WO2015130143A1 - Silsesquioxane complex polymer and method for preparing same - Google Patents

Abstract

The present invention relates to a silsesquioxane complex polymer and a method for preparing same, and more specifically, to a silsesquioxane complex polymer of which processability and physical characteristics are maximized by including, in a single polymer, a silsesquioxane ladder chain and a cage-type silsesquioxane which have a specific structure.

Description

Silsesquioxane composite polymer and preparation method thereof

The present invention relates to a silsesquioxane composite polymer and a manufacturing method thereof, and more particularly, to a silsesquioxane composite in which various silsesquioxane structures are introduced into one silsesquioxane polymer to maximize processability and physical properties. It relates to a polymer.

Silsesquioxane is used for various purposes in various fields. In particular, several attempts have been made to improve processability and maximize mechanical and physical properties, and research and development continue to this day. However, the silsesquioxane polymers developed so far are still insufficient to satisfy both processability and mechanical and physical properties.

Cage silsesquioxane, for example, has been applied to various aspects by showing physical properties that siloxane bonds can express. However, the cage silsesquioxane is a crystalline structure in itself and has a limited solubility in solution processing. As a result of applying the topographical structure, molecular units such as recrystallization are generated in the product itself, which causes a problem that performance reproducibility is not guaranteed. In another representative structure, the linear silsesquioxane has excellent solution processability and can compensate for the shortcomings of the cage-like structure, but has a disadvantage in that the physical property is less than the cage-type structure of the crystalline structure. In addition, since random silsesquioxane is polymerized in a free form, the limitation and reproducibility of application by gelation using Si-OH, Si-alkoxy, etc., which are unstable in a polymer, are applied. There is a problem that is difficult to secure.

Attempts have been made to control such silsesquioxane structures into specific structures according to industrial requirements. For example, U.S. Patent Publication No. US2011-0201827 attempts to control polyhedral silsesquioxane and draw unique advantages by using a silane coupling agent as a precursor, but this is also used as a substituent by connecting a cage type to a single linear. There was no significant improvement in physical properties.

Therefore, the present inventors have studied to make up for the above disadvantages of silsesquioxane and to maximize the advantages, designing a polymer structure of a specific structure and inducing the introduction of an easy curing process using an organic functional group introduced into the side chain. As a result, it was confirmed that the excellent physical properties can be maintained for a long time, can be used in various industrial aspects, such as the main material, additive material, coating material to complete the present invention.

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

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

It is another object of the present invention 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 one of the following Chemical Formulas 1 to 3:

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,

A is

And D is

And E is

Is,

Each Y is 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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C ₁ -C ₄₀ alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C ₂ -C ₄₀ alkenyl 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; An aralkyl group of C ₃ ~ C _40; C ₃ -C ₄₀ aryloxy group; Or a C ₃ to C ₄₀ arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C ₁ to C ₄₀ alkyl groups, C ₂ to C ₄₀ alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,

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

e is 1 or 2, preferably 1,

n is independently an integer of 1-20, Preferably it is 3-10.

In another aspect, the present invention is a first step of preparing a general formula (4) by mixing a basic catalyst and an organic solvent in the reactor and then adding an organic silane compound and condensation; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR ² ) ₂ structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step. The method of preparing the silsesquioxane composite polymer represented by Chemical Formula 1 to provide:

[Formula 4]

In the above, R ¹ , R ² , R ⁶ , D, a and d are as defined in formulas (1) to (3).

In another aspect, the present invention is a first step of preparing a general formula (4) by mixing a basic catalyst and an organic solvent in the reactor and then adding an organic silane compound and condensation; And after the first step, an excess organosilane compound is added in order to introduce Dd (OR ³ ) ₂ and Dd (OR ⁴ ) ₂ structures to Chemical Formula 4 as shown in Chemical Formula 2, and an acidic catalyst is added to the reactor to react the reaction solution. Adjusting the acidity and then stirring the second step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of removing the sole cage formation structure through a recrystallization and filtering process after the third step. The method of preparing silsesquioxane composite polymer represented by Chemical Formula 2 is provided.

In another aspect, the present invention is a first step of preparing a general formula (4) by mixing a basic catalyst and an organic solvent in the reactor and then adding an organic silane compound and condensation; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR ⁵ ) ₂ structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of converting the reaction solution into an acidic atmosphere by mixing the organic silane compound by introducing an acidic catalyst into the reactor in order to introduce an EeX ₂ structure at the end of the composite polymer after the third step. It provides a method for producing a silsesquioxane composite polymer represented by the formula (3).

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

The silsesquioxane composite polymer according to the present invention has excellent processability of linear silsesquioxane and excellent physical properties of cage-type silsesquioxane at the same time. , Heat resistance and the like can be given 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 1-3:

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,

A is

And D is

And E is

Is,

Each Y is 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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C ₁ -C ₄₀ alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C ₂ -C ₄₀ alkenyl 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; An aralkyl group of C ₃ ~ C _40; C ₃ -C ₄₀ aryloxy group; Or a C ₃ to C ₄₀ arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C ₁ to C ₄₀ alkyl groups, C ₂ to C ₄₀ alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,

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

e is 1 or 2, preferably 1,

n is independently an integer of 1-20, Preferably it is 3-10.

The silsesquioxane composite polymer represented by any one of Formulas 1 to 3 may be represented by R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ . It is a composite silsesquioxane polymer which has the indicated organic functional group, the repeating unit consists of a and d, and can selectively introduce e as a terminal unit.

N of the [(SiO _3/2 R) _{4 + 2n} O] structure introduced into the repeating unit [D] d of Formula 1 or 2 may be substituted with an integer of 1 to 20, preferably 3 to 10, and More preferably, the average n value is 4 to 5, and when n is 4, the substituted structure is represented by the following Formula 5:

[Formula 5]

Wherein R is as defined above.

In the present invention, _n of the [(SiO _3/2 R) _{4 + 2n} R] structure introduced into the repeating unit [E] e of Chemical Formula 3 may be substituted with an integer of 1 to 20, preferably 3 To 10, more preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by the following Chemical Formula 6:

[Formula 6]

Wherein R is as defined above.

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

Table 1

No	R1	R2	R6	R9	Y, R
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

TABLE 2

No	R1	R2	R6	R7	Y, R	n
2-1	OH, methoxy	H, methyl	ECHE	Alkyl siol	ECHE	1-8
2-2	OH, CF 3	H, ethyl	Phenyl	Phenyl	Phenyl	1-8
2-3	OH, methoxy	H, acetyltyl	Alkyl siol	methyl	methyl	1-8
2-4	CF 3 , methoxy	Vinyl, methyl	GlyP	Dodecyl	GlyP	1-8
2-5	OH, methoxy	H, methyl	POMMA	Alkyl siol	POMMA	1-8
2-6	OH, C 8 F 13	H, F	ECHE	Phenyl	Phenyl	1-8
2-7	OH, CF 3	CF 3 , methyl	ECHE	Octyl	methyl	1-8
2-8	OH, C 8 F 13	H, methyl	F	Alkyl siol	GlyP	1-8
2-9	OH, methoxy	H, CF 3	ECHE	POMMA	POMMA	1-8
2-10	OH, methoxy	H, methyl	Phenyl	Alkyl siol	ECHE	1-8
2-11	OH, C 8 F 13	Aryl, methyl	Alkyl siol	methyl	Hexyl	1-8
2-12	OH, alkyl siol	H, methacryl	Phenyl	GlyP	GlyP	1-8
2-13	OH, methoxy	H, methyl	Alkyl siol	POMMA	POMMA	1-8
2-14	OH, acrylic	H, octyl	methyl	ECHE	Aminopropyl	1-8
2-15	Vinyl, methoxy	H, methyl	methyl	Alkyl siol	Phenyl	1-8
2-16	Alkylamine	H, methyl	methyl	GlyP	GlyP	1-8
2-17	OH, ethyl, methyl	Alkyl siol, methyl	methyl	POMMA	POMMA	1-8
2-18	Acetoxy, methoxy	H, methyl	GlyP	ECHE	Aminopropyl	1-8
2-19	Propoxy, methoxy	H, CF 3	GlyP	Phenyl	Phenyl	1-8
2-20	OH, methoxy	H, methyl	Aminopropyl	methyl	Octyl	1-8
2-21	C 8 F 13 , methoxy	C 8 F 13 , methyl	GlyP	POMMA	POMMA	1-8
2-22	OH, aryl	H, profile	POMMA	profile	ECHE	1-8
2-23	OH, methoxy	F, methyl	POMMA	Phenyl	Phenyl	1-8
2-24	CF 3 , methacryl	H, methyl	POMMA	methyl	methyl	1-8
2-25	OH, methoxy	H, ethyl	Aminopropyl	GlyP	GlyP	1-8

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

TABLE 3

No	R3	R4	R6	R7	Y, R
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

Table 4

No	R3	R4	R6	R7	Y, R
4-1	OH, methoxy	H, methyl	ECHE	Alkyl siol	ECHE
4-2	OH, CF 3	H, ethyl	Phenyl	Phenyl	Phenyl
4-3	OH, methoxy	H, acetyltyl	Alkyl siol	methyl	methyl
4-4	CF 3 , methoxy	Vinyl, methyl	POMMA	Dodecyl	GlyP
4-5	OH, acrylic	H, methyl	POMMA	Alkyl siol	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 siol	ECHE
4-11	OH, C 8 F 13	Aryl, methyl	Alkyl siol	methyl	Hexyl
4-12	OH, methoxy	H, methacryl	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 siol	Phenyl
4-16	Alkylamine	H, methyl	Octyl	GlyP	GlyP
4-17	OH, methoxy	Alkyl siol, 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 Chemical Formula 3 may be a polymer described in Table 5 or 6 below.

Table 5

No	R5	R6	R7	R8	R10	Y R	X, 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

Table 6

No	R5	R6	R7	R8	R10	Y R	X, R
6-1	H, methyl	ECHE	ECHE	ECHE	Alkyl siol, methyl	ECHE	ECHE
6-2	H, ethyl	Phenyl	Phenyl	Phenyl	H, methyl	Phenyl	Phenyl
6-3	H, acetyltyl	Alkyl siol	methyl	methyl	H, CF 3	methyl	methyl
6-4	Vinyl, methyl	POMMA	Dodecyl	GlyP	H, methyl	EGCDX	GlyP
6-5	H, methyl	POMMA	Alkyl siol	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 siol	ECHE	H, acetyltyl	Phenyl	ECHE
6-11	Aryl, methyl	Alkyl siol	methyl	ECHE	Vinyl, methyl	methyl	ECHE
6-12	H, methacryl	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 siol	methyl	H, methyl	Phenyl	methyl
6-16	H, methyl	Octyl	GlyP	EGDCX	H, octyl	Phenyl	EGDCX
6-17	Alkyl siol, 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 siol	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, methacryl	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 siol	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 siol	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 siol	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 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 broad applicability. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.

In addition, the weight average molecular weight of the silsesquioxane composite polymer according to 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 the silsesquioxane can be improved simultaneously.

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

Method for preparing silsesquioxane composite polymer represented by Formula 1

Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 4; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR ² ) ₂ structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps. The prepared silsesquioxane composite polymer has a structure as shown in Formula 1-1.

[Formula 4]

[Formula 1-1]

Wherein R, R ¹ , R ² , R ⁶ , R ⁷ , D, Y, a and d are as defined in Formulas 1 to 3.

Method for producing silsesquioxane composite polymer represented by formula (2)

Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 4; And after adding the acid catalyst to the reactor in order to introduce the structures of Dd (OR ³ ) ₂ and Dd (OR ⁴ ) ₂ to Chemical Formula 4 after the first step, the reaction solution is acidified, and excess organic silane compound is added. A second step of adding and stirring; And a third step of adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic to perform a condensation reaction. And a composite polymer prepared by performing a purification step of removing the cage structure, which is a by-product generated solely, by recrystallization through a third step reaction, and has a structure as shown in Chemical Formula 2-1.

[Formula 2-1]

Wherein R, R ³ , R ⁴ , R ⁶ , R ⁷ , D, Y, a and d are as defined in Chemical Formulas 1 to 3.

Manufacturing method of silsesquioxane composite polymer represented by the formula (3)

Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 4; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR ⁵ ) ₂ structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. And a third step of adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic to perform a condensation reaction. And a fourth step of introducing an EeX ₂ structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. The prepared silsesquioxane composite polymer has a structure as shown in Chemical Formula 3-1.

[Formula 3-1]

Wherein R, R ⁵ , R ⁶ , R ⁷ , R ⁸ , D, Y, X, a, d and e are as defined in Formulas 1 to 3.

In the production method of the silsesquioxane composite polymer, a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation 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 catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Preferably, the amine based catalyst may be tetramethylammonium hydroxide (TMAH), and the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO ₃ ). The content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted. Within the above range, the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation. In addition, the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H ₂ SO ₄ , HNO ₃ , CH ₃ COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.

In the method for preparing 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 cellosolves, ketones such as lactate, acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan systems such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Polar solvents such as methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane and acro Various solvents, such as nitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, benzyl alcohol, can be used.

In addition, the organosilane-based compound of the silsesquioxane composite polymer of the present invention R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , 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 having an effect of improving chemical resistance of the silsesquioxane composite polymer and improving non-swelling property, or a composite polymer The organosilane compound containing an epoxy group or a (meth) acryl group which has the effect of increasing the hardening density of and improving the mechanical strength and hardness of a hardened layer can be used.

Specific examples of the organosilane compound include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 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-aminopropyltrimeth Methoxysilane, dimethyl tetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, You may use individually by 1 type or in combination of 2 or more types. It is more preferable to mix and use 2 or more types for the physical property of the composition currently manufactured.

Preferably the pH of the reaction solution of the first step of the present invention is preferably 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, the pH of the reaction solution of the third step is 8 It is preferably 1 to 11.5, and the pH of the reaction solution of the fourth step of preparing Formula 3 is preferably 1.5 to 4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.

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

Preferably, the coating composition comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 3, an organic solvent commonly used in the art that is compatible with the composite polymer, an initiator, and optionally a curing agent. It may further include additives such as plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.

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

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, In addition to polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the composite polymer, the initiator, the curing agent and optionally added additives.

In the coating composition of the present invention, the initiator or the 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 system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.

In the present invention, for the curing and post-reaction of the composite polymer, various initiators can be used, the initiator is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the composition, when included in the content within the above range, After transmission and coating stability can be satisfied at the same time.

In addition, when an unsaturated hydrocarbon or the like is introduced into the organic functional group, a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride. Hydroxy-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 quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl- Optical radical initiators such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t- Butylpaoxy maleic acid, t-part Hydroperoxide, 2,4-dichlorobenzoylperoxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butyl Thermal radical initiators such as peroxy) valerate and various mixtures thereof and the like can be used.

When the organic functional group contains an epoxy or the like, sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations). Iodonium, such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopentadiene-1-yl) s Fe cations such as [(1-methylethyl) benzene] -Fe and BF ₄ ^-, PF _{6 ^{-, SbF 6 - [BQ 4}} ] , such ^as-may be used in combination with onium salts (here, Q is a phenyl group substituted with at least a group of two or more fluorine or a trifluoromethyl group.).

In addition, the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like 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.

Moreover, according to the kind of said organic functional group, amine diamine, ethylenediamine, triethylene tetramine, tetraethylene pentamine, 1, 3- diamino propane, dipropylene triamine, 3- (2-amino ethyl) amino-propyl Amines, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadotecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, Hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-animocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane and the like can be used. .

In addition, as a curing accelerator for promoting the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogendifluoride, tetrabutylphosphonium dihydrogen tree Fluorine and the like can also be used.

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

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

The present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction. Can be. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, strength, and the like. It is preferably included in an amount of 0.1-10 parts by weight with respect to parts.

Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., BYK- 308, BYK-373, etc.), polymethylalkylsiloxanes (eg, BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxanes (eg, BYK-320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxanes (e.g., BYK-315, etc.), aralkyl modified methylalkyl polysiloxanes, e.g. , BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane (Polyester modified h ydroxy functional polydimethylsiloxane (e.g., BYK-370, etc.), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, e.g., BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, e.g. BYK-380, etc.), ionic polyacrylic (e.g., BYK- 381, etc.), polyacrylate (for example, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK -352, etc.), polymethacrylate type (Polymethacrylate, such as BYK-390, etc.), polyether acryl Lidimethylsiloxane (Polyether modified acryl functional polydimethylsiloxane, such as BYK-UV 3500, BYK-UV3530, etc.), Polyether siloxane (Polyether modified siloxane, such as BYK-347, etc.), Alcohol alkoxylates ( Alcohol alkoxylates, for example BYK-DYNWET 800, etc., acrylates (Acrylate, for example BYK-392, etc.), hydroxy silicone polyacrylates (Silicone modified polyacrylate (OH-functional), for example , BYK-Silclean 3700, etc.).

The coating composition of the present invention can be applied to a variety of materials to improve the high surface hardness, mechanical strength and heat resistance to 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 of a mobile phone or a display.

In the present invention, the method for coating the coating composition is known among spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, and the like. Of course, those skilled in the art can arbitrarily select and apply.

Since the silsesquioxane composite polymer prepared according to the present invention includes a linear silsesquioxane chain and a cage silsesquioxane chain composed of linear silsesquioxane polymers, the processability of the linear polymer and the crystalline silsesquioxane It can have excellent physical properties of, and is easy to cure through the organic functional groups included in the structure, it can be widely applied to the industry to apply the organic-inorganic hybridized polymer. In addition, since the basic optical properties, physical properties, heat resistance properties of the silicon is basically provided, it can be widely used as a main material, an additive, or various coating materials.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1 : Synthesis of Silsesquioxane A-D Structured Composite Polymer

In the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows.

Example 1-a Preparation of Catalyst

In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).

Example 1-b Synthesis of Linear Silsesquioxane Structure

To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.

Example 1-c Generation of a continuous cage structure

To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. 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 in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 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 cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, a portion was collected and analyzed by ²⁹ Si-NMR. As a result, analytical peaks of the structure introduced by using a phenyl group appeared as two sharp forms, and 50% of the AD polymer of Formula 1 without remaining by-products remained. It was confirmed that the above was manufactured. In addition, styrene conversion molecular weight was measured as 11,000. ²⁹ Si-NMR (CDCl ₃ ) δ -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

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

TABLE 7

Method of implementation	1-b Method Applicable Monomer	1-c method applied 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, ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy) propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, and ECHETMDS is Di (epoxycyclohexyethyl) tetraDSoxy Dimethoxyg ) 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 Structured Polymer

In order to manufacture a composite polymer having a D-A-D structure, the following example was used. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.

Example 2-a Generation of Excess Continuous Cage Structure

To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one 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. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 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 cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was analyzed and analyzed by ²⁹ Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the AD polymer of Formula 1 was prepared without any remaining by-products. I could confirm it. In addition, styrene conversion molecular weight was measured as 14,000. In addition, unlike the AD structure in the Si-NMR analysis, the peak around -68ppm, which was seen at the end of the A structure, disappeared, and the end of the A structure was converted into the D structure, thereby confirming that the DAD structure was generated. ²⁹ Si-NMR (CDCl ₃ ) δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, the 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.

Table 8

Method of implementation	1-b Method Applicable Monomer	2-a method applied 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, and ECHETMDS is Di (epoxycyclohexyethyl) tetraDSoxy Dimethoxyg ) 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 Structured Composite Polymer

The following example was used to prepare a composite polymer having an E-A-D structure. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out 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 were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 ° C at a temperature of 4 ° C. Stirred for a minute. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

Example 3-b Introduction of a Cage to the Terminal E Structure

After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was 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 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. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 3-c] Removal of By-products by Precipitation and Recrystallization, Obtaining the Result

After the reaction mixture was obtained 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 by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, in particular, the result of 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, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 9 below. In this case, the method used in Example 3 was equally applied.

Table 9

Method of implementation	1-b Method Applicable Monomer	1-c method applied monomer		3-a method applied monomer	3-b method applied 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, and ECHETMDS is Di (epoxycyclohexyethyl) tetraDSoxy Dimethoxyg ) 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 : Preparation and process of coating composition using silsesquioxane composite polymer

By using the silsesquioxane composite polymers 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

20 g of the silsesquioxane composite polymer represented by Formula 1 prepared in Example 1 was dissolved in methyl ethyl ketone at 20 wt% to prepare 100 g of a coating composition. Then, 5 parts by weight of diphenyl iodonium 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, SKC PET film, and Mayer coating was performed by dividing 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

50 g of the silsesquioxane composite polymer represented by Chemical Formula 3-1 prepared in Example was dissolved in 50% by weight in methyl ethyl ketone to prepare 100 g of a coating composition. 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, followed by stirring 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 a SKC-SG00L 250 um film, which is a SKC PET film, and No. 30 to 50 rods were divided into 5 units to perform Mayer coating. After coating, the resultant was obtained after curing for 10 minutes in a drying oven at 80 ℃.

[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 any composition. SKC-SG00L 250um film, SKC's PET film, was divided into 5 units of No. 30 to 50 rods and subjected to Mayer coating. It was.

Experimental Example 1

The weight average molecular weight and molecular weight distribution of the silsesquioxane resin prepared in Example 1 were used with a JASCO PU-2080 plus SEC system equipped with a RI-2031 plus refractive index detector and a UV-2075 plus UV detector (254 detection wavelength). It was measured by. THF was used at flow rate 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, the obtained silsesquioxane had a weight average molecular weight of 12,000 by SEC analysis and confirmed that the molecular weight distribution was 1.8.

Experimental Example 2

IR was measured using the ATR mode of the Perkin-Elmer FT-IR system Spectrum-GX. FT-IR analysis showed a broad bimodal (continuous double-shaped) absorption peak in the small amount of the structure obtained in Example 1-b at 950-1200 cm ⁻¹ , which was perpendicular to the silsesquioxane chain ( It is derived from the stretching vibration of siloxane bonds in the -Si-O-Si-R and horizontal (-Si-O-Si-) directions. Then, as a result of analyzing the deposit of the structure obtained in 1-c, it was confirmed that the peak appearing at 1200 cm ⁻¹ was further grown, thereby confirming the substitution of the cage structure. This result was not found in cage type (generally, molecular weight of 1,000 ~ 5,000), which is low in actual molecular weight, despite the growth of cage characteristic peaks. From this, it was confirmed that the introduction into 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), in particular, the composite polymer obtained in the formula of 3-1. The measurement was measured via TGA at a 10 ° C./min scan rate of 50-800 ° C. under nitrogen. As a result of the measurement, by replacing the cage structure at the terminal, it was confirmed that the amount of decomposition of Si-OH and Si-OR which was decomposed between 100-200 ° C. was significantly reduced.

Experimental Example 4

PC (I component Glastic polycarbonate) SKC's PET and PMMA (COPAN's OAS-800) transparent substrates using the polymer resins described in Tables 7 to 9 in the same manner as described in Example 4 Coating and curing were performed to determine the surface properties. The following experimental results are the results using the polymer resin prepared in Example 3, the coating composition using the polymer resins described in Tables 7 to 9, although not shown in the table showed a result equivalent to the polymer resin of Example 3.

Surface hardness In general, the pencil hardness method (JIS 5600-5-4) is generally rated at 500 g load, which is 3 kg horizontally at a rate of 0.5 mm per second at a 45-degree angle to the coating surface under a more severe 1 kgf load. The coating film was moved to evaluate the scratches. If five traces do not confirm the scratches more than two times, the pencil of the upper hardness is selected.If the scratches are more than two times, the pencil is selected and the pencil hardness lower than the pencil hardness is evaluated as the pencil hardness of the coating film. It was. The evaluation results confirmed the 9H hardness of the glass level regardless of the substrate type at a coating thickness of 10 um 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 wound 15 times by winding # 0000 steel wool at the tip of the iron hammer weighing about 1kg. The reciprocating test piece was rubbed, and the haze was measured. The test piece was rubbed 400 times, which is a more severe condition, and visually evaluated by haze measurement and a microscope. In the coating thickness of 5 um or more coating was confirmed that all excellent resistance to scratches generated on the surface.

-Evaluation of adhesive force (JIS K5600-5-6): Scrape the coating film with cutter blades at 1-5 mm intervals, attach cellophane tape on it, and judge the adhesiveness by the number of defects when pulling out the tape. The adhesive was judged by the number of falling made of 100, the results are shown in Table 10 below. The notation is "(100/100) not falling out of the number of 100" In the example of not falling 100 ("100/100)".

-Reliability Evaluation : Storing at 85%, 85 ° C reliability chamber for 240 hours and evaluating the bending characteristics. The flexural evaluation criteria were within ± 0.1 mm before the reliability evaluation, within ± 0.3 mm after the reliability evaluation, and the flexural characteristics evaluation results after the reliability storage were excellent in all the PET, PC, and PMMA substrates.

Table 10

Evaluation item		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)	Less than 6B	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
Scrath test (Steel wool, 1kg 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, the coating composition of the present invention not only shows a very good surface hardness and optical properties, but also excellent in other physical properties at the same time.

The silsesquioxane composite polymer according to the present invention has excellent processability of linear silsesquioxane and excellent physical properties of cage-type silsesquioxane at the same time. , Heat resistance and the like can be given to various materials.

Claims (17)

1. Silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 3:

   [Formula 1]

   

   [Formula 2]

   

   [Formula 3]

   

   In Chemical Formulas 1 to 3,

   A is

   

   And D is

   

   And E is

   

   Is,

   Each Y is 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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C ₁ -C ₄₀ alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C ₂ -C ₄₀ alkenyl 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; An aralkyl group of C ₃ ~ C _40; C ₃ -C ₄₀ aryloxy group; Or an C ₃ ~ C ₄₀ aryl siol group,

   a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500,

   e is 1 or 2,

   n is independently an integer of 1-20.
2. The method of 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 deuterium, halogen, amine group, (meth) acryl group, and siol group , An isocyanate group, a nitrile group, a nitro group, a phenyl group, an alkyl group of C ₁ to C ₄₀ which is unsubstituted or substituted with a cyclohexyl epoxy group, an alkenyl group of C ₂ to C ₄₀ , an amine group, an epoxy group, a cyclohexyl epoxy group, (meth) A silsesquioxane composite polymer comprising an acryl group, a siol group, a phenyl group or an isocyanate group.
3. The method of claim 1,

   a is 3 to 1000, and d is 1 to 500, the silsesquioxane composite polymer.
4. The method of claim 1,

   d is a silsesquioxane composite polymer, characterized in that 2 to 100.
5. The method of claim 1,

   Silsesquioxane composite polymer, characterized in that the average of n value is 4 to 5.
6. The method of claim 1,

   Linear silsesquioxane composite polymer, characterized in that the condensation degree of the linear silsesquioxane composite polymer of Formula 1 is 1 to 99.9% or more.
7. The method of 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.
8. Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 4; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR ² ) ₂ structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step.

   [Formula 4]

   

   Wherein R ¹ , R ² , R ⁶ , a, D and d are the same as defined in Chemical Formulas 1 to 3.
9. Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 4; And after the first step, an excess organosilane compound is added in order to introduce Dd (OR ³ ) ₂ and Dd (OR ⁴ ) ₂ structures to Chemical Formula 4 as shown in Chemical Formula 2, and an acidic catalyst is added to the reactor to react the reaction solution. Adjusting the acidity and then stirring the second step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of removing the single cage generation structure through a recrystallization and a filtering process after the third step, wherein the silsesquioxane composite polymer represented by Chemical Formula 2 is characterized in that it comprises:

   [Formula 4]

   

   Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , a, D and d are as defined in Chemical Formulas 1 to 3.
10. Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 4; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR ⁵ ) ₂ structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of converting the reaction solution into an acidic atmosphere by mixing the organic silane compound by introducing an acidic catalyst into the reactor in order to introduce an EeX ₂ structure at the end of the composite polymer after the third step. Method for producing a silsesquioxane composite polymer represented by the formula (3);

    [Formula 4]

    

    Wherein R ¹ , R ² , R ⁵ , R ⁶ , a, D, E, X, d and e are as defined in Formulas 1 to 3.
11. The method according to any one of claims 8 to 10,

    Method for producing a silsesquioxane composite polymer, characterized in that the mixed catalyst comprises a metal based catalyst and an amine based catalyst.
12. The method of claim 11,

    Method for producing a silsesquioxane composite polymer, characterized in that the ratio of the amine basic catalyst and the metal basic catalyst is 10 to 90: 10 to 90 parts by weight.
13. Coating composition comprising the silsesquioxane composite polymer according to claim 1.
14. The method of claim 13,

    The coating composition is a coating composition, characterized in that the solvent-free type.
15. The method of claim 13,

    Silsesquioxane composite polymer according to claim 1;

    Initiator; And

    Organic solvents;

    Coating composition, characterized in that it may comprise.
16. The method of claim 15,

    The silsesquioxane composite polymer is a coating composition, characterized in that 5 to 90 parts by weight based on 100 parts by weight of the coating composition.
17. The method of claim 15,

    The coating composition further comprises a curing agent, a plasticizer, or a sunscreen coating composition.