KR20150102864A - Silsesquioxane composite polymer and method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a silsesquioxane complex polymer and a method for manufacturing the same, more specifically, to a silsesquioxane complex polymer including, in a single polymer, a silsesquioxane chain and a cage-type silsesquioxane which have a specific structure, and thus, maximizing processability and physical characteristics.

Description

Technical Field [0001] The present invention relates to a silsesquioxane complex polymer and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a silsesquioxane complex polymer and a method for preparing the same, and more particularly, to a silsesquioxane composite polymer which maximizes workability and physical properties by introducing various silsesquioxane structures into one silsesquioxane polymer ≪ / RTI >

Silsesquioxane has been used for various purposes in various fields. In particular, various attempts have been made to improve the workability and maximize the mechanical and physical properties, and research and development are continuing to date. However, the silsesquioxane polymers developed so far have still not satisfied the processability, mechanical and physical properties at the same time.

For example, cage silsesquioxane has been shown to exhibit physical properties that siloxane bonds can be expressed, and has been applied to various aspects. However, since it has a crystalline structure in itself, its solubility in solution processing is limited, and K There is a problem that the reproducibility of the performance is not ensured due to the reformation of the molecular unit such as the recrystallization phenomenon in the result of applying the topography structure itself. As another representative structure, the ladder silsesquioxane has a superior solution processability and can solve the disadvantages of the cage type structure, but has a disadvantage that it does not meet the cage type structure in which the physical property is a crystalline type structure. In addition, since the random type silsesquioxane is polymerized in a free form, the limitation and reproducibility to be applied by gelation using Si-OH and Si-alkoxy which are unstable in the polymer There is a problem that is difficult to secure.

Attempts have been made to control the structure of silsesquioxane to a specific structure in accordance with the requirements of the industry. For example, U.S. Patent Publication No. 2011-0201827 attempts to control the polyhedral silsesquioxane using a silane coupling agent as a precursor and draws its unique advantages, but this is also an example of a single linear type, The improvement of the physical properties was not largely promoted.

Therefore, the inventors of the present invention have studied to improve the disadvantages of the silsesquioxane as described above and to maximize the advantages thereof. As a result, the present inventors have designed a polymer structure of a specific structure and introduced an easy curing process using organic functional groups introduced into the side chain As a result, it has been confirmed that excellent physical properties can be sustained for a long time and can be used in various industrial fields such as main material, additive material, and coating material, thus completing the present invention.

In order to solve the above problems, the present invention provides a silsesquioxane complex polymer comprising a linear silsesquioxane chain and a cage silsesquioxane having a specific structure in one polymer to maximize processability and physical properties .

It is another object of the present invention to provide a process for producing the silsesquioxane complex polymer.

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

In order to accomplish the above object, the present invention provides a silsesquioxane complex polymer represented by any of the following formulas (1) to (3):

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

이고, D는

이고, E는

이며,A is

And D is

And E is

Lt;

Y is independently 0, NR ⁹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O]

X is independently at each occurrence 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 and R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or a C ₃ to C ₄₀ aryl radical which is optionally substituted by a substituent selected from the group consisting of deuterium, halogen, an amine group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group, a phenyl group, a cyclohexyl epoxy group It is included, and C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, an amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylic group, between olgi, a phenyl group or isocyanate,

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 to 20, preferably 3 to 10.

The present invention also relates to a process for preparing a compound of formula (I), which comprises: a first step of mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the compound; And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ² ) ₂ structure into the general formula (4) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; And a third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to carry out a condensation reaction, and a third step of preparing the silsesquioxane complex polymer represented by the general formula (1) to provide:

[Chemical Formula 4]

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

The present invention also relates to a process for preparing a compound of formula (I), which comprises: a first step of mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the compound; And an excess amount of an organosilane compound is added to introduce the Dd (OR ³ ) ₂ and Dd (OR ⁴ ) ₂ structures into the general formula ( ⁴ ) after the first step, and the acid catalyst is added to the reaction mixture A second step of adjusting the pH to acidic and then stirring; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of removing the single cage-forming structure through a recrystallization and a filtering process after the third step. The silsesquioxane complex polymer according to claim 1,

The present invention also relates to a process for preparing a compound of formula (I), which comprises: a first step of mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the compound; And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ⁵ ) ₂ structure into the general formula (4) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of introducing an EeX ₂ structure into the end of the composite polymer after the third step, and then introducing an acidic catalyst into the reactor to convert the reaction solution into an acidic atmosphere and mixing and stirring the organosilane compound And a silsesquioxane complex polymer represented by the following general formula (3).

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

The silsesquioxane complex polymer according to the present invention has both the ease of processing of linear silsesquioxane and excellent physical properties of cage silsesquioxane, so that it is possible to obtain excellent physical properties, optical characteristics , Heat resistance characteristics, and the like can be imparted to various materials.

Hereinafter, the present invention will be described in detail.

The present invention provides a silsesquioxane complex polymer represented by any one of the following formulas (1) to (3):

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

이고, D는

이고, E는

이며,A is

And D is

And E is

Lt;

Y is independently 0, NR ⁹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O]

X is independently at each occurrence 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 and R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or a C ₃ to C ₄₀ aryl radical which is optionally substituted by a substituent selected from the group consisting of deuterium, halogen, an amine group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group, a phenyl group, a cyclohexyl epoxy group It is included, and C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, an amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylic group, between olgi, a phenyl group or isocyanate,

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 to 20, preferably 3 to 10.

Any one silsesquioxane composite polymer represented in the above Chemical Formulas 1 to 3 is the ^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 8, R 9, or R ¹⁰ Is a complex silsesquioxane polymer having an organic functional group and having repeating units a and d and capable of selectively introducing e as a terminal unit.

N in the [(SiO _3/2 R) _{4 + 2 n} O] structure introduced into the repeating unit [D] d of the above formula 1 or 2 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 when n is 4, the substituted structure is represented by the following formula 5:

[Chemical Formula 5]

Wherein R is as defined above.

In the present invention, _n in the [(SiO3 / _2R ) _{4 + 2nR} ] structure introduced into the repeating unit [E] e of the above formula (3) may be substituted with an integer of 1 to 20, preferably 3 And more preferably an average n value of 4 to 5. For example, when n is 4, the substituted structure is represented by the following formula (6): < EMI ID =

[Chemical Formula 6]

Wherein R is as defined above.

As a specific example, the silsesquioxane complex polymer of Formula 1 may be a polymer described in Tables 1 and 2 below. In the following Tables 1 to 6, ECHE means (Epoxycyclohexyl) ethyl, GlyP means Glycidoxypropyl, and POMMA means (Methacryloyloxy) propyl. n is independently 1 to 8;

No R1 R2 R6 R9 Y of 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

No R1 R2 R6 R7 Y of R 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, acetyl 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, alkylaryl 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 complex polymer of Formula 2 may be a polymer described in Tables 3 and 4.

No R3 R4 R6 R7 Y of 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

No R3 R4 R6 R7 Y of R 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, acetyl 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 complex polymer of Formula 3 may be a polymer as shown in Table 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, acetyl 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, acetyl 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, acetyl 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, acetyl 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, acetyl 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 silsesquioxane complex polymer of the present invention can be adjusted to have a degree of condensation of 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 the terminal Si and the central Si can be adjusted from 50% to 0.01% with respect to the bonding group of the entire polymer.

The silsesquioxane complex polymer according to the present invention may have a weight average molecular weight of 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 simultaneously improved.

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

Process for producing silsesquioxane complex polymer represented by formula (1)

Mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ² ) ₂ structure into the general formula (4) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; And a third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to perform a condensation reaction. The prepared silsesquioxane complex polymer has a structure represented by the following formula (1-1).

[Chemical Formula 4]

[Formula 1-1]

Wherein R, R ¹ , R ² , R ⁶ , R ⁷ , D, Y, a and d are as defined in the general formulas (1) to (3).

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

Mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And an acidic catalyst is added to the reactor to introduce the Dd (OR ³ ) ₂ and Dd (OR ⁴ ) ₂ structures into the formula (4) after the first step, the reaction liquid is adjusted to be acidic, A second step of adding and stirring; And a third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a third step, the cage structure as a by-product, which is produced alone, is removed by recrystallization. The resulting complex polymer has a structure as shown in Formula 2-1 below.

[Formula 2-1]

Wherein R, R ³ , R ⁴ , R ⁶ , R ⁷ , D, Y, a and d are as defined in the general formulas (1) to (3).

Process for producing silsesquioxane complex polymer represented by formula (3)

Mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ⁵ ) ₂ structure into the general formula (4) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; And a third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of introducing an EeX ₂ structure into the end of the complex polymer after the third step, and then introducing an acidic catalyst into the reactor to convert the reaction solution into an acidic atmosphere and mixing and stirring the organosilane compound. The prepared silsesquioxane complex polymer has a structure as shown in Formula 3-1 below.

[Formula 3-1]

Wherein ^{R, R 5, R 6,} R 7, R 8, D, Y, X, a, d and e are as defined in the formula 1-3.

In the process for preparing the silsesquioxane complex polymer, a basic catalyst, preferably a mixed catalyst of two or more basic catalysts, is used, neutralized and acidified with an acid catalyst to induce rehydrolysis, and two or more basic catalysts , The acidity and the basicity can be continuously controlled in a single reactor.

At this time, the basic catalyst may be prepared by appropriately combining two or more materials selected from metal-based basic catalysts selected from the group consisting of Li, Na, K, Ca and Ba and amine-based basic catalysts. 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 optionally controlled in the ratio of the amine-based basic catalyst to the metal-based basic catalyst in the range of 10 to 90: 10 to 90 parts by weight. Within the above range, the reactivity between the functional group and the catalyst during hydrolysis can be minimized, and defects of the organic functional groups such as Si-OH or Si-alkoxy are remarkably reduced and the degree of condensation can be freely controlled. The acidic catalyst may be any acidic substance commonly used in the art. For example, it may be a general acidic substance such as HCl, H ₂ SO ₄ , HNO ₃ and CH ₃ COOH, Organic acid materials such as latic acid, tartaric acid, maleic acid, and citric acid can also be applied.

In the process for preparing the silsesquioxane complex polymer of the present invention, the organic solvent may be any organic solvent conventionally used in the art, and examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Ketones such as acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Methylene-2-pyrrolidone, but also polar solvents such as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, Nitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol and the like can be used.

The organosilane compound may be a silsesquioxane complex polymer of the present invention represented by any one of formulas 1 to 3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ may be used. In particular, an organosilane compound containing a phenyl group or an amino group, which has an effect of increasing the chemical resistance of the silsesquioxane complex polymer to improve the non-swelling property, An epoxy group or an organosilane compound containing a (meth) acrylic group may be used, which has the effect of increasing the curing density of the cured layer and improving the mechanical strength and hardness of the cured layer.

Specific examples of the organosilane compound include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 (Methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3-hydroxybutyltrimethoxysilane) , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Diphenyltetramethoxysiloxane, and the like, and the like. These may be used singly or in combination of two or more. It is more preferable to use a mixture of two or more kinds for the properties of the final composition.

Preferably, the pH of the reaction solution of the first step of the present invention is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, and the pH of the reaction solution of the third step is preferably 8 To 11.5, and the pH of the reaction solution of the fourth step for preparing the compound of formula (3) is preferably from 1.5 to 4. When the silsesquioxane complex polymer is within the above range, the yield of the silsesquioxane complex polymer to be produced is high, and the mechanical properties of the silsesquioxane complex polymer can be improved.

The present invention also provides a coating composition comprising the silsesquioxane complex polymer represented by any one of Chemical Formulas 1 to 3 above. When the silsesquioxane complex polymer is a liquid, the coating composition can be solely coated in a non-solvent type, and in the case of a solid phase, an organic solvent can be included. The coating composition may further comprise an initiator or a curing agent.

Preferably, the coating composition comprises the silsesquioxane complex polymer represented by any one of the above formulas (1) to (3), an organic solvent commonly used in the art having compatibility with the complex polymer and an initiator, , A plasticizer, an ultraviolet screening agent, and other functional additives to improve curability, heat resistance, ultraviolet shielding, and plasticizing effect.

In the coating composition of the present invention, the silsesquioxane complex polymer is preferably contained in an amount of at least 5 parts by weight, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight, Is preferably included in the negative amount. Within the above range, the mechanical properties of the cured film of the coating composition can 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, But are not limited to, polar solvents such as tetrahydrofuran and tetrahydrofuran; polar solvents such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, But are not limited to, various solvents such as dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide and benzyl alcohol. The amount of the organic solvent is included in the balance excluding the complex polymer, the initiator, the curing agent, and optionally the additive.

In the coating composition of the present invention, the initiator or the curing agent may be appropriately selected depending on the organic functional group contained in the silsesquioxane complex polymer.

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

In the present invention, various initiators may 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. When the initiator is included in the content within the above range, Post-permeability and coating stability can be satisfied at the same time.

When an unsaturated hydrocarbon or the like is introduced into the organic functional group, a radical initiator may be used. Examples of the radical initiator include trichloro acetophenone, diethoxy acetophenone, 2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) 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-methylbutylate), 3,3- A photo radical initiator such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenylethane- Butylpoxomaleic acid, t-butyl Di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butyl Peroxy) valerate, and various mixtures thereof can be used.

When the organic functional group includes an epoxy or the like, a photopolymerization initiator (cation) such as triphenylsulfonium, diphenyl-4- (phenylthio) phenylsulfonium or the like sulfonium-based, diphenyliodonium or bis Iodonium such as iodonium, iodonium such as phenyldiazonium, ammonium such as 1-benzyl-2-cyanopyridinium or 1- (naphthylmethyl) -2- cyanopyridinium, Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, and (2,4- (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.).

Examples of the cationic initiator that acts by heat include cationic or protonic acid catalysts such as triflic acid salt, boron trifluoride ether complex, boron trifluoride, etc., various onium salts such as ammonium salts, phosphonium salts and sulfonium salts, and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation. These initiators can also be added in various mixing forms, and can be mixed with various radical initiators described above. Do.

Depending on the type of the organic functional group, amine curing agents such as ethylenediamine, triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane, dipropylenetriamine, 3- (2-aminoethyl) Amine, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxal tridecane- (4-aminomyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, and the like can be used as the initiator .

As the curing accelerator for accelerating the curing action, triazine compounds such as acetoguanamine, benzoguanamine and 2,4-diamino-6-vinyl-s-triazine, imidazole compounds such as 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, Diazabicyclo [4.3.0] nonane-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p- ) Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphoniumhydrogen difluoride, tetrabutylphosphonium dihydrogentry, Fluorine and the like may also be used.

Examples of the anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadonic anhydride, Acid anhydride curing agents such as phthalic anhydride, dodecenylsuccinic anhydride and 2,4-diethylglutaric anhydride can 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.

The present invention may further include additives such as an ultraviolet absorber, an antioxidant, a defoaming agent, a leveling agent, a water repellent agent, a flame retardant, and an adhesion improver for the purpose of improving hardness, strength, durability and moldability through a curing process or a post reaction . Such an additive is not particularly limited in its use, but may be suitably added within a range that does not impair the properties of the substrate, that is, the properties such as flexibility, light transmittance, heat resistance, hardness and strength. It is preferable that each of the above additives is included independently in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition.

Examples of additives usable in the present invention include polyether-modified polydimethylsiloxane (BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK- BYK-330, BYK-341, BYK-344, BYK-307, BYK-333 and BYK-310), polyether modified hydroxyfunctional poly-dimethyl- siloxane 308 and BYK-373), polymethylalkylpolysiloxane (e.g., BYK-077 and BYK-085), polyether modified methylalkylpolysiloxane (e.g., BYK-320, BYK-325 and the like), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315 and the like), Aralkyl modified methylalkyl polysiloxane BYK-322, BYK-323, etc.), polyester hydroxypolydimethylsiloxane (polyester modified h ydroxy functional polydimethylsiloxane such as BYK-370), polyester acrylic modified polydimethylsiloxane (e.g. BYK-371, BYK-UV 3570 etc.), polyether-polyester hydroxy Polyether modified dimethylpolysiloxane (e.g., BYK-345, BYK-348, BYK-346, and BYK-375), a polydimethylsiloxane-based polydimethylsiloxane (e.g., BYK- BYK-UV3510, BYK-332 and BYK-337), non-ionic acrylic copolymers (e.g. BYK-380), ionic acrylic copolymers (e.g. BYK- 381, etc.), polyacrylate (e.g., BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK- -352, etc.), polymethacrylate (e.g., BYK-390, etc.), polyether acrylate (E.g., BYK-UV 3530 and BYK-UV3530), polyether modified siloxane (e.g., BYK-347 and the like), alcohol alkoxylate-based (E.g., BYK-DYNWET 800), acrylate (e.g., BYK-392), silicone-modified polyacrylate (OH-functional) , BYK-Silclean 3700, etc.).

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

In the present invention, the method of coating the coating composition may be performed by a known method such as spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, It is needless to say that a person skilled in the art can arbitrarily select and apply it.

Since the silsesquioxane complex polymer prepared according to the present invention contains a linear silsesquioxane chain composed of a linear silsesquioxane polymer and a kage-type silsesquioxane chain, the ease of processing of the linear polymer and the crystalline silsesquioxane Inorganic hybrid polymer can be applied widely to the whole industry to which the organic-inorganic hybrid polymer is applied since it can have excellent physical properties of the organic-inorganic hybrid polymer and can be hardened through the organic functional group included in the structure. In addition, since it basically includes excellent optical properties, physical properties, and heat resistance characteristics of silicon, it can be widely used as a host material, an additive, or various coating materials.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

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

The synthesis step progressed stepwise through continuous hydrolysis and condensation as follows.

[Example 1-a] Preparation of catalyst

For controlling the basicity, a catalyst 1a was prepared by mixing a 25 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) with a 10 wt% aqueous potassium hydroxide (KOH) 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, stirred at room temperature for 1 hour, - (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, 15 parts by weight of tetrahydrofuran was added dropwise, and the mixture was further stirred for 5 hours. After removing the catalyst and impurities by filtration, the SI-OH functional group generated at the end of the reaction was identified by IR analysis (3200 cm ^-1 ), and the molecular weight was measured As a result, it was confirmed that the silsesquioxane having a linear structure such as the structure of the formula (4) had a molecular weight in terms of 8,000 styrene.

[Example 1-c] Production of continuous cage structure

To the mixed solution of Example 1-b was added 5 parts by weight of a 0.36 wt% aqueous solution of HCl very slowly, adjusted to have an acidic pH, and stirred at a temperature of 4 캜 for 30 minutes. Then, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to stabilize 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 D structure is formed in which alkoxy is opened separately from the linear polymer. A small amount of the sample was taken out and analyzed by 1 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. Then, 1 part by weight of phenyltrimethoxysilane was added dropwise at a time, and the mixture was stirred for 15 minutes, and 20 parts by weight of the catalyst prepared in 1-a was added. After mixing for 4 hours, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and the tetrahydrofuran in the mixed solution was removed under vacuum so that the whole reactant was converted into the aqueous solution mixture. After 4 hours of mixing, a part of the mixture was taken out and analyzed by ²⁹ Si-NMR. As a result, the analysis peak of the structure introduced by using the phenyl group appeared as two sharp shapes and the AD polymer as shown in formula (1) Or more. The molecular weight in terms of styrene was measured to be 11,000. ²⁹ Si-NMR (CDCl ₃ )? -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp)

The silsesquioxane complex polymer was prepared by applying the monomers described in Table 7 below. At this time, the preparation method was applied equally to the methods used in Examples 1-b and 1-c.

practice
Way
1-b method
Applied 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 represents 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS represents Glycidoxypropytrimethoxysilane, MAPTMS represents methacryloyloxy propyltrimethoxysilane, PTMS represents Phenyltrimethoxysilane, MTMS represents Methyltrimethoxysilane, ECHETMDS represents Di (epoxycyclohexyethyl) tetramethoxy disiloxane, GPTMDS represents Di ) tetramethoxy disiloxane, MAPTMDS is Di (methacryloyloxy) propy, PTMDS is Di (phenyl) tetramethoxy disiloxane, and MTMDS is 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 of the DAD structure. The catalyst and the linear structure were prepared in the same manner as in Examples 1-a and 1-b, and the production was carried out in the following manner to produce a continuous DAD structure.

[Example 2-a] Production of excessive continuous cage structure

To the mixed solution of Example 1-b was added 5 parts by weight of a 0.36 wt% aqueous solution of HCl very slowly, adjusted to have an acidic pH, and stirred at a temperature of 4 캜 for 30 minutes. Then, 25 parts by weight of diphenyltetramethoxydisiloxane used in Example 1-b was added dropwise at a time to stabilize 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. At this time, a precursor of D structure is formed in which alkoxy is opened separately from the linear polymer. A small amount of the sample was taken out and analyzed by 1 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. Then, 1 part by weight of phenyltrimethoxysilane was added dropwise at a time, and the mixture was stirred for 15 minutes, and 20 parts by weight of the catalyst prepared in 1-a was added. After mixing for 4 hours, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and the tetrahydrofuran in the mixed solution was removed under vacuum so that the whole reactant was converted into the aqueous solution mixture. After 4 hours of mixing, some of the fractions were taken out and analyzed by ²⁹ Si-NMR. As a result, the analysis peak of the structure introduced by using the phenyl group appeared as two sharp shapes and the AD polymer of formula 1 was produced without any residual by- I could confirm. The molecular weight in terms of styrene was measured to be 14,000. In addition, in Si-NMR analysis, peaks near -68 ppm observed at the end of the A structure disappeared unlike the AD structure, and it was confirmed that the end of the A structure was converted into the D structure to generate DAD structure. _{^{29 Si-NMR (CDCl 3)}} δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, the silsesquioxane complex polymer was prepared by applying the monomers described in Table 8 below. At this time, the manufacturing method was the same as the method used in Example 2 above.

practice
Way 1-b method
Applied 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 represents 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS represents Glycidoxypropytrimethoxysilane, MAPTMS represents methacryloyloxy propyltrimethoxysilane, PTMS represents Phenyltrimethoxysilane, MTMS represents Methyltrimethoxysilane, ECHETMDS represents Di (epoxycyclohexyethyl) tetramethoxy disiloxane, GPTMDS represents Di ) tetramethoxy disiloxane, MAPTMDS is Di (methacryloyloxy) propy, PTMDS is Di (phenyl) tetramethoxy disiloxane, and MTMDS is Di (Methyl) tetramethoxy disiloxane.

Example 3 : Synthesis of Silsesquioxane E-A-D Structure Composite Polymer

The following examples were used to prepare a complex polymer of the EAD structure. The catalyst and the linear structure were prepared in the same manner as in Example 1, and then, the production was carried out in the following manner to produce the EAD structure.

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

20 parts by weight of methylene chloride was added dropwise to the AD mixture obtained in Example 1-c without further purification, 5 parts by weight of a 0.36% by weight aqueous solution of HCl was added dropwise, the pH was adjusted to be acidic, Lt; / RTI > Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, the portions which were not hydrolyzed yet in the molecular structure were easily converted into the hydrolyzate in the acidic aqueous solution layer separated from the solvent, and E was introduced at the terminal unit by condensation in the organic solvent layer and the separated reaction product. 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] Cage introduction into the terminal E structure

The resulting organic layer obtained in Example 3-a was prepared without further purification, and 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 which the reaction was proceeding at once to stabilize hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again, To adjust the pH of the mixed solution. At this time, the cage-type polymer is introduced at the end of the E structure, and the reaction proceeds continuously in the reactor to form the polymer of Formula 3. However, since it was obtained with other by-products, a separate purification was required. Thereafter, the temperature was changed to room temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 3-c] Removal of by-products by precipitation and recrystallization, yielding the product

After completion of the reaction 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 decompression. Thereafter, the solution was precipitated twice in methanol to remove unreacted monomers, dissolved in tetrahydrofuran and an aqueous solution mixed in a weight ratio of 9.5: 0.5 by weight to 30 parts by weight, and stored at -20 캜 for 2 days. This is to prevent recrystallization of the material which is not introduced into the polymer and closed by the cage structure, so that purification can be easily performed.

     After completion of the recrystallization process, the obtained solid materials were filtered to obtain a polymer of formula (3) together with various by-products through vacuum depressurization. In addition, when the GPC results are compared with the NMR results, it can be seen that the complex polymer can be obtained without problems since the shaper type cage shape is obtained as a result of the low molecular weight obtained independently in the polymer growth of each step there was. At this time, the molecular weight was 17,000 in terms of styrene, and the results of Formula 3 were 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)

The silsesquioxane complex polymer was prepared by applying the monomers described in Table 9 below. At this time, the manufacturing method was the same as the method used in Example 3 above.

practice
Way 1-b method
Applied Monomer 1-c method
Applied Monomer 3-a
Way
Applied Monomer 3-b
Way
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 represents 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS represents Glycidoxypropytrimethoxysilane, MAPTMS represents methacryloyloxy propyltrimethoxysilane, PTMS represents Phenyltrimethoxysilane, MTMS represents Methyltrimethoxysilane, ECHETMDS represents Di (epoxycyclohexyethyl) tetramethoxy disiloxane, GPTMDS represents Di ) tetramethoxy disiloxane, MAPTMDS is Di (methacryloyloxy) propy, PTMDS is Di (phenyl) tetramethoxy disiloxane, and MTMDS is Di (Methyl) tetramethoxy disiloxane.

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

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

[Example 4-1] Preparation of photocurable coating composition

20 g of the silsesquioxane complex polymer represented by the 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 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 μm film of SKC company 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 캜 for 10 minutes, and UV irradiation was performed for 10 seconds on a 100 mW / cm ² lamp using a UV apparatus to obtain a resultant product.

[Example 4-3] Preparation of thermosetting coating composition

50 g of the silsesquioxane complex polymer represented by the formula (3-1) prepared in the Example was dissolved in methyl ethyl ketone in 50 wt% to prepare 100 g of a coating composition. 3 parts by weight of 1,3-diaminopropane, 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 SKC-SG00L 250 μm film of SKC company PET film, and Meyer coating was performed by dividing No. 30-50 rods into 5 units. After coating, the result was obtained after curing in a drying oven at 80 DEG C for 10 minutes.

[Example 4-5] Self-curing of the formulas (1), (2) and (3)

The results obtained in Examples 1, 2 and 3 were cured through heat without any additional composition. SKC-SG00L PET film (SKC-SG00L 250 μm film) was divided into 5 units of No. 30 ~ 50 rods and Mayer coating was applied. After curing for 2 hours in a drying oven at 100 ° C, Respectively.

[Experimental Example 1]

The weight average molecular weight and molecular weight distribution of the silsesquioxane resin prepared in Example 1 was measured using JASCO PU-2080 plus SEC system equipped with RI-2031 plus refractive index detector and UV-2075 plus UV detector (254 detection wavelength) Respectively. 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 silsesquioxane obtained had a weight average molecular weight of 12,000 and a molecular weight distribution of 1.8.

[Experimental Example 2]

The 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 bond) absorption peak appeared at 950 to 1200 cm ^-1 in a small amount of the structure taken in Example 1-b, -Si-O-Si-R) and the stretching vibration of the siloxane bond in the horizontal (-Si-O-Si-) direction. As a result of analyzing the structure of the structure obtained in 1-c, it was confirmed that the peak appeared at 1200 cm ^-1 further increased the substitution of the cage-type structure. This is because, in connection with the results of the GPC analysis analyzed in Experimental Example 1, it was found that despite the growth of the cage-type characteristic peaks, the cage type (generally having a molecular weight of about 1,000 to 5,000) , It was confirmed that the structure was introduced 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 by using a thermal gravimetric analyzer (TGA). In particular, the complex polymer obtained in the formula (3-1) was measured. Measurements were taken over TGA at 10 [deg.] C / min scan speed under nitrogen at 50-800 [deg.] C. As a result of the substitution of the cage-type structure at the end of the measurement results, it was confirmed that the decomposition amount of Si-OH and Si-OR decomposed at 100-200 ° C was significantly reduced.

[Experimental Example 4]

PC (Glastic polycarbonate product of IC component company) SKC company PET and PMMA (OAS-800 product of COPAN company) Using the polymer resin described in Tables 7 to 9 on the transparent substrate, coating composition Coated, and cured to measure surface properties. The results of the following experiment are the results of using the polymer resin prepared in Example 3, and the coating compositions using the polymer resins shown in Tables 7 to 9 are not the same as those of the polymer resin of Example 3, though they are not shown in the table.

- Surface hardness measurement : In general, the pencil hardness method (JIS 5600-5-4) is generally evaluated with a load of 500 g, which is a 1 kgf load, which is a stricter condition, and a pencil is horizontally moved at a rate of 0.5 mm per second The coating film was scratched by scraping. If no trace of scratching is found more than 2 times in the 5th experiment, the pencil of the upper hardness is selected. If the scratching marks are more than 2 times, the pencil is selected and pencil hardness lower than the pencil hardness is evaluated by pencil hardness Respectively. The evaluation results confirmed the glass level of 9H hardness regardless of the substrate type at coating thicknesses of 10 μm or more.

- Scratch test measurement: 400 times evaluation of steel wool # 0000 at 1 kgf The wear evaluation method (JIS K5600-5-9) by steel wool was performed by winding a # 0000 steel wool around the tip of a steel hammer weighing about 1 kg The reciprocating test specimen was rubbed and its haze was measured. The 400 specimens, which were more severe conditions, were rubbed and subjected to haze measurement and visual inspection with a microscope. It was confirmed that coatings having a coating thickness of 5 μm or more have excellent resistance to scratches on the surface.

- Adhesion evaluation (JIS K5600-5-6): Scratch the coating film with a cutter blade at intervals of 1-5 mm and attach a cellophane tape on it. When the adhesive tape is pulled out, it is judged as adhesive detachment number. And adhesion was judged to be a falling number among 100 pieces. The results are shown in Table 10 below. The notation is expressed as "(the number not falling down / 100)" as the number of the 100 not falling down.

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

Evaluation items PET-0.2 PC PMMA Before coating After coating Before coating After coating Before coating After coating Coating thickness - 10 탆 - 10 탆 - 10 탆 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-400 nm 91.2 91.7 89.2 89.0 90.4 90.2 UV-vis-450 nm 91.5 93.0 90.1 90.2 91.5 91.2 UV-vis-500 nm 92.4 93.4 91.4 91.6 91.9 91.6 YI (ASTM D1925) -0.38 -0.19 -0.15 0.05 0.14 0.24 Scrath test
(Steel wool, 1kg load _f,
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 shows not only excellent surface hardness and optical properties, but also excellent physical properties at the same time.

Claims (17)

Silsesquioxane complex polymer represented by any one of the following formulas (1) to (3):
[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,
A is

And D is

And E is

Lt;
Y is independently 0, NR ⁹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O]
X is independently at each occurrence 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 and R ¹⁰ are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or an aryl radical of C ₃ to C ₄₀ ,
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 are each independently an integer of 1 to 20; The method according to claim 1,
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently selected from the group consisting of deuterium, a halogen, an amine group, (Meth) acrylate group, an isocyanate group, a nitrile group, a nitro group, a phenyl group, a C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a cyclohexyl epoxy group, a C ₂ to C ₄₀ alkenyl group, an amine group, an epoxy group, a cyclohexyl epoxy group, An acrylic group, a silyl group, a phenyl group, or an isocyanate group. The method according to claim 1,
a is from 3 to 1000, and d is from 1 to 500. The silsesquioxane complex polymer according to claim 1, The method according to claim 1,
and d is 2 to 100. The silsesquioxane complex polymer according to claim 1, The method according to claim 1,
and the average value of n is 4 to 5. The silsesquioxane complex polymer according to claim 1, The method according to claim 1,
Wherein the linear silsesquioxane complex polymer of Formula 1 has a degree of condensation of 1 to 99.9% or more. The method according to claim 1,
The linear silsesquioxane complex polymer of Formula 1 has a weight average molecular weight of 1,000 to 1,000,000. Mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ² ) ₂ structure into the general formula (4) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; And a third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to carry out a condensation reaction. The silsesquioxane complex polymer according to claim 1,
[Chemical Formula 4]

Wherein R ¹ , R ² , R ⁶ , a, D and d are as defined in formulas (1) to (3). Mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And an excess amount of an organosilane compound is added to introduce the Dd (OR ³ ) ₂ and Dd (OR ⁴ ) ₂ structures into the general formula ( ⁴ ) after the first step, and the acid catalyst is added to the reaction mixture A second step of adjusting the pH to acidic and then stirring; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of removing the single cage-forming structure through a recrystallization and a filtering process after the third step. The silsesquioxane complex polymer according to claim 1,
[Chemical Formula 4]

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , a, D and d are as defined in the general formulas (1) to (3). Mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ⁵ ) ₂ structure into the general formula (4) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of introducing an EeX ₂ structure into the end of the composite polymer after the third step, and then introducing an acidic catalyst into the reactor to convert the reaction solution into an acidic atmosphere and mixing and stirring the organosilane compound A method for producing the silsesquioxane complex polymer represented by the general formula (3);
[Chemical 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,
Wherein the mixed catalyst comprises a metal-based basic catalyst and an amine-based basic catalyst. 12. The method of claim 11,
Wherein the ratio of the amine-based basic catalyst to the metal-based basic catalyst is from 10 to 90: 10 to 90 parts by weight. A coating composition comprising the silsesquioxane complex polymer according to claim 1. 14. The method of claim 13,
Wherein the coating composition is a solventless type. 14. The method of claim 13,
The silsesquioxane complex polymer according to claim 1,
Initiator; And
Organic solvent;
≪ / RTI > 16. The method of claim 15,
Wherein the silsesquioxane complex polymer is 5 to 90 parts by weight based on 100 parts by weight of the coating composition. 16. The method of claim 15,
Wherein the coating composition further comprises a curing agent, a plasticizer, or an ultraviolet screening agent.