethoxysilane) with 2 g of ethanol, taking 0.85 g, and injecting it into a vacuum deposition vessel (Korean Patent No. 10-1025005).

Example 3-2 : A coating solution was prepared by mixing the compound prepared in Synthesis Example 1 and the compound prepared in Synthesis Example 4 in a ratio of 3 to 1 among the above synthesis examples.

6 g of synthesized ethylbis (uretanopropyltriethoxysilane) and 2 g of 2,2'-oxybis(methylene)bis[2-ethyl-1,3-bis(uretanopropyltriethoxysilane)] After mixing, dilute with 2 g of ethanol, take 0.85 g, and inject into a vacuum deposition container (Korean Patent No. 10-1025005) to prepare a dry coating agent.

Example 3-3 : A coating solution was prepared by mixing the compound prepared in Synthesis Example 1 and the compound prepared in Synthesis Example 8 in a ratio of 3 to 1 among the above Synthesis Examples.

After mixing 6g of synthesized ethylbis(uretanopropyltriethoxysilane) and 2g of 1,3-benzenebis(uretanopropyltriethoxysilane), dilute with 2g of ethanol, take 0.85g, and A dry coating agent was prepared by injecting it into Korean Patent No. 10-1025005).

Example 3-4 : A coating solution was prepared by mixing the compound prepared in Synthesis Example 1 and the compound prepared in Synthesis Example 11 in a ratio of 7 to 3 among the above Synthesis Examples.

After mixing 6 g of synthesized ethylbis (uretanopropyltriethoxysilane) and 2 g of bis[3-(triethoxysilylpropoxy)-2-hydropropoxyethoxy]ethane, diluted with 2g of ethanol and 0.85g The dry coating agent was prepared by taking the , and injecting it into a container for vacuum deposition (Korean Patent No. 10-1025005).

Example 4: Dry coating (vacuum deposition)

Example 4-1 : In a vacuum vaporizer (Univec Φ2050), a tempered glass (0.21T) of SCHOTT, which is used for window glass for a cell phone camera, is mounted, and the coating agent for deposition prepared in Example 3-1 is put into the E-beam port, and the vacuum degree is 5x10 ^- When reaching ⁵ torr, argon etching (flow rate 20 sccm, 120v) was performed for 5 minutes using an ion gun mounted on a vacuum evaporator to activate the surface of the mounted tempered glass. Then, the coating agent prepared in Example 3-1 was applied at an e-beam power of 3.8%, and the coating was performed twice for 2 minutes to a thickness of 50 nm to achieve 100 nm. Then, the anti-reflection coating is coated in the order of SiO ₂ (40 nm), Ti ₃ O ₅ (18.7 nm), SiO ₂ (38.2 nm), Ti ₃ O ₅ (33.4 nm), SiO ₂ (100.9 nm) and exhausted. Samples were prepared.

Example 4-2 : A coating sample was prepared in the same manner as in Example 4-1, except that the coating agent for deposition prepared in Example 3-2 was used instead of the coating agent for deposition prepared in Example 3-1.

Example 4-3 : A coating sample was prepared in the same manner as in Example 4-1, except that the coating agent for deposition prepared in Example 3-3 was used instead of the coating agent for deposition prepared in Example 3-1.

Example 4-4 : A coating sample was prepared in the same manner as in Example 4-1, except that the coating agent for deposition prepared in Example 3-4 was used instead of the coating agent for deposition prepared in Example 3-1.

Comparative Example 1: Bare Glass

Comparative Example 1-1 : Corning's 'Gorilla Glass 5 (GG5)' was used as bare glass.

Comparative Example 1-2 : Using the tempered glass (0.21T) of SCHOTT, which is used as a window glass for a mobile phone camera, the same procedure as in Example 4-1 was performed, but Examples 3-1, 3-2, 3-3 or 3- No coating agent of 4 was used.

Comparative Example 1-3 : LK Lab's 'Micro Cover Glass (borosilicate 3.3 glass, 0.13-0.16 mm)' was used as a bare glass.

Hereinafter, a characteristic test of the glass specimen prepared in the present invention is disclosed.

<Optical properties>

Transmittance and reflectance at a wavelength of 240 to 1,000 nm were measured using a UV-VIS spectrometer (HITACH, U-4100).

For the coating samples prepared in Examples 2-1 and 2-2, the transmittance of the optical properties of Comparative Example 1-1 was measured using a spectrometer and compared to FIG. 1, and the reflectance was measured and shown in FIG. 2 shown in The optical transmittance of the glass coated according to the present invention was almost similar to that of the bare glass, and the reflectance was 0.5 to 1% lower than that of the bare glass. It was found that application to fields requiring optical properties is possible.

<Impact strength characteristics (GIT ; Glass Impact Test)>

To prevent scattering of glass destroyed by falling weight, the specimen glass prepared in a polyethylene bag (thickness less than 0.6mm) is mounted on the lower jig (ring outer diameter 50.8mm, inner diameter 25.4mm) of the Impact Tester (CKSI, Lab-Q E602SS) After mounting a steel ball (diameter 12mm) on the upper part of the glass to match the lower part of the rail, an aluminum hammer weighing 60 g was raised in 5 cm increments to record the height (cm) of the stage before destruction. A photograph of the GIT equipment being measured is disclosed in FIG. 3 .

The coating samples prepared in Examples 2-1 and 2-2 were compared with Comparative Example 1-1 to measure the impact resistance height, and the results are shown in FIG. 4 . Three samples were measured for each sample, and the average value was indicated by a red triangle. As compared with the bare glass of Comparative Example 1-1, the fracture heights of Examples 2-1 and 2-2 prepared according to the present invention were nearly doubled, confirming that the breakage prevention properties due to impact were excellent.

<Surface pressure characteristics (ROR ; Ring on Ring)>

In the lower layer of UTM (Universal Testing Machine; Taeshin Precision Machinery, TSU-500), between the outer ring (diameter: 30mm) and the inner ring (diameter: 15mm), the prepared glass specimen is attached to both sides of the glass specimen with protective films attached and compressed. The maximum strength until failure was measured by applying pressure at a speed of 100 mm/min, and the load cell used was 5KN. The measurement method was measured according to ASTM C1499 Standard, and the mounted state is shown in FIG. 5 .

The surface pressure characteristics were measured by comparing the coating samples prepared in Examples 2-1 and 2-2 with Comparative Example 1-1, and the results are shown in FIG. 6 . Three samples were measured for each sample, and the average value was indicated by a red triangle. Compared to the bare glass of Comparative Example 1-1, the strength of Examples 2-1 and 2-2 prepared according to the present invention was twice or more, confirming that the anti-break properties were excellent.

In the case of camera lens or camera lens cover glass, in order to look beautiful or to give optical properties (transmittance, reflectance control, etc.) . When a metal oxide (ceramic) such as SiO ₂ or TiO ₂ is coated on glass (including tempered glass), it is easily broken by impact or pressure compared to uncoated glass when a metal oxide that is harder than glass is laminated and coated. will have This was disclosed in Comparative Example 1-2 in FIG. On the other hand, in the case of the sample glass prepared according to Example 4-4 in Example 4-1 of the present invention, it was confirmed that the surface pressure strength (ROR) was recovered above the level of bare glass that was not treated with anything.

<Pen Drop Attributes>

The glass prepared in Examples 2-3-1 to 2-3-21 prepared by the method of Example 2-3 above was mounted on a metal (SUS) plate, and a ballpoint pen of 'BIC' (a yellow general ballpoint pen, including a cap) 5.7 g) with the cap on the back, with the pointed end of the ball-point pen facing the mounted glass surface, raised at an interval of 1 cm in height, dropped until the glass specimen broke, and then recorded the height just before breaking to check the anti-break properties. In order to prevent scattering of broken glass, a PET protective film (0.25t) was laminated on both sides of the glass specimens prepared in Examples 2-3-1 to 2-3-21, with the coated side facing up, 5 each. The value immediately before breaking was recorded, and the average value of each and the median average excluding the maximum and minimum values among the five were converted and recorded, and it is shown in Table 1 below.

Compared to Comparative Example 1-3 in which nothing was treated, all of Examples 2-3-1 to 2-3-21 had excellent anti-break properties.

Claims (13)

A compound for a strength-reinforcing coating agent comprising a structure represented by the following Chemical Formula 1 or 2:
[Formula 1]
A-[BR ¹ -Si(OR ² ) _3-n ] _m
[Formula 2]
(E) _k -[BR ¹ -Si(OR ² ) _3-n ] _m
In Formulas 1 and 2,
R ¹ is a direct bond or a substituted or unsubstituted aliphatic group having 1 to 10 carbon atoms;
R ² is a substituted or unsubstituted aliphatic group having 1 to 5 carbon atoms;
each B is independently a linker connecting the siloxane group, which is a terminal functional group, to the main chain;
A is a substituted or unsubstituted straight-chain and branched aliphatic or aromatic group having 1 to 40 carbon atoms;
E is C _1-3 alkyleneoxyC _1-3 alkylene, provided that the terminal E is C _1-3 alkyloxyC _1-3 alkylene;
n is an integer from 0 to 2;
m is an integer from 1 to 6;
k is an integer from 1 to 20; According to claim 1, wherein B is -NH-, -O-, -C(=O)O-, -CH ₂ O-, -CH ₂ SRO-, -CH ₂ SROC(=O)-, -CH ₂ SRC(=O)O-, -CH ₂ SRNHC(=O)-, -CH ₂ SROC(=O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SRC(=O)-, - CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROC(=O)-, -CH ₂ SO ₂ RC(=O)O-, -CH ₂ SO ₂ RNHC(=O)-, -CH ₂ SO ₂ ROC (=O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SO ₂ RC(=O)-, CH ₂ O(CH ₂ ) ₃ S(CH ₂ ) ₂ NH-, -OC(=O )RO-, -OC(=O)ROC(=O)-, -OC(=O)RC(=O)O-, -OC(=O)RNHC(=O)-, -OC(=O) ROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC(=O)RC(=O)-, -C(=O)ORO-, -C(=O)OROC(=O) -, -C(=O)ORC(=O)O-, -C(=O)ORNHC(=O)-, -C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O) -, -C(=O)ORC(=O)-, -ORO-, -OROC(=O)-, -ORC(=O)O-, -ORNHC(=O)-, -OROC(=O) (CH ₂ ) ₂ OC(=O)-, -ORC(=O)-, -NHRO-, -NHC(=O)O-, -NHROC(=O)-, -NHRC(=O)O-, -NHRNHC(=O)-, -NHROC(=O)(CH ₂ ) ₂ OC(=O)-, -NHRC(=O)-, -CH ₂ RO-, -CH ₂ ROC(=O)-, -CH ₂ RC(=O)O-, -CH ₂ RNHC(=O)-, -OCH ₂ CHOHCH ₂ -, -OCH ₂ CHOHCH ₂ O-, -CH ₂ ROC(=O)(CH ₂ ) ₂ OC (=O)-, -OC ₆ H ₄ RO-, -OC ₆ H ₄ ROC(=O)-, -OC ₆ H ₄ RC(=O)O-, -OC ₆ H ₄ RNHC(=O)- , -OC ₆ H ₄ ROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ RC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)-, -OC ₆ H ₄ C(=O)ORC(=O)O-, -OC ₆ H ₄ C(=O)ORO-, -OC ₆ H ₄ C(=O)ORNHC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ C(= O)ORC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)-, -OC ₆ H ₄ C(=O)NHRC(=O)O-, -OC ₆ H ₄ C (=O)NHRO-, -OC ₆ H ₄ C(=O)NHRNHC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)(CH ₂ ) ₂ OC(=O)- And -OC ₆ H ₄ C(=O)NHRC(=O)- is an aliphatic or aromatic group selected from the group, wherein R is hydrogen or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, Compounds for strength-reinforcing coatings. The compound according to claim 1, wherein the total molecular weight is 200 to 4,000 g/mol. A compound for a strength-reinforcing coating agent comprising a structure represented by the following Chemical Formula 3 or 4:
[Formula 3]
X-{A-[BR ¹ -Si(OR ² ) _3-n ] _m } _l
[Formula 4]
X-{(E) _k -[BR ¹ -Si(OR ² ) _3-n ] _m } _l
In Formulas 3 and 4,
R ¹ is a direct bond or a substituted or unsubstituted aliphatic group having 1 to 10 carbon atoms;
R ² is a substituted or unsubstituted aliphatic group having 1 to 5 carbon atoms;
each B is independently a linker connecting the siloxane group, which is a terminal functional group, to the main chain;
A is a substituted or unsubstituted straight-chain and branched aliphatic or aromatic group having 1 to 40 carbon atoms;
E is C _1-3 alkyleneoxyC _1-3 alkylene, provided that the terminal E is C _1-3 alkyloxyC _1-3 alkylene;
n is an integer from 0 to 2;
m is an integer from 1 to 6;
k is an integer from 1 to 20;
X is one of O, S, N, C and P;
l is a valency of X, and is an integer selected from 2 to 6. According to claim 4, wherein B is -NH-, -O-, -C(=O)O-, -CH ₂ O-, -CH ₂ SRO-, -CH ₂ SROC(=O)-, -CH ₂ SRC(=O)O-, -CH ₂ SRNHC(=O)-, -CH ₂ SROC(=O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SRC(=O)-, - CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROC(=O)-, -CH ₂ SO ₂ RC(=O)O-, -CH ₂ SO ₂ RNHC(=O)-, -CH ₂ SO ₂ ROC (=O)(CH ₂ ) ₂ OC(=O)-, -CH ₂ SO ₂ RC(=O)-, CH ₂ O(CH ₂ ) ₃ S(CH ₂ ) ₂ NH-, -OC(=O )RO-, -OC(=O)ROC(=O)-, -OC(=O)RC(=O)O-, -OC(=O)RNHC(=O)-, -OC(=O) ROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC(=O)RC(=O)-, -C(=O)ORO-, -C(=O)OROC(=O) -, -C(=O)ORC(=O)O-, -C(=O)ORNHC(=O)-, -C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O) -, -C(=O)ORC(=O)-, -ORO-, -OROC(=O)-, -ORC(=O)O-, -ORNHC(=O)-, -OROC(=O) (CH ₂ ) ₂ OC(=O)-, -ORC(=O)-, -NHRO-, -NHC(=O)O-, -NHROC(=O)-, -NHRC(=O)O-, -NHRNHC(=O)-, -NHROC(=O)(CH ₂ ) ₂ OC(=O)-, -NHRC(=O)-, -CH ₂ RO-, -CH ₂ ROC(=O)-, -CH ₂ RC(=O)O-, -CH ₂ RNHC(=O)-, -OCH ₂ CHOHCH ₂ -, -OCH ₂ CHOHCH ₂ O-, -CH ₂ ROC(=O)(CH ₂ ) ₂ OC (=O)-, -OC ₆ H ₄ RO-, -OC ₆ H ₄ ROC(=O)-, -OC ₆ H ₄ RC(=O)O-, -OC ₆ H ₄ RNHC(=O)- , -OC ₆ H ₄ ROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ RC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)-, -OC ₆ H ₄ C(=O)ORC(=O)O-, -OC ₆ H ₄ C(=O)ORO-, -OC ₆ H ₄ C(=O)ORNHC(=O)-, -OC ₆ H ₄ C(=O)OROC(=O)(CH ₂ ) ₂ OC(=O)-, -OC ₆ H ₄ C(= O)ORC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)-, -OC ₆ H ₄ C(=O)NHRC(=O)O-, -OC ₆ H ₄ C (=O)NHRO-, -OC ₆ H ₄ C(=O)NHRNHC(=O)-, -OC ₆ H ₄ C(=O)NHROC(=O)(CH ₂ ) ₂ OC(=O)- And -OC ₆ H ₄ C(=O)NHRC(=O)- is an aliphatic or aromatic group selected from the group, wherein R is hydrogen or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, Compounds for strength-reinforcing coatings. According to claim 4, wherein the total molecular weight is 200 to 4,000 g / mol, the strength-reinforcing coating compound. The compound for a coating agent for strength reinforcement according to any one of claims 1 to 6; And a solvent; Containing, strength-reinforcing coating agent. 8. The method of claim 7, wherein the solvent is methanol, ethanol, isopropanol, butanol, methyl cellosolve, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, hexane, heptane, An octane, benzene, toluene, xylene-based coating agent that is selected from the group consisting of, and combinations thereof. A method for producing tempered glass, comprising wet coating a glass substrate using the strength reinforcing coating agent according to claim 7 . The method of claim 9, wherein the wet coating is performed using spin coating, spray coating, spindle coating, bar coating, flow coating, slot die coating or gravure printing. A method of manufacturing tempered glass, comprising dry coating a glass substrate using the strength reinforcing coating agent according to claim 7 . The method of claim 11 , wherein the dry coating is performed by vacuum deposition by heating with an e-beam or resistance heating method at a vacuum degree of 1x10 ^-3 torr or more. The method of claim 11 , wherein an anti-reflection coating or a color coating is additionally performed, and the additional coating is performed by vacuum deposition of e-beam or resistance heating or sputtering method.

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