KR102363820B1 - Silsesquioxane composite polymer and method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a silsesquioxane composite polymer and a method for manufacturing the same, and more particularly, to include a linear silsesquioxane chain of a specific structure and a cage-type silsesquioxane in one polymer to maximize processability and physical properties It relates to a silsesquioxane composite polymer.

Description

Silsesquioxane composite polymer and manufacturing method thereof

The present invention relates to a silsesquioxane composite polymer and a method for manufacturing the same, and more particularly, to a silsesquioxane composite that maximizes processability and physical properties by introducing various silsesquioxane structures into one silsesquioxane polymer It is about polymers.

Silsesquioxane has been used for various purposes in various fields. In particular, several attempts have been made to improve processability and maximize mechanical and physical properties, and R&D continues to this day. However, the silsesquioxane polymers developed so far are still insufficient to simultaneously satisfy processability and mechanical and physical properties.

For example, cage-type silsesquioxane shows physical properties that can be expressed by siloxane bonds and is applied in various fields. Reorganization of the molecular unit such as recrystallization occurs in the result of applying the topographical structure itself, resulting in a problem that the reproducibility of the performance is not guaranteed. As another representative structure, the linear (ladder) silsesquioxane has excellent solution processability and has a structure that can compensate for the shortcomings of the cage-type structure, but has a disadvantage in that the physical properties do not reach the cage-type structure, which is a crystalline structure. In addition, because random type silsesquioxane is polymerized in a free form, it is necessary to gel it using Si-OH, Si-alkoxy, etc., which are unstable in the polymer, and apply the limitations and reproducibility. There are problems that are difficult to guarantee.

Attempts have been made to control the structure of this silsesquioxane to a specific structure in accordance with the requirements of the industry. For example, US Patent Publication No. US2011-0201827 uses a silane coupling agent as a precursor to control polyhedral silsesquioxane and to derive unique advantages, but this is also an example of using only a substituent by connecting a cage type to a single linear. The improvement of the physical properties could not be greatly improved.

Therefore, the present inventors have studied to supplement the disadvantages of silsesquioxane as described above and to maximize the advantages. As a result, the polymer structure of a specific structure was designed and an easy curing process was introduced using the organic functional group introduced in the side chain. As a result, the present invention was completed by confirming that excellent physical properties can be maintained for a long time and can be used in various industrial fields such as main material, additive material, and coating material.

In order to solve the above problems, the present invention provides a silsesquioxane composite polymer that maximizes processability and physical properties by including a linear silsesquioxane chain of a specific structure and a cage-type silsesquioxane in one polymer aim to do

Another object of the present invention is to provide a method for preparing the silsesquioxane composite polymer.

Another object of the present invention is to provide a silsesquioxane coating composition comprising the silsesquioxane composite polymer.

In order to achieve the above object, the present invention provides a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 3:

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

이고, D는

이고, E는

이며,A is

and D is

and E is

is,

Y is each independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],

each X is independently R ¹⁰ or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group or unsubstituted, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alke Nyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₃ ~ C ₄₀ heteroaryl group, C ₇ ~ C ₄₀ aralkyl group, C ₆ ~ C ₄₀ aryloxy group, or C ₆ ~ C ₄₀ aryl thiol group, preferably deuterium, halogen, amine group, (meth) acryl group, thiol group, isocyanate Group, nitrile group, nitro group, phenyl group, or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, amine group, epoxy group, cyclohexyl epoxy group, (meth) acrylic group substituted or unsubstituted with a phenyl group or a cyclohexyl epoxy group , a thiol group, a phenyl group or an isocyanate group,

a and d are each independently an integer from 1 to 100,000, preferably a is from 3 to 1000, d is from 1 to 500, more preferably a is from 5 to 300, and d is from 2 to 100,

e is 1 or 2, preferably 1,

n is each independently an integer of 1 to 20, preferably 3 to 10.

구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하는 것을 특징으로 하는 화학식 1로 표시되는 실세스퀴옥산 복합고분자의 제조방법을 제공한다:In addition, the present invention is a first step of preparing the following formula (4) by mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing; and in Formula 4 after the first step

a second step of adding an acid catalyst to the reactor to adjust the reaction solution to acidity to introduce the structure, then adding an organosilane compound and stirring; and a third step of carrying out a condensation reaction by converting the reaction solution to basic by adding a basic catalyst to the reactor after the second step. to provide:

[Formula 4]

In the above, R ¹ , R ² , R ⁶ , a and d are as defined in Formulas 1 to 3.

및

구조를 화학식 2와 같이 도입하기 위하여 유기실란 화합물을 첨가하고, 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 제3단계 이후 재결정과 필터과정을 통하여, 단독 cage 생성 구조를 제거하는 제4단계를 포함하는 것을 특징으로 하는 화학식 2로 표시되는 실세스퀴옥산 복합고분자의 제조방법을 제공한다.In addition, the present invention is a first step of preparing the following formula (4) by mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing; and in Formula 4 after the first step

and

a second step of adding an organosilane compound to introduce the structure as shown in Chemical Formula 2, adjusting the reaction solution to acidity by adding an acid catalyst to the reactor, and then stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and a fourth step of removing the single cage-forming structure through recrystallization and filtering after the third step.

구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에

구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하는 것을 특징으로 하는 화학식 3으로 표시되는 실세스퀴옥산 복합고분자의 제조방법을 제공한다.In addition, the present invention is a first step of preparing the following formula (4) by mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing; and in Formula 4 after the first step

a second step of adding an acid catalyst to the reactor to adjust the reaction solution to acidity to introduce the structure, then adding an organosilane compound and stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and at the end of the composite polymer after the third step.

In order to introduce the structure, an acid catalyst is introduced into the reactor to convert the reaction solution into an acidic atmosphere, and a fourth step of mixing and stirring an organosilane compound. A manufacturing method is provided.

The present invention also provides a silsesquioxane coating composition comprising the silsesquioxane composite polymer.

The silsesquioxane composite polymer according to the present invention has both the processing ease of linear silsesquioxane and the excellent physical properties of cage-type silsesquioxane at the same time. , heat resistance, etc. can be imparted to various materials.

Hereinafter, the present invention will be described in detail.

The present invention provides a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 3:

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

이고, D는

이고, E는

이며,A is

and D is

and E is

is,

Y is each independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],

each X is independently R ¹⁰ or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group or unsubstituted, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alke Nyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₃ ~ C ₄₀ heteroaryl group, C ₇ ~ C ₄₀ aralkyl group, C ₆ ~ C ₄₀ aryloxy group, or C ₆ ~ C ₄₀ aryl thiol group, preferably deuterium, halogen, amine group, (meth) acryl group, thiol group, isocyanate Group, nitrile group, nitro group, phenyl group, or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, amine group, epoxy group, cyclohexyl epoxy group, (meth) acrylic group substituted or unsubstituted with a phenyl group or a cyclohexyl epoxy group , a thiol group, a phenyl group or an isocyanate group,

a and d are each independently an integer from 1 to 100,000, preferably a is from 3 to 1000, d is from 1 to 500, more preferably a is from 5 to 300, and d is from 2 to 100,

e is 1 or 2, preferably 1,

n is each independently an integer of 1 to 20, preferably 3 to 10.

,

로 구성되고, 말단단위로

를 선택적으로 도입할 수 있는 복합 실세스퀴옥산 고분자이다.The silsesquioxane composite polymer represented by any one of Formulas 1 to 3 is R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ It has the indicated organic functional group, and the repeating unit is

,

is composed of, and as a terminal unit

It is a complex silsesquioxane polymer that can be selectively introduced.

에 도입된[(SiO_3/2R)_4+2nO] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 5와 같다:The repeating unit of Formula 1 or 2

n of the [(SiO _3/2 R) _4+2n O] structure introduced into may be substituted with an integer of 1 to 20, preferably 3 to 10, and more preferably an average n value of 4 to 5 And, when n is 4, the substituted structure is represented by the following Chemical Formula 5:

[Formula 5]

In the above formula, R is as defined above.

에 도입된[(SiO_3/2R)_4+2nR] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 6과 같다: In the present invention, the repeating unit of Formula 3

n of the [(SiO _3/2 R) _4+2n R] structure introduced into may be substituted with an integer of 1 to 20, preferably 3 to 10, more preferably an average n value of 4 to 5 And, for example, when expressing a substituted structure when n is 4, it is as follows:

[Formula 6]

In the above formula, R is as defined above.

As a specific example, the silsesquioxane composite polymer of Formula 1 may be the polymers shown in Tables 1 and 2 below. In Tables 1 to 6, ECHE means (Epoxycyclohexyl)ethyl, GlyP means Glycidoxypropyl, and POMMA means (methacryloyloxy)propyl, and when two or more are described, it means mixed use. n is each independently 1 to 8;

No R1 R2 R6 R9 R of Y 1-1 OH, methoxy H, methyl ECHE ECHE ECHE 1-2 OH, methoxy H, methyl phenyl phenyl phenyl 1-3 OH, methoxy H, methyl methyl methyl methyl 1-4 OH, methoxy H, methyl GlyP GlyP GlyP 1-5 OH, methoxy H, methyl POMMA POMMA POMMA 1-6 OH, methoxy H, methyl ECHE phenyl phenyl 1-7 OH, methoxy H, methyl ECHE methyl methyl 1-8 OH, methoxy H, methyl ECHE GlyP GlyP 1-9 OH, methoxy H, methyl ECHE POMMA POMMA 1-10 OH, methoxy H, methyl phenyl ECHE ECHE 1-11 OH, methoxy H, methyl phenyl methyl methyl 1-12 OH, methoxy H, methyl phenyl GlyP GlyP 1-13 OH, methoxy H, methyl phenyl POMMA POMMA 1-14 OH, methoxy H, methyl methyl ECHE ECHE 1-15 OH, methoxy H, methyl methyl phenyl phenyl 1-16 OH, methoxy H, methyl methyl GlyP GlyP 1-17 OH, methoxy H, methyl methyl POMMA POMMA 1-18 OH, methoxy H, methyl GlyP ECHE ECHE 1-19 OH, methoxy H, methyl GlyP phenyl phenyl 1-20 OH, methoxy H, methyl GlyP methyl methyl 1-21 OH, methoxy H, methyl GlyP POMMA POMMA 1-22 OH, methoxy H, methyl POMMA ECHE ECHE 1-23 OH, methoxy H, methyl POMMA phenyl phenyl 1-24 OH, methoxy H, methyl POMMA methyl methyl 1-25 OH, methoxy H, methyl POMMA GlyP GlyP

No R1 R2 R6 R7 R of Y n 2-1 OH, methoxy H, methyl ECHE alkyl thiol ECHE 1 to 8 2-2 OH, CF ₃ H, ethyl phenyl phenyl phenyl 1 to 8 2-3 OH, methoxy H, acetyltyl alkyl thiol methyl methyl 1 to 8 2-4 CF ₃ ,methoxy vinyl, methyl GlyP dodecyl GlyP 1 to 8 2-5 OH, methoxy H, methyl POMMA alkyl thiol POMMA 1 to 8 2-6 OH, C ₈ F ₁₃ H, F ECHE phenyl phenyl 1 to 8 2-7 OH, CF ₃ CF ₃ ,methyl ECHE octyl methyl 1 to 8 2-8 OH, C ₈ F ₁₃ H, methyl F alkyl thiol GlyP 1 to 8 2-9 OH, methoxy H, CF ₃ ECHE POMMA POMMA 1 to 8 2-10 OH, methoxy H, methyl phenyl alkyl thiol ECHE 1 to 8 2-11 OH, C ₈ F ₁₃ aryl, methyl alkyl thiol methyl hexyl 1 to 8 2-12 OH, alkyl thiol H, methacrylic phenyl GlyP GlyP 1 to 8 2-13 OH, methoxy H, methyl alkyl thiol POMMA POMMA 1 to 8 2-14 OH, acrylic H, octyl methyl ECHE aminopropyl 1 to 8 2-15 vinyl, methoxy H, methyl methyl alkyl thiol phenyl 1 to 8 2-16 alkylamine H, methyl methyl GlyP GlyP 1 to 8 2-17 OH, ethyl, methyl Alkyl thiol, methyl methyl POMMA POMMA 1 to 8 2-18 acetoxy, methoxy H, methyl GlyP ECHE aminopropyl 1 to 8 2-19 propoxy, methoxy H, CF ₃ GlyP phenyl phenyl 1 to 8 2-20 OH, methoxy H, methyl aminopropyl methyl octyl 1 to 8 2-21 C ₈ F ₁₃ ,methoxy C ₈ F ₁₃ ,methyl GlyP POMMA POMMA 1 to 8 2-22 OH, aryl H, profile POMMA profile ECHE 1 to 8 2-23 OH, methoxy F, methyl POMMA phenyl phenyl 1 to 8 2-24 CF ₃ , Methacrylic H, methyl POMMA methyl methyl 1 to 8 2-25 OH, methoxy H, ethyl aminopropyl GlyP GlyP 1 to 8

As a specific example, the silsesquioxane composite polymer of Formula 2 may be the polymers shown in Tables 3 and 4 below.

No R3 R4 R6 R7 R of Y 3-1 H, methyl H, methyl ECHE ECHE ECHE 3-2 H, methyl H, methyl phenyl phenyl phenyl 3-3 H, methyl H, methyl methyl methyl methyl 3-4 H, methyl H, methyl GlyP GlyP GlyP 3-5 H, methyl H, methyl POMMA POMMA POMMA 3-6 H, methyl H, methyl ECHE phenyl phenyl 3-7 H, methyl H, methyl ECHE methyl methyl 3-8 H, methyl H, methyl ECHE GlyP GlyP 3-9 H, methyl H, methyl ECHE POMMA POMMA 3-10 H, methyl H, methyl phenyl ECHE ECHE 3-11 H, methyl H, methyl phenyl methyl methyl 3-12 H, methyl H, methyl phenyl GlyP GlyP 3-13 H, methyl H, methyl phenyl POMMA POMMA 3-14 H, methyl H, methyl methyl ECHE ECHE 3-15 H, methyl H, methyl methyl phenyl phenyl 3-16 H, methyl H, methyl methyl GlyP GlyP 3-17 H, methyl H, methyl methyl POMMA POMMA 3-18 H, methyl H, methyl GlyP ECHE ECHE 3-19 H, methyl H, methyl GlyP phenyl phenyl 3-20 H, methyl H, methyl GlyP methyl methyl 3-21 H, methyl H, methyl GlyP POMMA POMMA 3-22 H, methyl H, methyl POMMA ECHE ECHE 3-23 H, methyl H, methyl POMMA phenyl phenyl 3-24 H, methyl H, methyl POMMA methyl methyl 3-25 H, methyl H, methyl POMMA GlyP GlyP

No R3 R4 R6 R7 R of Y 4-1 OH, methoxy H, methyl ECHE alkyl thiol ECHE 4-2 OH, CF ₃ H, ethyl phenyl phenyl phenyl 4-3 OH, methoxy H, acetyltyl alkyl thiol methyl methyl 4-4 CF ₃ ,methoxy vinyl, methyl POMMA dodecyl GlyP 4-5 OH, acrylic H, methyl POMMA alkyl thiol octyl 4-6 vinyl, methoxy H, F ECHE phenyl POMMA 4-7 alkylamine CF ₃ ,methyl ECHE octyl methyl 4-8 OH, ethyl, methyl H, methyl F aminopropyl GlyP 4-9 acetoxy, methoxy H, CF ₃ aminopropyl POMMA hexyl 4-10 propoxy, methoxy H, methyl phenyl alkyl thiol ECHE 4-11 OH, C ₈ F ₁₃ aryl, methyl alkyl thiol methyl hexyl 4-12 OH, methoxy H, methacrylic phenyl GlyP GlyP 4-13 CF ₃ ,methoxy H, methyl octyl POMMA POMMA 4-14 OH, acrylic H, octyl methyl ECHE aminopropyl 4-15 vinyl, methoxy H, methyl octyl alkyl thiol phenyl 4-16 alkylamine H, methyl octyl GlyP GlyP 4-17 OH, methoxy Alkyl thiol, methyl methyl POMMA POMMA 4-18 acetoxy, methoxy H, methyl GlyP ECHE aminopropyl 4-19 propoxy, methoxy H, CF ₃ GlyP aminopropyl phenyl 4-20 OH, methoxy H, methyl aminopropyl methyl octyl 4-21 propoxy, methoxy C ₈ F ₁₃ ,methyl GlyP POMMA POMMA 4-22 OH, methoxy H, profile POMMA profile ECHE 4-23 C ₈ F ₁₃ ,methoxy F, methyl POMMA phenyl phenyl 4-24 OH, aryl H, methyl GlyP methyl GlyP 4-25 OH, methoxy H, ethyl aminopropyl GlyP GlyP

As a specific example, the silsesquioxane composite polymer of Formula 3 may be a polymer shown in Tables 5 or 6 below.

No R5 R6 R7 R8 R10 Y of R X of R 5-1 H, methyl ECHE ECHE ECHE H, methyl ECHE ECHE 5-2 H, methyl phenyl phenyl phenyl H, methyl phenyl phenyl 5-3 H, methyl methyl methyl methyl H, methyl methyl methyl 5-4 H, methyl GlyP EGCDX GlyP H, methyl EGCDX GlyP 5-5 H, methyl POMMA POMMA POMMA H, methyl POMMA POMMA 5-6 H, methyl ECHE ECHE phenyl H, methyl ECHE phenyl 5-7 H, methyl ECHE ECHE methyl H, methyl ECHE methyl 5-8 H, methyl ECHE ECHE GlyP H, methyl ECHE GlyP 5-9 H, methyl ECHE ECHE POMMA H, methyl ECHE POMMA 5-10 H, methyl ECHE phenyl ECHE H, methyl phenyl ECHE 5-11 H, methyl ECHE methyl ECHE H, methyl methyl ECHE 5-12 H, methyl ECHE GlyP ECHE H, methyl GlyP ECHE 5-13 H, methyl ECHE POMMA ECHE H, methyl POMMA ECHE 5-14 H, methyl phenyl phenyl ECHE H, methyl phenyl ECHE 5-15 H, methyl phenyl phenyl methyl H, methyl phenyl methyl 5-16 H, methyl phenyl phenyl EGDCX H, methyl phenyl EGDCX 5-17 H, methyl phenyl phenyl POMMA H, methyl phenyl POMMA 5-18 H, methyl phenyl ECHE phenyl H, methyl ECHE phenyl 5-19 H, methyl phenyl methyl phenyl H, methyl methyl phenyl 5-20 H, methyl phenyl GlyP phenyl H, methyl GlyP phenyl 5-21 H, methyl phenyl POMMA phenyl H, methyl POMMA phenyl 5-22 H, methyl methyl methyl ECHE H, methyl methyl ECHE 5-23 H, methyl methyl methyl phenyl H, methyl methyl phenyl 5-25 H, methyl methyl methyl GlyP H, methyl methyl GlyP 5-25 H, methyl methyl methyl POMMA H, methyl methyl POMMA 5-26 H, methyl methyl ECHE methyl H, methyl ECHE methyl 5-27 H, methyl methyl phenyl methyl H, methyl phenyl methyl 5-28 H, methyl methyl GlyP methyl H, methyl GlyP methyl 5-29 H, methyl methyl POMMA methyl H, methyl POMMA methyl 5-30 H, methyl GlyP GlyP ECHE H, methyl GlyP ECHE 5-31 H, methyl GlyP GlyP phenyl H, methyl GlyP phenyl 5-32 H, methyl GlyP GlyP methyl H, methyl GlyP methyl 5-33 H, methyl GlyP GlyP POMMA H, methyl GlyP POMMA 5-34 H, methyl GlyP ECHE GlyP H, methyl ECHE GlyP 5-35 H, methyl GlyP phenyl GlyP H, methyl phenyl GlyP 5-36 H, methyl GlyP methyl GlyP H, methyl methyl GlyP 5-37 H, methyl GlyP POMMA GlyP H, methyl POMMA GlyP 5-35 H, methyl POMMA POMMA ECHE H, methyl POMMA ECHE 5-39 H, methyl POMMA POMMA phenyl H, methyl POMMA phenyl 5-40 H, methyl POMMA POMMA methyl H, methyl POMMA methyl 5-41 H, methyl POMMA POMMA GlyP H, methyl POMMA GlyP 5-42 H, methyl POMMA ECHE POMMA H, methyl ECHE POMMA 5-43 H, methyl POMMA phenyl POMMA H, methyl phenyl POMMA 5-44 H, methyl POMMA methyl POMMA H, methyl methyl POMMA 5-45 H, methyl POMMA GlyP POMMA H, methyl GlyP POMMA

No R5 R6 R7 R8 R10 Y of R X of R 6-1 H, methyl ECHE ECHE ECHE Alkyl thiol, methyl ECHE ECHE 6-2 H, ethyl phenyl phenyl phenyl H, methyl phenyl phenyl 6-3 H, acetyltyl alkyl thiol methyl methyl H, CF ₃ methyl methyl 6-4 vinyl, methyl POMMA dodecyl GlyP H, methyl EGCDX GlyP 6-5 H, methyl POMMA alkyl thiol POMMA C ₈ F ₁₃ ,methyl POMMA POMMA 6-6 H, F ECHE phenyl phenyl H, profile ECHE phenyl 6-7 CF ₃ ,methyl ECHE octyl methyl F, methyl ECHE methyl 6-8 H, methyl F aminopropyl GlyP H, methyl ECHE GlyP 6-9 H, CF ₃ aminopropyl POMMA POMMA H, ethyl ECHE POMMA 6-10 H, methyl phenyl alkyl thiol ECHE H, acetyltyl phenyl ECHE 6-11 aryl, methyl alkyl thiol methyl ECHE vinyl, methyl methyl ECHE 6-12 H, methacrylic phenyl GlyP ECHE H, methyl GlyP ECHE 6-13 H, methyl octyl POMMA ECHE H, F POMMA ECHE 6-14 H, octyl methyl ECHE ECHE CF ₃ ,methyl phenyl ECHE 6-15 H, methyl octyl alkyl thiol methyl H, methyl phenyl methyl 6-16 H, methyl octyl GlyP EGDCX H, octyl phenyl EGDCX 6-17 Alkyl thiol, methyl methyl POMMA POMMA H, acetyltyl phenyl POMMA 6-18 H, methyl GlyP GlyP phenyl vinyl, methyl ECHE phenyl 6-19 H, CF ₃ POMMA POMMA phenyl H, methyl methyl phenyl 6-20 H, methyl ECHE aminopropyl phenyl H, F GlyP phenyl 6-21 C ₈ F ₁₃ ,methyl alkyl thiol phenyl phenyl CF ₃ ,methyl POMMA phenyl 6-22 H, profile GlyP GlyP ECHE H, methyl methyl ECHE 6-23 F, methyl POMMA POMMA phenyl H, CF ₃ methyl phenyl 6-24 H, methyl ECHE aminopropyl GlyP H, methyl methyl GlyP 6-25 H, ethyl aminopropyl phenyl POMMA aryl, methyl methyl POMMA 6-26 H, acetyltyl methyl octyl methyl H, methacrylic ECHE methyl 6-27 vinyl, methyl POMMA POMMA methyl H, methyl phenyl methyl 6-28 H, methyl methyl methyl methyl H, octyl GlyP methyl 6-29 H, F dodecyl GlyP methyl H, methyl POMMA methyl 6-30 CF ₃ ,methyl alkyl thiol octyl ECHE vinyl, methyl GlyP ECHE 6-31 H, methyl phenyl POMMA phenyl H, methyl GlyP phenyl 6-32 H, octyl octyl methyl methyl H, F GlyP methyl 6-33 H, methyl aminopropyl GlyP POMMA CF ₃ ,methyl GlyP POMMA 6-34 H, methyl POMMA hexyl GlyP H, methyl ECHE GlyP 6-35 H, acetyltyl alkyl thiol ECHE GlyP H, methyl phenyl GlyP 6-36 vinyl, methyl methyl hexyl GlyP H, methyl methyl GlyP 6-37 H, methyl GlyP GlyP GlyP H, methyl POMMA GlyP 6-38 H, F POMMA POMMA ECHE H, methyl POMMA ECHE 6-39 CF ₃ ,methyl ECHE aminopropyl phenyl H, methyl POMMA phenyl 6-40 H, methyl alkyl thiol phenyl methyl H, methyl POMMA methyl 6-41 vinyl, methyl GlyP GlyP GlyP H, methyl POMMA GlyP 6-42 H, methyl POMMA POMMA POMMA H, methyl ECHE POMMA 6-43 H, F ECHE aminopropyl POMMA H, methyl phenyl POMMA 6-44 CF ₃ ,methyl aminopropyl phenyl POMMA H, methyl methyl POMMA 6-45 H, methyl POMMA GlyP POMMA H, methyl GlyP POMMA

The degree of condensation of the silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability and obtain wide applicability. That is, the content of the alkoxy group bonded to Si at the ends and the center can be controlled from 50% to 0.01% of the total polymer bonding group.

In addition, the weight average molecular weight of the silsesquioxane composite polymer in the present invention may be 1,000 to 1,000,000, preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. In this case, the processability and physical properties of silsesquioxane can be improved at the same time.

The silsesquioxane composite polymer of the present invention can be prepared by continuously controlling basicity and acidity using a basic catalyst and an acid catalyst in one reactor, and one of the following manufacturing methods can be used.

Method for producing a silsesquioxane composite polymer represented by Formula 1

구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함한다. 제조된 실세스퀴옥산 복합 고분자는 하기 화학식 1-1과 같은 구조를 가진다.A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following Chemical Formula 4; and in Formula 4 after the first step

a second step of adding an acid catalyst to the reactor to adjust the reaction solution to acidity to introduce the structure, then adding an organosilane compound and stirring; and a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic. The prepared silsesquioxane composite polymer has a structure as shown in Formula 1-1 below.

[Formula 4]

[Formula 1-1]

In the above formula, R, R ¹ , R ² , R ⁶ , R ⁷ , Y, a and d are as defined in Formulas 1 to 3.

Method for producing a silsesquioxane composite polymer represented by Formula 2

및

구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 제3단계 반응을 거쳐, 단독으로 생성되는 부산물인 cage 구조를 재결정으로 제거하여주는 정제단계를 진행하면 제조된 복합 고분자 하기 화학식 2-1과 같은 구조를 가진다.A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following Chemical Formula 4; and in Formula 4 after the first step

and

a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidity in order to introduce the structure, then adding an excess of an organosilane compound and stirring; and a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; And through the third step reaction, when the purification step of removing the cage structure, which is a by-product, by recrystallization is performed, the prepared composite polymer has a structure as shown in Chemical Formula 2-1 below.

[Formula 2-1]

In the above formula, R, R ³ , R ⁴ , R ⁶ , R ⁷ , D, Y, a and d are as defined in Formulas 1 to 3.

Method for producing a silsesquioxane composite polymer represented by the formula (3)

구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에

구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함한다. 제조된 실세스퀴옥산 복합 고분자는 하기 화학식 3-1과 같은 구조를 가진다. A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following Chemical Formula 4; and in Formula 4 after the first step

a second step of adding an acid catalyst to the reactor to adjust the reaction solution to acidity to introduce the structure, then adding an organosilane compound and stirring; and a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and at the end of the composite polymer after the third step.

In order to introduce the structure, an acid catalyst is introduced into the reactor to convert the reaction solution into an acidic atmosphere, and a fourth step of mixing and stirring the organosilane compound is included. The prepared silsesquioxane composite polymer has a structure as shown in Formula 3-1 below.

[Formula 3-1]

In the above formula, R, R ⁵ , R ⁶ , R ⁷ , R ⁸ , Y, X, a, d and e are as defined in Formulas 1 to 3.

In the method for producing the silsesquioxane complex polymer, a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and this is neutralized and acidified with an acidic catalyst to induce re-hydrolysis, and again two or more basic catalysts are used. Acidity and basicity can be continuously adjusted in one reactor by carrying out the condensation in a basic manner using a mixed catalyst of

In this case, the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal-based basic catalyst and an amine-based basic catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Preferably, the amine-based basic catalyst is tetramethylammonium hydroxide (TMAH), and the metal-based basic catalyst is potassium hydroxide (KOH) or sodium bicarbonate (NaHCO ₃ ). The content of each component in the mixed catalyst may be arbitrarily adjusted in a ratio of preferably 10 to 90: 10 to 90 parts by weight of the amine-based basic catalyst and the metal-based basic catalyst. If it is within the above range, it is possible to minimize the reactivity of the functional group with the catalyst during hydrolysis, and this has the advantage that defects of organic functional groups such as Si-OH or Si-alkoxy are significantly reduced, so that the degree of condensation can be freely controlled. In addition, the acid catalyst may be used without limitation as long as it is an acidic material commonly used in the art, for example, a general acidic material such as HCl, H ₂ SO ₄ , HNO ₃ , CH ₃ COOH may be used, In addition, organic acidic substances such as latic acid, tartaric acid, maleic acid, and citric acid can be applied.

In the method for producing the silsesquioxane composite polymer of the present invention, the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Alcohols such as cellosolve, ketones such as lactate, acetone, and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- In addition to polar solvents such as methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acro Various solvents such as nitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, and benzyl alcohol can be used.

In addition, as the organosilane-based compound, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , the silsesquioxane complex polymer of the present invention, of Formulas 1 to 3, An organic silane containing R ⁹ , or R ¹⁰ may be used, and in particular, an organic silane compound containing a phenyl group or an amino group, which has the effect of improving the non-swelling property by increasing the chemical resistance of the silsesquioxane composite polymer, or a composite polymer An organic silane compound containing an epoxy group or a (meth)acryl group, which has the effect of improving the mechanical strength and hardness of the cured layer by increasing the curing density of the cured layer, may be used.

Specific examples of the organosilane compound include (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3 -glycidoxypropyl) dimethylethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrime oxysilane, dimethyltetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, Among these, it can also be used individually by 1 type or in combination of 2 or more types. It is more preferable to use a mixture of two or more for the physical properties of the final composition.

Preferably, the pH of the reaction solution in the first step of the present invention is preferably 9 to 11.5, the pH of the reaction solution in the second step is preferably 2 to 4, and the pH of the reaction solution in the third step is 8 to 11.5, and the pH of the reaction solution in the fourth step of preparing Formula 3 is preferably 1.5 to 4. When it is within the above range, the yield of the prepared silsesquioxane composite polymer may be high, and mechanical properties of the prepared silsesquioxane composite polymer may be improved.

The present invention also provides a coating composition comprising a silsesquioxane composite polymer represented by any one of Formulas 1 to 3. When the silsesquioxane composite polymer is liquid, the coating composition can be coated alone as a solvent-free type, and when the silsesquioxane composite polymer is in a solid state, it may be configured by including an organic solvent. In addition, the coating composition may further include an initiator or a curing agent.

Preferably, the coating composition includes a silsesquioxane complex polymer represented by any one of Chemical Formulas 1 to 3, an organic solvent commonly used in the art that is compatible with the complex polymer, and an initiator, and optionally a curing agent , plasticizers, sunscreens, and other functional additives may be additionally included to improve curability, heat resistance, UV protection, and plasticizing effect.

In the coating composition of the present invention, the silsesquioxane composite polymer is preferably included in an amount of at least 5 parts by weight or more, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the coating composition. It is preferably included in a negative amount. When within the above range, the mechanical properties of the cured film of the coating composition may be further improved.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and cellosolve; ketones such as lactate, acetone, and methyl (isobutyl) ethyl ketone; glycols such as ethylene glycol; Furan-based solvents such as tetrahydrofuran, polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Various solvents such as dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrynitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, and benzyl alcohol may be used, but are not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the complex polymer, initiator, curing agent, and optionally added additives.

In addition, in the coating composition of the present invention, the initiator or curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.

As a specific example, when an organic type capable of post-curing, such as an unsaturated hydrocarbon, a thiol type, an epoxy type, an amine type, an isocyanate type, etc. is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change by heat or light can be achieved within the polymer itself, but preferably, the curing process can be achieved by diluting it in the organic solvent as described above.

In the present invention, various initiators can be used for curing and post-reaction of the composite polymer, and the initiator is preferably included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition. Post-transmittance and coating stability can be satisfied at the same time.

In addition, when an unsaturated hydrocarbon is introduced into the organic functional group, a radical initiator may be used, and the radical initiator includes trichloro acetophenone, diethoxy acetophenone, 1-phenyl-2-hydro Roxy-2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl)-2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide), camphor quinone, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl- Photoradical initiators such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, and 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t- Butylparoxy maleic acid, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, N-butyl-4, Thermal radical initiators such as 4'-di(t-butylperoxy)valerate and various mixtures thereof may be used.

In addition, when an epoxy etc. are contained in the said organic functional group, as a photoinitiator (cation), sulfonium types, such as triphenylsulfonium, diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium, or bis (dode iodonium such as silphenyl) iodonium, diazonium such as phenyldiazonium, ammonium such as 1-benzyl-2-cyanopyrininium and 1-(naphthylmethyl)-2-cyanopridinium, (4- Methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate iodonium, bis(4-t-butylphenyl)hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafluoroborate, tri-p-toylsulfonium hexafluorophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- A combination of Fe cations such as cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe and [BQ ₄ ] ^-onium salts such as BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- may be used. (Wherein, Q is a phenyl group substituted with at least two or more fluorine or trifluoromethyl groups).

In addition, as a cationic initiator acting by heat, a cationic or protonic acid catalyst such as triflate, boron trifluoride ether complex, boron trifluoride, etc., various onium salts such as ammonium salt, phosphonium salt and sulfonium salt, and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide, etc. can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above Do.

In addition, depending on the type of the organic functional group, amine curing agents ethylenediamine, triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane, dipropylenetriamine, 3-(2-aminoethyl)amino-propyl amine, N,N'-bis(3-aminopropyl)-ethylenediamine, 4,9-dioxadothecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, Hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis(4-animocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, etc. can be used. .

In addition, as a curing accelerator for accelerating the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, and 2-methylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, imidazole compounds such as 1-methylimidazole, 1, 5-diazabicyclo[4.3.0]nonene-5,1,8-diazabicyclo[5.4.0]undecene-7, triphenylphosphine, diphenyl(p-triyl)phosphine, tris(alkylphenyl) ) Phosphine, tris (alkoxyphenyl) phosphine, ethyl triphenyl phosphonium phosphate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate, tetrabutyl phosphonium hydrogen difluoride, tetrabutyl phosphonium dihydrogen tri Fluorine or the like may also be used.

In addition, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetra Acid anhydride curing agents such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2,4-diethyl glutaric anhydride can also be widely used.

The curing agent is preferably included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition.

In the present invention, additives such as UV absorbers, antioxidants, defoamers, leveling agents, water repellents, flame retardants, and adhesion improvers are additionally included for the purpose of improving hardness, strength, durability, moldability, etc. through the curing process or post-reaction. can These additives are not particularly limited in their use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, physical properties such as flexibility, light transmittance, heat resistance, hardness, and strength. Preferably, the additives are each independently included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition.

Additives usable in the present invention include polyether-modified polydimethylsiloxane (for example, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, manufactured by BYK). BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), Polyether modified hydroxyfunctional poly-dimethyl-siloxane (for example, BYK- 308, BYK-373, etc.), polymethylalkylpolysiloxane (eg, BYK-077, BYK-085, etc.), polyether modified methylalkylpolysiloxane (eg, BYK-320, BYK-325, etc.), polyester poly-methyl-alkyl-siloxane (Polyester modified poly-methyl-alkyl-siloxane, e.g., BYK-315, etc.), Aralkyl modified methylalkyl polysiloxane, e.g. , BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, for example, BYK-370, etc.), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, For example, BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy polydimethylsiloxane (Polyeher-polyester modified hydroxy functional polydimethylsiloxane, for example, BYK-375, etc.), polyether polydimethylsiloxane acid (Poly) ether modified dimethylpolysiloxane, for example, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), non-ionic acrylic copolymer, for example, BYK -380, etc.), ionic polyacrylic copolymer (eg, BYK-381, etc.), polyacrylate (eg, BYK-353, BYK-356, BYK-354, BYK-355) , BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352, etc.), polymethacrylate-based (Polymethacrylate, for example, BYK-390, etc.), polyether acrylic polydimethylsiloxane-based (Polyether modified acryl functional polydimethylsiloxane, for example, BYK-UV 3500, BYK-UV3530, etc.), polyether siloxane-based (Polyether modified siloxane, for example, BYK-347, etc.), alcohol alkoxylates, such as For example, BYK-DYNWET 800, etc.), acrylate-based (Acrylate, such as BYK-392, etc.), hydroxy silicone polyacrylate (OH-functional), such as BYK-Silclean 3700 etc.) and the like.

The coating composition of the present invention can be applied to various materials to improve the high surface hardness, mechanical strength and heat resistance of the material. The thickness of the coating may be arbitrarily controlled, and may be 0.01 to 500 um, preferably 0.1 to 300 um, more preferably 1 to 100 um. For example, the material may be metal, ceramic, plastic, wood, paper, glass or fiber, and a specific article coated on a more specific material may be a protective film for a mobile phone or display.

In the present invention, the method for coating the coating composition is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, among known methods. It goes without saying that those skilled in the art can arbitrarily select and apply it.

Since the silsesquioxane composite polymer prepared according to the present invention includes a linear silsesquioxane chain and a cage-type silsesquioxane chain composed of a linear silsesquioxane polymer, the ease of processing of the linear polymer and the crystalline silsesquioxane chain Since it can have excellent physical properties of , and it is easy to cure through the organic functional group included in the structure, it can be widely applied to the overall industry to which the organic-inorganic hybrid polymer is to be applied. In addition, since it has the excellent optical properties, physical properties, and heat resistance properties of silicone, it can be widely used as a main material, additive, or various coating materials.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples.

Example 1 : Synthesis of silsesquioxane A-D structure composite polymer

As for the synthesis step, continuous hydrolysis and condensation were carried out step by step.

[Example 1-a] Preparation of catalyst

For basicity control, catalyst 1a was prepared by mixing 10 wt% potassium hydroxide (KOH) aqueous solution with 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution.

[Example 1-b] Synthesis of linear silsesquioxane structure

5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, and 1 part by weight of the catalyst prepared in Example 1-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and after stirring at room temperature for 1 hour, 2 20 parts by weight of -(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and then 15 parts by weight of tetrahydrolurane was added dropwise, followed by further stirring for 5 hours. After removing the catalyst and impurities by collecting the mixed solution during stirring, washing twice, and filtering, the SI-OH functional group generated at the terminal group was confirmed through IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that silsesquioxane having a linear structure such as the structure of Chemical Formula 4 had a molecular weight equivalent to 8,000 styrene.

[Example 1-c] Creation of a continuous cage structure

To the mixed solution of Example 1-b, 5 parts by weight of 0.36 wt% HCl aqueous solution was added dropwise very slowly, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 °C for 30 minutes. Then, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at once to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a precursor of the D structure in which the alkoxy is open is formed separately from the linear polymer. After taking a small sample and analyzing it with H-NMR and IR to check the residual ratio of methoxy, when the residual ratio is 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution is slowly added dropwise to adjust the pH to acid. gave. Then, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that a cage-type polymer was produced in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR. As a result, the analysis peak of the structure introduced using a phenyl group appeared as two sharp peaks, and the AD polymer as in Formula 1 was 50% It could be confirmed that the above was manufactured. In addition, the molecular weight in terms of styrene was measured to be 11,000. ²⁹ Si-NMR (CDCl ₃ ) δ -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, a silsesquioxane composite polymer was prepared by applying the monomers described in Table 7 below. At this time, the manufacturing method was equally applied to the method used in Examples 1-b and 1-c.

practice
method
1-b method
Applicable monomer 1-c method
Applicable monomer Molecular Weight
(Mw) precursor introduction of cage One ECHETMS PTMDS PTMS 11,000 1-1 PTMS PTMDS PTMS 8,000 1-2 MTMS MTMDS MTMS 48,000 1-3 GPTMS GPTMDS GPTMS 25,000 1-4 MAPTMS MAPTMDS MAPTMS 21,000 1-5 ECHETMS ECHETMDS ECHETMS 3,000 1-6 ECHETMS MTMDS MTMS 9,000 1-7 ECHETMS GPTMDS GPTMS 11,000 1-8 ECHETMS MAPTMDS MAPTMS 18,000 1-9 PTMS ECHETMDS ECHETMS 36,000 1-10 PTMS MTMDS MTMS 120,000 1-11 PTMS GPTMDS GPTMS 11,000 1-12 PTMS MAPTMDS MAPTMS 110,000 1-13 MTMS ECHETMDS ECHETMS 18,000 1-14 MTMS PTMDS PTMS 5,000 1-15 MTMS GPTMDS GPTMS 80,000 1-16 MTMS MAPTMDS MAPTMS 35,000 1-17 GPTMS ECHETMDS ECHETMS 7,000 1-18 GPTMS PTMDS PTMS 120,000 1-19 GPTMS MTMDS MTMS 100,000 1-20 GPTMS MAPTMDS MAPTMS 4,000 1-21 MAPTMS ECHETMDS ECHETMS 35,000 1-22 MAPTMS PTMDS PTMS 2,800 1-23 MAPTMS MTMDS MTMS 8,000 1-24 MAPTMS GPTMDS GPTMS 180,000

In Table 7 above, ECHETMS is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy)propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, ECHETMDS is Di(epoxycyclohexyethyl) tetramethoxy disiloxane, ECHETMDS is Di(epoxycyclohexyethyl) tetramethoxy disiloxane ) tetramethoxy disiloxane, MAPTMDS stands for Di(methacryloyloxy)propy, PTMDS stands for Di(phenyl)tetramethoxy disiloxane, and MTMDS stands for Di(Methyl)tetramethoxy disiloxane.

Example 2 : Synthesis of silsesquioxane D-A-D structure composite polymer

The following examples were used to prepare a composite polymer having a DAD structure. For the preparation of the catalyst and the linear structure, the methods of Examples 1-a and 1-b were used in the same manner, and then, the preparation was carried out in the following manner in order to generate a continuous DAD structure.

[Example 2-a] Creation of an excess of continuous cage structure

To the mixed solution of Example 1-b, 5 parts by weight of 0.36 wt% HCl aqueous solution was added dropwise very slowly, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 °C for 30 minutes. After that, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at a time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state to adjust the pH of the mixed solution. At this time, a precursor of the D structure in which the alkoxy is open is formed separately from the linear polymer. After taking a small sample and analyzing it with H-NMR and IR to check the residual ratio of methoxy, when the residual ratio is 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution is slowly added dropwise to adjust the pH to acid. gave. Then, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that a cage-type polymer was produced in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR. As a result, the analysis peaks of the structure introduced using a phenyl group appeared as two sharp shapes, indicating that an AD polymer as in Formula 1 was prepared without separately remaining by-products. could check In addition, the molecular weight in terms of styrene was measured to be 14,000. In addition, unlike the AD structure in the Si-NMR analysis, the peak near -68ppm that was seen at the end of the A structure disappeared, confirming that the end of the A structure was all converted to the D structure to form a DAD structure. ²⁹ Si-NMR (CDCl ₃ ) δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, a silsesquioxane composite polymer was prepared by applying the monomers described in Table 8 below. At this time, the manufacturing method was equally applied to the method used in Example 2.

practice
method 1-b method
Applicable monomer 2-a method
Applicable monomer Molecular Weight
(Mw) precursor introduction of cage 2 ECHETMS PTMDS PTMS 14,000 2-1 PTMS PTMDS PTMS 9,000 2-2 MTMS MTMDS MTMS 52,000 2-3 GPTMS GPTMDS GPTMS 30,000 2-4 MAPTMS MAPTMDS MAPTMS 24,000 2-5 ECHETMS ECHETMDS ECHETMS 6,000 2-6 ECHETMS MTMDS MTMS 12,000 2-7 ECHETMS GPTMDS GPTMS 13,000 2-8 ECHETMS MAPTMDS MAPTMS 21,000 2-9 PTMS ECHETMDS ECHETMS 38,000 2-10 PTMS MTMDS MTMS 150,000 2-11 PTMS GPTMDS GPTMS 18,000 2-12 PTMS MAPTMDS MAPTMS 123,000 2-13 MTMS ECHETMDS ECHETMS 23,000 2-14 MTMS PTMDS PTMS 9,000 2-15 MTMS GPTMDS GPTMS 91,000 2-16 MTMS MAPTMDS MAPTMS 41,000 2-17 GPTMS ECHETMDS ECHETMS 12,000 2-18 GPTMS PTMDS PTMS 131,000 2-19 GPTMS MTMDS MTMS 110,000 2-20 GPTMS MAPTMDS MAPTMS 6,000 2-21 MAPTMS ECHETMDS ECHETMS 38,000 2-22 MAPTMS PTMDS PTMS 5,000 2-23 MAPTMS MTMDS MTMS 12,000 2-24 MAPTMS GPTMDS GPTMS 192,000

In Table 8, ECHETMS is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy)propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, ECHETMDS is Di(epoxycyclohexyethyl) tetramethoxy disiloxane, ECHETMDS is Di(epoxycyclohexyethyl) tetramethoxy disiloxane ) tetramethoxy disiloxane, MAPTMDS stands for Di(methacryloyloxy)propy, PTMDS stands for Di(phenyl)tetramethoxy disiloxane, and MTMDS stands for Di(Methyl)tetramethoxy disiloxane.

Example 3 : Synthesis of silsesquioxane E-A-D structure composite polymer

The following examples were used to prepare EAD-structured composite polymers. The catalyst and the linear structure were prepared in the same manner as in Example 1, and then the EAD structure was prepared by the following method.

[Example 3-a] Generation of chain terminal E structure

To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride was added dropwise without separate purification, and 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted to have acidity, and the pH was adjusted to 30 at a temperature of 4°C. stirred for minutes. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, the parts that have not yet been hydrolyzed in the molecular structure are easily converted into hydrolysates in the acidic aqueous solution layer separated from the solvent, and are condensed with the generated separate reactants in the organic solvent layer to introduce E into the terminal unit. After stirring for 5 hours, the stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

[Example 3-b] Incorporation of cage into end E structure

After the organic layer obtained in Example 3-a was prepared without further purification, the ends were converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in which the reaction is in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state to adjust the pH of the mixed solution. At this time, a cage-type polymer is introduced at the end of the E structure, and the reaction proceeds continuously in the reactor to form a polymer as shown in Chemical Formula 3. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

[Example 3-c] Removal of by-products through precipitation and recrystallization, obtaining the result

After obtaining the mixture in which the reaction was completed in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed under reduced pressure. Thereafter, by precipitation twice in methanol, unreacted monomers were removed, and 30 parts by weight was dissolved in a solvent in which tetrahydrofuran and aqueous solution were mixed at a weight ratio of 9.5:0.5 and stored at a temperature of -20 °C for 2 days. This is to promote recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Formula 3 was obtained along with various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, and in particular, the result of Chemical Formula 3 is as follows.

²⁹ Si-NMR (CDCl ₃ ) δ -68.2, -71.8 (sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad)

In addition, a silsesquioxane composite polymer was prepared by applying the monomers described in Table 9 below. At this time, the manufacturing method was equally applied to the method used in Example 3.

practice
method 1-b method
Applicable monomer 1-c method
Applicable monomer 3-a
method
Applicable monomer 3-b
method
Applicable monomer Mw precursor introduction of cage 3 ECHETMS PTMDS PTMS MTMDS MAPTMS 17,000 3-1 ECHETMS ECHETMDS ECHETMS ECHETMDS ECHETMS 12,000 3-2 PTMS PTMDS PTMS PTMDS PTMS 18,000 3-3 MTMS MTMDS MTMS MTMDS MTMS 59,000 3-4 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 41,000 3-5 MAPTMS MAPTMDS MAPTMS MAPTMDS MAPTMS 31,000 3-6 ECHETMS ECHETMDS ECHETMS PTMDS PTMS 16,000 3-7 ECHETMS ECHETMDS ECHETMS MTMDS MTMS 12,000 3-8 ECHETMS ECHETMDS ECHETMS GPTMDS GPTMS 16,000 3-9 ECHETMS ECHETMDS ECHETMS MAPTMDS MAPTMS 92,000 3-10 ECHETMS PTMDS PTMS ECHETMDS ECHETMS 25,000 3-11 ECHETMS MTMDS MTMS ECHETMDS ECHETMS 38,000 3-12 ECHETMS GPTMDS GPTMS ECHETMDS ECHETMS 56,000 3-13 ECHETMS MAPTMDS MAPTMS ECHETMDS ECHETMS 97,000 3-14 PTMS PTMDS PTMS ECHETMDS ECHETMS 24,000 3-15 PTMS PTMDS PTMS MTMDS MTMS 31,000 3-16 PTMS PTMDS PTMS ECHETMDS ECHETMS 21,000 3-17 PTMS PTMDS PTMS MAPTMDS MAPTMS 64,000 3-18 PTMS ECHETMDS ECHETMS PTMDS PTMS 120,000 3-19 PTMS MTMDS MTMS PTMDS PTMS 210,000 3-20 PTMS GPTMDS GPTMS PTMDS PTMS 23,000 3-21 PTMS MAPTMDS MAPTMS PTMDS PTMS 160,000 3-22 MTMS MTMDS MTMS ECHETMDS ECHETMS 63,000 3-23 MTMS MTMDS MTMS PTMDS PTMS 52,000 3-24 MTMS MTMDS MTMS GPTMDS GPTMS 73,000 3-25 MTMS MTMDS MTMS MAPTMDS MAPTMS 98,000 3-26 MTMS ECHETMDS ECHETMS MTMDS MTMS 41,000 3-27 MTMS PTMDS PTMS MTMDS MTMS 15,000 3-28 MTMS GPTMDS GPTMS MTMDS MTMS 110,000 3-29 MTMS MAPTMDS MAPTMS MTMDS MTMS 45,000 3-30 GPTMS GPTMDS GPTMS ECHETMDS ECHETMS 35,000 3-31 GPTMS GPTMDS GPTMS PTMDS PTMS 33,000 3-32 GPTMS GPTMDS GPTMS MTMDS MTMS 48,000 3-33 GPTMS GPTMDS GPTMS MAPTMDS MAPTMS 29,000 3-34 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 19,000 3-35 GPTMS PTMDS PTMS GPTMDS GPTMS 156,000 3-36 GPTMS MTMDS MTMS GPTMDS GPTMS 116,000 3-37 GPTMS MAPTMDS MAPTMS GPTMDS GPTMS 12,000 3-38 MAPTMS MAPTMDS MAPTMS ECHETMDS ECHETMS 31,000 3-39 MAPTMS MAPTMDS MAPTMS PTMDS PTMS 28,000 3-40 MAPTMS MAPTMDS MAPTMS MTMDS MTMS 35,000 3-41 MAPTMS MAPTMDS MAPTMS GPTMDS GPTMS 31,000 3-42 MAPTMS ECHETMDS ECHETMS MAPTMDS MAPTMS 57,000 3-43 MAPTMS PTMDS PTMS MAPTMDS MAPTMS 9,000 3-44 MAPTMS MTMDS MTMS MAPTMDS MAPTMS 19,000 3-45 MAPTMS GPTMDS GPTMS MAPTMDS MAPTMS 213,000

In Table 9, ECHETMS is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy)propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, ECHETMDS is Di(epoxycyclohexyethyl) tetramethoxy disiloxane ) tetramethoxy disiloxane, MAPTMDS stands for Di(methacryloyloxy)propy, PTMDS stands for Di(phenyl)tetramethoxy disiloxane, and MTMDS stands for Di(Methyl)tetramethoxy disiloxane.

Example 4 : Manufacturing and process of coating composition using silsesquioxane complex polymer

Using the silsesquioxane composite polymer obtained in Examples 1, 2 and 3, a curing process was induced by itself or a coating composition was prepared.

[Example 4-1] Preparation of photocurable coating composition

A coating composition of 100 g was prepared by dissolving 20 g of the silsesquioxane complex polymer represented by Formula 1 prepared in Example 1 at 20 wt % in methyl ethyl ketone. Then, 5 parts by weight of diphenyliodonium and 1 part by weight of BYK-347 were added to 100 parts by weight of the coating composition and stirred for 10 minutes to prepare a photocurable coating composition.

[Example 4-2] Curing of photocurable coating composition

The coating composition prepared in Example 4-1 was applied to SKC-SG00L 250 um film, which is SKC's PET film, and Mayer coating was performed by dividing the No. 30-50 rod into 5 units. Thereafter, the solvent was removed at a temperature of 80° C. for 10 minutes, and UV was irradiated for 10 seconds in a 100 mW/cm ² lamp using UV equipment to obtain a result.

[Example 4-3] Preparation of thermosetting coating composition

100 g of a coating composition was prepared by dissolving 50 g of the silsesquioxane composite polymer represented by Chemical Formula 3-1 prepared in Example at 50 wt % in methyl ethyl ketone. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition and stirred for 10 minutes to prepare a thermosetting coating composition.

[Example 4-4] Curing of thermosetting coating composition

The coating composition prepared in Example 4-3 was applied to SKC-SG00L 250 um film, which is a PET film by SKC, and Mayer coating was performed by dividing No. 30 to 50 rods into 5 units. After coating, the result was obtained after curing for 10 minutes in a drying oven at 80 °C.

[Example 4-5] Self-curing of Chemical Formulas 1, 2 and 3 obtained through Examples

The results obtained in Examples 1, 2 and 3 were cured through heat without a separate composition. The SKC-SG00L 250 um film, which is SKC's PET film, was divided into 5 units of No. 30 ~ 50 rods and subjected to Mayer coating, and the result was obtained after curing in a drying oven at 100 ° C for 2 hours. did

[Experimental Example 1]

The weight average molecular weight and molecular weight distribution of the silsesquioxane resin prepared in Example 1 was measured using a JASCO PU-2080 plus SEC system equipped with RI-2031 plus refractive index detector and UV-2075 plus UV detector (254detection wavelength). and measured. THF was used at a flow rate of 1 at 40 °C, and samples were separated through four columns (Shodex-GPC KF-802, KF-803, KF-804 and KF-805). As a result, it was confirmed by SEC analysis that the obtained silsesquioxane had a weight average molecular weight of 12,000 and a molecular weight distribution of 1.8.

[Experimental Example 2]

IR was measured using the ATR mode of the Perkin-Elmer FT-IR system Spectrum-GX. As a result of FT-IR analysis, a broad bimodal (continuous double shape) absorption peak appeared at 950 to 1200 cm ^-1 in the structure taken in a small amount in the process of Example 1-b, which is a vertical ( -Si-O-Si-R) and the horizontal (-Si-O-Si-) direction are derived from the stretching vibration of the siloxane bond. Then, as a result of analyzing the extract of the structure obtained in 1-c, it was confirmed that the peak appearing at 1200 cm ^-1 was further grown, confirming the substitution of the cage-type structure. When this was analyzed in conjunction with the GPC analysis results analyzed in Experimental Example 1, despite the growth of the cage-shaped characteristic peak, the cage type with a low actual molecular weight (generally about 1,000 to 5,000 molecular weight) was not observed alone. It was confirmed that it was introduced in the expected structure in the chain.

[Experimental Example 3]

The thermal stability of the structures prepared in Examples 1, 2 and 3 was confirmed using a thermal gravimetric analyzer (TGA), and in particular, the composite polymer obtained in Formula 3-1 was measured. Measurements were made via TGA at 10 °C/min scan rate of 50-800 °C under nitrogen. As a result of the measurement, it was confirmed that the amount of decomposition of Si-OH and Si-OR, which was decomposed between 100-200 °C, was significantly reduced by replacing the cage-type structure at the end.

[Experimental Example 4]

PC (I-Component's Glastic polycarbonate product) SKC's PET and PMMA (COPAN's OAS-800 product) Using the polymer resins shown in Tables 7 to 9 on a transparent substrate, the coating composition was prepared in the same manner as in Example 4. After coating and curing, the surface properties were measured. The following experimental results are results using the polymer resin prepared in Example 3, and although not described in the table, the coating compositions using the polymer resins described in Tables 7 to 9 showed comparable results to the polymer resin of Example 3.

- Surface hardness measurement : In general, the pencil hardness method (JIS 5600-5-4) is generally evaluated with a 500 g load. Under a harsher condition, a 1 kgf load, the pencil is horizontally 3 mm at a speed of 0.5 mm per second at a 45 degree angle to the coated surface. It moved and scraped the coating film and evaluated it as a scratch mark. If no traces of scratches are confirmed more than twice in 5 experiments, select a pencil of higher hardness, and if there are more than two scratches, select a pencil, and the pencil hardness one level lower than the pencil hardness is evaluated as the pencil hardness of the coating film did As a result of the evaluation, all glass-level 9H hardness was confirmed regardless of the substrate type at a coating thickness of 10 μm or more.

- Scratch test measurement: Steel wool #0000 is evaluated 400 times at 1 kgf The wear evaluation method by steel wool (JIS K5600-5-9) is 15 times by winding #0000 steel wool around the tip of a hammer weighing about 1 kg. The reciprocating test piece was rubbed and the haze value was measured, and the test piece, which is a more severe condition, was rubbed 400 times, and the haze was measured and visually evaluated with a microscope. It was confirmed that all coatings with a coating thickness of 5 μm or more had excellent resistance to scratches on the surface.

- Adhesion evaluation (JIS K5600-5-6): Scratch the coating film at intervals of 1-5 mm with a cutter blade and attach cellophane tape on it. Adhesiveness was judged by the number of falling pieces out of 100, and the results are shown in Table 10 below. The notation is "(Number that does not fall/100)" as the number that does not fall out of 100.

- Reliability evaluation : 85%, stored in a 85 ℃ reliability chamber for 240 hours and evaluated for bending characteristics. The warpage evaluation criteria were within ±0.1 mm before reliability evaluation, within ±0.3 mm after reliability evaluation, and the results of evaluation of bending characteristics after reliability storage were excellent in all substrates of PET, PC, and PMMA.

Evaluation items PET-0.2 PC PMMA before coating after coating before coating after coating before coating after coating coating thickness - 10 μm - 10 μm - 10 μm Surface hardness (1kg _f ) 2B 9H (5/5) 6B or less 9H (5/5) 2H 9H (5/5) adhesion - pass
(100/100) - pass
(100/100) - pass
(100/100) Transmittance (%) UV-vis-400nm 91.2 91.7 89.2 89.0 90.4 90.2 UV-vis-450nm 91.5 93.0 90.1 90.2 91.5 91.2 UV-vis-500nm 92.4 93.4 91.4 91.6 91.9 91.6 YI (ASTMD1925) -0.38 -0.19 -0.15 0.05 0.14 0.24 Scratch test
(Steel wool, 1 kg _f load,
400 times) Fail pass Fail pass Fail pass Haze (%) 0.15 0.14 0.15 0.11 0.05 0.03

As shown in Table 10, it can be confirmed that the coating composition of the present invention not only exhibits very excellent surface hardness and optical properties, but is also excellent in other physical properties.

Claims (21)

A silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
A is

and D is

and E is

is,
Y is each independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
each X is independently R ¹⁰ or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group or unsubstituted, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alke Nyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₃ ~ C ₄₀ heteroaryl group, C ₇ ~ C ₄₀ aralkyl group, C ₆ ~ C ₄₀ aryloxy group, or C ₆ ~ C ₄₀ aryl thiol group,
a and d are each independently an integer from 1 to 100,000,
e is 1 or 2,
n is each independently an integer from 1 to 20; According to claim 1,
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently an amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; phenyl group; isocyanate group; Deuterium, halogen, amine group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl group, or unsubstituted C ₁ ~ C ₄₀ alkyl group or C ₂ ~ C ₄₀ Silsesquioxane composite polymer, characterized in that it is an alkenyl group. According to claim 1,
a is 3 to 1000, and d is 1 to 500 silsesquioxane composite polymer. According to claim 1,
d is a silsesquioxane composite polymer, characterized in that 2 to 100. According to claim 1,
Silsesquioxane composite polymer, characterized in that the average of n values is 4 to 5. delete According to claim 1,
Linear silsesquioxane composite polymer, characterized in that the weight average molecular weight of the linear silsesquioxane composite polymer of Formula 1 is 1,000 to 1,000,000. A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following Chemical Formula 4; and in Formula 4 after the first step

a second step of adding an acid catalyst to the reactor to adjust the reaction solution to acidity to introduce the structure, then adding an organosilane compound and stirring; and a third step of performing a condensation reaction by converting the reaction solution to basic by adding a basic catalyst to the reactor after the second step. :
[Formula 4]

[Formula 1]

The A is

and D is

is,
Y is each independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
The R, R ¹ , R ² , R ⁶ , R ⁷ and R ⁹ are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group or unsubstituted, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alke Nyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₃ ~ C ₄₀ heteroaryl group, C ₇ ~ C ₄₀ aralkyl group, C ₆ ~ C ₄₀ aryloxy group, or C ₆ ~ C ₄₀ aryl thiol group,
Wherein a and d are each independently an integer of 1 to 100,000,
Each of n is independently an integer from 1 to 20. A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following Chemical Formula 4; and in Formula 4 after the first step

and

a second step of adding an organosilane compound to introduce the structure as shown in Chemical Formula 2, adjusting the reaction solution to acidity by adding an acid catalyst to the reactor, and then stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and a fourth step of removing the single cage-forming structure through recrystallization and filtering after the third step.
[Formula 4]

[Formula 2]

The A is

and D is

is,
Y is each independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
Wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁹ are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group or unsubstituted, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alke Nyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₃ ~ C ₄₀ heteroaryl group, C ₇ ~ C ₄₀ aralkyl group, C ₆ ~ C ₄₀ aryloxy group, or C ₆ ~ C ₄₀ aryl thiol group,
Wherein a and d are each independently an integer of 1 to 100,000,
Each of n is independently an integer from 1 to 20. A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following Chemical Formula 4; and in Formula 4 after the first step

a second step of adding an acid catalyst to the reactor to adjust the reaction solution to acidity to introduce the structure, then adding an organosilane compound and stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and at the end of the composite polymer after the third step.

In order to introduce the structure, an acid catalyst is introduced into the reactor to convert the reaction solution into an acidic atmosphere, and a fourth step of mixing and stirring an organosilane compound. manufacturing method;
[Formula 4]

[Formula 3]

The A is

and D is

and E is

ego,
Y is each independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
wherein each X is independently R ¹⁰ or [(SiO _3/2 R) _4+2n R], and at least one is [(SiO _3/2 R) _4+2n R],
Wherein R, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acryl group, thiol group, isocyanate group, nitrile group, nitro group or unsubstituted, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alke Nyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₃ ~ C ₄₀ heteroaryl group, C ₇ ~ C ₄₀ aralkyl group, C ₆ ~ C ₄₀ aryloxy group, or C ₆ ~ C ₄₀ aryl thiol group,
Wherein a and d are each independently an integer from 1 to 100,000,
wherein e is 1 or 2,
Each of n is independently an integer from 1 to 20. 9. The method of claim 8,
The basic catalyst added in any one of the first and third steps is a mixed catalyst of two or more basic catalysts,
The mixed catalyst is a method for producing a silsesquioxane composite polymer comprising a metal-based basic catalyst and an amine-based basic catalyst. 12. The method of claim 11,
The method for producing a silsesquioxane composite polymer, characterized in that the ratio of the amine-based basic catalyst to the metal-based basic catalyst is 10 to 90: 10 to 90 parts by weight. 10. The method of claim 9,
The basic catalyst added in any one of the first and third steps is a mixed catalyst of two or more basic catalysts,
The mixed catalyst is a method for producing a silsesquioxane composite polymer comprising a metal-based basic catalyst and an amine-based basic catalyst. 14. The method of claim 13,
The method for producing a silsesquioxane composite polymer, characterized in that the ratio of the amine-based basic catalyst to the metal-based basic catalyst is 10 to 90: 10 to 90 parts by weight. 11. The method of claim 10,
The basic catalyst added in any one of the first and third steps is a mixed catalyst of two or more basic catalysts,
The mixed catalyst is a method for producing a silsesquioxane composite polymer comprising a metal-based basic catalyst and an amine-based basic catalyst. 16. The method of claim 15,
The method for producing a silsesquioxane composite polymer, characterized in that the ratio of the amine-based basic catalyst to the metal-based basic catalyst is 10 to 90: 10 to 90 parts by weight. A coating composition comprising the silsesquioxane composite polymer according to claim 1 . 18. The method of claim 17,
The coating composition is a coating composition, characterized in that the solvent-free type. 18. The method of claim 17,
The silsesquioxane composite polymer according to claim 1;
initiator; and
organic solvents;
A coating composition comprising a. 20. The method of claim 19,
The coating composition, characterized in that the silsesquioxane composite polymer is 5 to 90 parts by weight based on 100 parts by weight of the coating composition. 20. The method of claim 19,
The coating composition is a coating composition, characterized in that it further comprises a curing agent, a plasticizer, or a sunscreen.