TW201546125A - Silsesquioxane composite polymer and method for manufacturing thereof - 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

Yttrium sesquioxane composite polymer and preparation method thereof (1) Field of invention

The present invention relates to a sesquisesquioxane composite polymer and a method for producing the same, and more particularly to a linear sesquioxane chain and a composite comprising a specific structure in a sesquisesquioxane polymer. The sesquioxane complex polymer which maximizes processability and physical properties of the chain and the cage sesquioxanes.

Background of the invention

The sesquioxanes are used in various fields in various fields. In particular, there have been several attempts to improve the processability and maximize the mechanical and physical properties, and research and development are still continuing. However, the previously developed sesquisquioxane polymer has insufficient deficiencies in satisfying both processability and mechanical physical properties.

For example, clathazin sesquioxane is used in various fields because it exhibits physical properties that exhibit a siloxane bond, but it is itself a crystalline structure, and there is a limit to solubility in solution processing, and a cage structure is applied. The result is the following: the weight of molecular units such as self-recrystallization Group, performance reproducibility cannot be guaranteed. In other representative structures, a linear sesquioxane-based solution is excellent in workability and can compensate for the disadvantages of the cage structure, but has a disadvantage that the physical properties are not as good as the cage structure of the crystal structure. Further, since the random type sesquisquioxane is polymerized in a free form, it is necessary to use a random type of Si-OH or Si-alkoxy group which is unstable in the polymer. The sesquioxane gel is limited by application and there is a problem that it is difficult to ensure reproducibility.

With regard to the structures of the above sesquiseses, it is continually attempted to control a specific structure according to the needs of the industry. As an example, U.S. Patent Publication No. US2011-0201827 attempts to control polyhedral sesquises using a decane coupling agent as a precursor to create unique advantages, but on the other hand, the cages are connected in a single unit. In the case of a linear shape and only a substituent, only the actual physical properties cannot be greatly improved. Therefore, the inventors of the present invention conducted research to compensate for the disadvantages of the above-mentioned sesquisestames to maximize the benefits, and as a result, confirmed that the polymer structure of a specific structure was designed, and the organic function introduced in the side chain was utilized. The initiation is carried out by simply introducing a hardening step, and as a result, excellent physical properties can be maintained for a long period of time, and thus can be used for various industrial materials such as main raw materials, added raw materials, and coating materials;

Summary of invention

In order to solve the problems as described above, it is an object of the present invention to provide a linear sesquioxane chain containing a specific structure in a polymer. And a sesquisquioxane composite polymer which has a cage-shaped sesquioxanes to maximize processability and physical properties.

Further, an object of the present invention is to provide a method for producing the above-described sesquisesquioxane composite polymer.

Moreover, it is an object of the present invention to provide a sesquinal sesquioxane coating composition comprising the above-described sesquisesquioxane composite polymer.

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

In the above chemical formulas 1 to 3, A is , B is E is , Y is independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], and at least one is [(SiO _3/2 R) _4+2n O], and X is independently R ¹⁰ or [ (SiO _3/2 R) _4+2n R], and at least one is [(SiO _3/2 R) _4+2n R], 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; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) acrylonitrile; thiol; isocyanate; Nitro; phenyl; substituted by hydrazine, halogen, amine, epoxy, (meth) acryl thiol, thiol, isocyanate, nitrile, nitro, phenyl or unsubstituted C ₁ to C ₄₀ alkyl; C ₂ to C ₄₀ alkenyl; C ₁ to C ₄₀ alkoxy; C ₃ to C ₄₀ cycloalkyl; C ₃ to C ₄₀ heterocycloalkyl; C ₆ -C ₄₀ aryl; C ₃ -C ₄₀ heteroaryl; C ₃ -C ₄₀ aralkyl; C ₃ -C ₄₀ aryloxy; or C ₃ -C ₄₀ aryl thiol, Preferably, C ₁ ~ is substituted or unsubstituted with hydrazine, halogen, amine, (meth) acryl fluorenyl, thiol, isocyanate, nitrile, nitro, phenyl, cyclohexyl epoxy. C alkyl, C ₄₀ alkenyl group of ₂ ~ C ₄₀ of, a group, an epoxy group, a cyclohexyl epoxy group, a (meth)acrylylene group, a thiol group, a phenyl group or an isocyanate group, and a and d are each independently an integer of from 1 to 100,000, preferably a from 3 to 1,000. , d is from 1 to 500, and further preferably a is from 5 to 300, d is from 2 to 100, and e is 1 or 2, preferably 1, and n is independently an integer of from 1 to 20, preferably from 3 to 10. .

Moreover, the present invention provides a surface strengthening method for a transparent substrate, which comprises applying a coating composition comprising the sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 9 on a transparent substrate and It hardens.

Further, the present invention provides an electronic article comprising the surface-reinforced transparent substrate.

Further, the present invention provides a protective sheet comprising the above surface-reinforced transparent substrate.

Further, the present invention provides a sesquisesquioxane composite polymer represented by Chemical Formula 1, which is characterized by comprising the following steps: a first step of adding an organic catalyst and an organic solvent to a reactor, and then adding an organic solvent The decane compound is condensed to produce the following chemical formula 4; a second step, after the first step, adding an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then adding the organodecane compound and stirring to Dd ( The OR ² ) ₂ structure is introduced into the chemical formula 4; and the third step, after the second step, a basic catalyst is added to the reactor to convert the reaction liquid to basicity and a condensation reaction is carried out.

In the above formula, R ¹ , R ² , R ⁶ , D, a and d are identical to those defined in Chemical Formulas 1 to 3.

Further, the present invention provides a sesquisesquioxane composite polymer represented by Chemical Formula 2, which comprises the steps of: a first step of mixing an alkaline catalyst and an organic solvent in a reactor, and then adding an organic compound; a decane compound is condensed to produce the above chemical formula 4; a second step, after the first step, an acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, and then an excess of the organic decane compound is added and stirred, as in the chemical formula The Dd(OR ³ ) ₂ and Dd(OR ⁴ ) ₂ structures are generally introduced into the chemical formula 4; in the third step, after the second step, a basic catalyst is added to the reactor to convert the reaction liquid into a base. The condensation reaction is carried out; and the fourth step, after the third step, is followed by a recrystallization and filtration process to remove the individual cage formation structure.

Further, the present invention provides a sesquisesquioxane composite polymer represented by Chemical Formula 3, which comprises the following steps: a first step of adding an organic decane compound after mixing a basic catalyst and an organic solvent in a reactor And condensing to produce the chemical formula 4; the second step, after the first step, adding an acid catalyst to the reactor to adjust the reaction liquid to be acidic, and then adding the organodecane compound and stirring to introduce Dd into the chemical formula 4 ( a structure of OR ⁵ ) ₂ ; a third step, after the second step, adding a basic catalyst to the reactor to convert the reaction liquid to basicity and performing a condensation reaction; and a fourth step, which is the third step After the step, an acid catalyst is introduced into the reactor to convert the reaction liquid into an acidic ambient gas, and the organic decane compound is mixed and stirred to introduce the EeX ₂ structure to the end of the composite polymer.

Further, the present invention provides a sesquinal sesquioxane coating composition comprising the above-described sesquisesquioxane composite polymer.

The sesquisesquioxane composite polymer of the present invention has both the processability of linear sesquioxanes and the excellent physical properties of the cage sesquioxanes, whereby when the coating solution is produced, Excellent physical properties, optical properties, heat resistance properties, and the like are imparted to various raw materials by a simple hardening step.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

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

[Chemical Formula 3]

In the above Chemical Formulas 1 to 3, A is , B is , E is , Y is independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], and at least one is [(SiO _3/2 R) _4+2n O], and X is independently R ¹⁰ or [ (SiO _3/2 R) _4+2n R], and at least one is [(SiO _3/2 R) _4+2n R], 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; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) acrylonitrile; thiol; isocyanate; Nitro; phenyl; substituted by hydrazine, halogen, amine, epoxy, (meth) acryl thiol, thiol, isocyanate, nitrile, nitro, phenyl or unsubstituted C ₁ to C ₄₀ alkyl; C ₂ to C ₄₀ alkenyl; C ₁ to C ₄₀ alkoxy; C ₃ to C ₄₀ cycloalkyl; C ₃ to C ₄₀ heterocycloalkyl; C ₆ -C ₄₀ aryl; C ₃ -C ₄₀ heteroaryl; C ₃ -C ₄₀ aralkyl; C ₃ -C ₄₀ aryloxy; or C ₃ -C ₄₀ aryl thiol, Preferably, C ₁ ~ is substituted or unsubstituted with hydrazine, halogen, amine, (meth) acryl fluorenyl, thiol, isocyanate, nitrile, nitro, phenyl, cyclohexyl epoxy. C alkyl, C ₄₀ alkenyl group of ₂ ~ C ₄₀ of, a group, an epoxy group, a cyclohexyl epoxy group, a (meth)acrylylene group, a thiol group, a phenyl group or an isocyanate group, and a and d are each independently an integer of from 1 to 100,000, preferably a from 3 to 1,000. , d is from 1 to 500, and further preferably a is from 5 to 300, d is from 2 to 100, and e is 1 or 2, preferably 1, and n is independently an integer of from 1 to 20, preferably from 3 to 10. .

The sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 3 is as follows: R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^8. An organic functional group represented by R ⁹ and R ¹⁰ and having a repeating unit which is constituted in the form of a and d, and which can be selectively introduced into the terminal by the terminal unit.

n in the [(SiO _3/2 R) _4+2n O] structure introduced in the repeating unit [D]d of the above Chemical Formula 1 or 2 may be replaced by an integer of 1 to 20, preferably 3 to 10, and further Preferably, the average n value is 4 to 5, and when the above n is 4, if the substituted structure is represented, it is as shown in the following Chemical Formula 5:

In the above formula, R is identical to the content defined in the above.

In the present invention, n in the [(SiO _3/2 R) _4+2n R] structure introduced in the repeating unit [E]e of the above Chemical Formula 3 may be replaced by an integer of 1 to 20, preferably 3 to 10, and further preferably an average n value of 4 to 5, for example, if the structure in which the above n is 4 is substituted, as shown in the following Chemical Formula 6:

In the above formula, R is identical to the content defined in the above.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 1 may be a polymer described in the following Tables 1 to 2. In the following Tables 1 to 6, ECHE means (epoxycyclohexyl)ethyl, GlyP means glycidoxypropyl, POMMA means (methacryloxy)propyl, and two are described. In the case of the above, it means mixed use. n is independently 1 to 8.

As a specific example, the above-mentioned chemical formula 2 sesquisesquioxane composite high score The polymer may be a polymer described in the following Tables 3 and 4.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 3 may be a polymer described in the following Tables 5 and 6.

The above-mentioned sesquisesquioxane composite polymer of the present invention can be adjusted to have a wide range of applicability in order to secure excellent storage stability, and the degree of condensation can be adjusted to 1 to 99.9% or more. That is, the content of the alkoxy group bonded to the terminal and the center of Si can be adjusted to 50% to 0.01% with respect to the bonding group of the entire polymer.

Further, the weight average of the sesquioxane complex polymer of the present invention The molecular weight may be from 1,000 to 1,000,000, preferably from 5,000 to 100,000, and further preferably from 7,000 to 50,000. In this case, the processability and physical properties of the sesquioxanes can be simultaneously improved.

The sesquisesquioxane composite polymer of the present invention can be produced by continuously adjusting the alkali and the pH by using a basic catalyst and an acid catalyst in a single reactor, and any of the following production methods can be used.

Method for producing sesquisesquioxane composite polymer represented by chemical formula 1

The sesquisesquioxane composite polymer represented by the above Chemical Formula 1 of the present invention comprises the following steps: a first step of mixing an alkali catalyst and an organic solvent in a reactor, then adding an organic decane compound and condensing The following chemical formula 4 is produced; a second step, after the first step, an acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, and then the organodecane compound is added and stirred to form a Dd(OR ² ) ₂ structure. After introducing the chemical formula 4; and the third step, after the second step, a basic catalyst is added to the reactor to convert the reaction liquid to basicity and a condensation reaction is carried out. The produced sesquisesquioxane composite polymer has a structure of the following Chemical Formula 1-1.

[Chemical Formula 1-1]

In the above formula, R, R ¹ , R ² , R ⁶ , R ⁷ , D, Y, a and e are identical to those defined in Chemical Formulas 1 to 3.

Method for producing sesquisesquioxane composite polymer represented by chemical formula 2

When the following steps are carried out, the produced composite polymer has a structure of the following chemical formula 2-1, and the steps are: a first step of adding an organic decane compound after mixing the basic catalyst and the organic solvent in the reactor And condensing to produce the following chemical formula 4; the second step, after the first step, adding an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then adding the organodecane compound and stirring to [D]d (OR ² ) ₂ is introduced into the chemical formula 4; in the third step, after the second step, a basic catalyst is added to the reactor to convert the reaction liquid to basicity and a condensation reaction is carried out; and a purification step is performed. The cage structure which is separately produced as a by-product by the reaction of the third step is removed by recrystallization.

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

Method for producing sesquisesquioxane composite polymer represented by chemical formula 3

The method includes the following steps: after mixing a basic catalyst and an organic solvent in a reactor, adding an organic decane compound and condensing to produce the following chemical formula 4; a second step, after the first step, in the reactor After adding an acidic catalyst and adjusting the reaction solution to be acidic, an organodecane compound is added and stirred to introduce a Dd(OR ⁵ ) ₂ structure to Chemical Formula 4; a third step, which is added to the reactor after the above second step a basic catalyst converts the reaction liquid to alkaline and performs a condensation reaction; and a fourth step, after the third step, the acid catalyst is introduced into the reactor to convert the reaction liquid into an acidic environmental gas, and the mixture is mixed. The organic decane compound is stirred and introduced to introduce the EeX ₂ structure to the end of the composite polymer. The produced sesquisesquioxane composite polymer has a structure of the following Chemical Formula 3-1.

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

In the method for producing the above-mentioned sesquisesquioxane composite polymer, it is preferred to use a mixed catalyst of two or more kinds of basic catalysts as the basic catalyst. By re-hydrolysis by neutralization and acidification using an acidic catalyst, and condensing under alkaline conditions using a mixed catalyst of two or more kinds of basic catalysts, the acidity can be continuously adjusted in one reactor and Alkalinity.

In this case, the basic catalyst may be a metal-based basic catalyst selected from the group consisting of Li, Na, K, Ca, and Ba, and two or more selected from the group consisting of amine-based basic catalysts. Made by combining. Preferably, the amine-based basic catalyst may be tetramethylammonium hydroxide (TMAH), and the metal-based basic catalyst may be potassium hydroxide (KOH) or sodium hydrogencarbonate (NaHCO ₃ ). In the above mixed catalyst, the content of each component is preferably such that the ratio of the amine-based basic catalyst to the metal-based basic catalyst can be arbitrarily adjusted within a ratio of 10 to 90:10 to 90 parts by weight. In the case of the above range, there is an advantage that the reactivity of the functional group and the catalyst can be minimized upon hydrolysis, whereby the defects of the organic functional group such as Si-OH or Si-alkoxy group are remarkably reduced. Thereby, the degree of condensation can be freely adjusted. Further, the acidic catalyst can be used without limitation as long as it is an acidic substance generally used in the art, and for example, an ordinary acidic substance such as HCl, H ₂ SO ₄ , HNO ₃ or CH ₃ COOH can be used. Organic acid substances such as lactic acid, tartaric acid, maleic acid, and citric acid can also be used.

In the method for producing a sesquisquioxane composite polymer of the present invention, the organic solvent may be used without limitation as long as it is an organic solvent generally used in the art. For example, not only methanol, ethanol or isopropanol can be used. Alcohols such as butanol and 赛路苏, lactic acid, ketones such as acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan such as tetrahydrofuran, and dimethylformamide a polar solvent such as dimethylacetamide or N-methyl-2-pyrrolidone. Hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile can also be used. Various solvents such as (acrylonitrile), dichloromethane, octadecylamine, aniline, dimethylhydrazine, and benzyl alcohol.

Further, as the above organic decane-based compound, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in} Chemical Formulas 1 to 3 containing the sesquisesquioxane composite polymer of the present invention can be used. As the organic decane of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , it is preferred to use an organic group containing a phenyl group or an amine group which has an effect of increasing the chemical resistance of the sesquioxane complex polymer and improving the non-swelling property. A decane compound or an organic decane compound having an epoxy group or a (meth) acrylonitrile group having an effect of increasing the hardening density of the composite polymer to increase the mechanical strength and hardness of the hardened layer.

Specific examples of the above organic decane-based compound include (3-glycidoxypropyl)trimethoxynonane, (3-glycidoxypropyl)triethoxydecane, and (3-glycidol). Oxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)dimethylethoxydecane, 3-(methacryloxy)propyltrimethoxydecane, 3, 4-epoxybutyltrimethoxydecane, 3,4-epoxybutyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4 - Epoxycyclohexyl)ethyltriethoxydecane, aminopropyltriethoxydecane, vinyltriethoxydecane, vinyltris-tert-butoxydecane, vinyltriisobutoxydecane , vinyl triisopropoxy decane, vinyl triphenoxy decane, phenyl triethoxy decane, phenyl trimethoxy decane, aminopropyl trimethoxy decane, N-phenyl-3-amine Propyltrimethoxydecane, dimethyltetramethoxyoxirane, diphenyltetramethoxyanthracene Etc.; one of these may be used alone or in combination of two or more. In order to obtain the physical properties of the composition to be finally produced, it is more preferable to use two or more kinds of the mixture.

Preferably, the pH of the reaction liquid in the first step of the present invention is preferably from 9 to 11.5, the pH of the reaction liquid in the second step is preferably from 2 to 4, and the pH of the reaction liquid in the third step is preferably 8 to 11.5, the pH of the reaction liquid for the fourth step of the chemical formula 3 is preferably from 1.5 to 4. When it is in the above range, not only the yield of the produced sesquisesquioxane composite polymer is high, but also the mechanical properties of the produced sesquisesquioxane composite polymer can be improved.

Furthermore, the present invention provides a coating composition comprising the sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1-3. When the sulfonium sesquioxane composite polymer is in the form of a liquid, the above coating composition may be applied alone without a solvent, and when the sesquisesquioxane composite polymer is in a solid state, the above coating composition It may be composed of an organic solvent. Further, the coating composition may further comprise a starter or a hardener.

It is preferable that the coating composition is characterized by comprising a sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 3 and an organic compound generally used in the art which is compatible with the above composite polymer. The solvent and the initiator may optionally and additionally contain additives such as a curing agent, a plasticizer, an ultraviolet blocking agent, and other functional additives to improve curability, heat resistance, ultraviolet blocking, plasticizing effect, and the like.

In the coating composition of the present invention, the above-mentioned sesquisesquioxane composite polymer preferably contains at least 5 parts by weight or more, preferably 5 parts by weight to 90 parts by weight, based on 100 parts by weight of the coating composition. It is preferably contained in an amount of 10 to 50 parts by weight. If it is within the above range, it may be further mentioned Mechanical properties of the cured film of the high coating composition.

As the organic solvent, not only alcohols such as methanol, ethanol, isopropanol, butanol, and sarcosyl, but also lactic acid, ketones such as acetone and methyl (isobutyl) ethyl ketone, and ethylene glycol can be used. For the polar solvents such as glycols, tetrahydrofuran, etc., polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, hexane, cyclohexane, and cyclohexanone may also be used. , toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, dichloromethane, octadecylamine Various solvents such as aniline, dimethyl hydrazine, and benzyl alcohol are not limited thereto. The amount of the above organic solvent is the balance after removing the composite polymer, the initiator, and the optional additive.

Further, in the coating composition of the present invention, the above-mentioned initiator or curing agent can be appropriately selected and used depending on the organic functional group contained in the sesquisesquioxane composite polymer.

As a specific example, when the organic functional group is introduced into an organic system which can be post-cured, such as an unsaturated hydrocarbon, a thiol type, an epoxy type, an amine type, or an isocyanate type, various hardening by heat or light can be used. In this case, although it is possible to change the heat or light in the polymer itself, it is preferred to obtain a curing step by diluting it in such an organic solvent.

Further, in the present invention, for the curing of the composite polymer and the subsequent reaction, various initiators may be used, and the above-mentioned initiator is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight based on the total weight of the composition. When the content in the above range is satisfied, the transmittance after curing and the coating stability can be simultaneously satisfied.

Further, when introducing an unsaturated hydrocarbon or the like into the above organic functional group, a radical initiator may be used, and as the radical initiator, trichloroacetophenone or diethoxybenzene may be used. Diethoxy acetophenone, 1-phenyl-2-hydroxyl-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1-(4-methylthienyl)-2- Benzylpropan-1-one, (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (trimethyl Benzoyl diphenylphosphine oxide), camphorquinone, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylbutyrate) dimethyl ester, 3, 3-dimethyl-4-methoxy-diphenyl ketone, p-methoxydiphenyl ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2 - Photoial free radical initiator such as diphenylethane-1-one, tert-butylperoxy maleic acid, tert-butyl hydroperoxide, 2,4-dichlorobenzamide peroxide , 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, N-4,4'-di(t-butylperoxy)pentanoic acid, etc. A free radical initiator, and various mixtures of the foregoing, and the like.

Further, when the organic functional group contains an epoxy group or the like, a lanthanide such as triphenylsulfonium or diphenyl-4-(phenylthio)phenylhydrazine can be used as the photopolymerization initiator (cation). , diphenyl hydrazine or bis(dodecylphenyl) fluorene, etc., diazonium such as phenyldiazonium, 1-benzyl-2-cyanopyridinium or 1-(naphthylmethyl)- Ammonium such as 2-cyanopyridinium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-phosphonium hexafluorophosphate, bis(4-t-butylphenyl)hexafluorophosphate Barium phosphate, barium diphenyl hexafluorophosphate, barium diphenyl trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolylsulfonium triflate, and Fe cations such as (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe and BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- etc. [BQ ₄ ] ^-鎓 salts Combination (here, Q is a phenyl group substituted with at least 2 or more fluorine or trifluoromethyl groups).

Further, as the cationic initiator which acts by heat, a cationic system such as a trifluoromethanesulfonate, a boron trifluoride ether complex or a boron trifluoride or a protonic acid can be used without limitation. Catalyst, various salts of ammonium salts, barium salts and barium salts, and methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide, etc. It may be added in various mixed forms, and may also be mixed with various radical initiators as described above.

Further, depending on the kind of the above-mentioned organic functional group, an amine hardener such as ethylenediamine, tri-ethylidene tetraamine, tetraethylidene pentaamine, 1,3-diaminopropane, and di-propyltriamine can be used. , 3-(2-Aminoethyl)amino-propylamine, N,N'-bis(3-aminopropyl)-ethylenediamine, 4,9-dioxadecane-1, 12-Diamine, 4,7,10-trioxatridecane-1,13-diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-diaminomethylcyclohexane Alkane, bis(4-aminocyclohexyl)methane, lower An enediamine, a 1,2-diaminocyclohexane or the like.

Further, as a hardening accelerator for promoting the above hardening action, acetamidine may also be used. Benzoguanamine, 2,4-diamino-6-vinyl-second three Wait three a compound, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-benzimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, 1-methylimidazole, etc. Compound, 1,5-diazabicyclo[4.3.0]nonene-5,1,8-diazabicyclo[5.4.0]undecene-7, triphenylphosphine, diphenyl (p-toluene) Phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogen fluoride , tetrabutylphosphonium dihydrotrifluoride, and the like.

Further, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and A can also be widely used. Tetrahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 2,4-diethylpentane An acid anhydride hardener such as an acid anhydride.

The above hardener is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the composition.

Further, in the present invention, in order to improve hardness, strength, durability, moldability, and the like after the hardening step or the subsequent reaction, an ultraviolet absorber, an antioxidant, an antifoaming agent, a leveling agent, and a water repellent may be additionally contained. Additives such as flame retardants and subsequent improvers. The additive is not particularly limited in its use, and can be appropriately added insofar as it does not impair the properties of the substrate, that is, the properties such as flexibility, light transmittance, heat resistance, hardness, and strength. The above additives are preferably contained independently in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the composition.

Examples of the additive which can be used in the present invention include polyether-modified polydimethylsiloxane (for example, BYK-300, BYK-301, BYK-302, and BYK-331 which are BYK products). BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), Polyether modified hydroxyfunctional poly -dimethyl-siloxane, such as BYK-308 from BYK, BYK-373, etc., polymethylalkyl siloxane (Methylalkylpolysiloxane (such as BYK-077, BYK-085, etc.), polyether polymethylalkyl siloxane (Polyether modified methylalkylpolysiloxane, such as BYK-320, BYK-325, etc., Polyester modified poly-methyl-alkyl-siloxane (such as BYK-315, etc.), aralkyl polymethyl alkyl decaneane (Aralkyl modified Methylalkyl polysiloxane (such as BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370, etc.), polyester propylene fluorenyl polydimethyl methoxy oxane (Acrylic functional polyester modified polydimethylsiloxane (such as BYK-371, BYK-UV3570, etc.), polyether-polyester modified hydroxy functional polydimethylsiloxane (such as BYK-375, etc.), poly Polyether modified dimethylpolysiloxane (such as BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic acid (Non-ionic) Acrylic copol Ymer (for example, BYK-380, etc.), ionic polyacrylic acid (Ion acrylic copolymer, such as BYK-381, etc.), polyacrylate (Polyacrylate, such as BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361N, BYK-357, BYK-358N, BYK-352, etc.), polymethacrylate (Polymethacrylate, such as BYK-390, etc.), polyether propylene fluorenyl polydimethyl decane (Polyether modified acryl functional polydimethylsiloxane (such as BYK-UV3500, BYK-UV3530, etc.), polyether siloxane) (Polyether modified A siloxane (for example, BYK-347, etc.), an alcohol alkoxylates (such as BYK-DYNWET800, etc.), an acrylate (Acrylate (for example, BYK-392, etc.), and a fluorinated polyacrylate (Silicone modified polyacrylate). OH-functional), such as BYK-Silclean 3700, etc.).

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

In the present invention, as for the method of applying the above coating composition, the manufacturer can of course spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating. A known method such as cloth, spin coating, curtain coating, spray coating, gravure coating or the like is arbitrarily selected and used.

The sesquisesquioxane composite polymer produced by the present invention may have a thread because it contains a linear sesquioxane chain and a cage sesquioxane chain composed of a linear sesquiacetyl polymer. The processability of the polymer and the excellent physical properties of the crystalline sesquioxanes are easily cured by the organic functional groups contained in the above structure, and thus can be widely applied to all organic-inorganic hybridizations to be used. The industry of molecules. Further, it is basically provided with excellent optical properties, physical properties, heat resistance properties, and the like, and can be widely used as a main component, an additive, or various coating materials.

In the following, the preferred embodiments are set forth to understand the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

Example 1 : Synthesis of a composite polymer of an oxime sesquioxane AD structure

The synthesis step is carried out in stages by continuous hydrolysis and condensation.

[Example 1-a] Manufacture of catalyst

In order to adjust the alkalinity, a 10% by weight aqueous solution of potassium hydroxide (Potassium hydroxide: KOH) was mixed with a 25% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) to prepare a catalyst 1a.

[Example 1-b] Synthesis of linear sesquioxalic acid structure

5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, and 1 part by weight of the catalyst prepared in the above Example 1-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and the mixture was stirred at room temperature for 1 hour, and then added dropwise. 20 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and 15 parts by weight of tetrahydrofuran were further added dropwise thereto, and the mixture was further stirred for 5 hours. The mixed solution in the stirring was dripped, and after removing and filtering the catalyst and the impurities by washing twice, the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group was confirmed by IR (Infrared) analysis. When the molecular weight was measured, it was confirmed that the linear heptasilane having a linear structure of the structure of Chemical Formula 4 has a molecular weight of 8,000 in terms of styrene.

[Example 1-c] Generation of continuous cage structure

To the mixed solution of the above Example 1-b, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise to obtain stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst produced in Example 1-a was again added. The pH of the mixed solution was adjusted to an alkaline state. At this time, an alkoxy-open D structure precursor is separately formed separately from the linear polymer. A small amount of the sample was dropped, and the residual ratio of methoxy was confirmed by H-NMR (Nuclear Magnetic Resonance) and IR analysis. Then, when the residual ratio was 20%, 0.36 wt% was gradually added dropwise. The pH was adjusted to be acidic by 10 parts by weight of an aqueous HCl solution. Thereafter, 1 part by weight of phenyltrimethoxysilane (Phenyltrimethoxysilane) was added dropwise thereto and stirred for 15 minutes, and then 20 parts by weight of a catalyst produced in 1-a was added. After mixing and stirring for 4 hours, it was confirmed that a polymer having a cage form was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After mixing and stirring for 4 hours, a part of the solution was dropped and analyzed by ²⁹ Si-NMR. As a result, it was confirmed that two analytical peaks of a structure in which a phenyl group was introduced in a sharp form were used, and it was confirmed that 50% or more of the composition was produced. The AD polymer of Chemical Formula 1 has no additional by-products. Further, the molecular weight in terms of styrene was measured to be 11,000.

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

Further, a sesquisesquioxane composite polymer was produced using the monomers described in Table 7 below. At this time, the manufacturing method uses the above-described Embodiments 1-b and 1-c in a peer-to-peer manner. The method used.

In the above Table 7, ECHETMS means 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, GPTMS means glycidoxypropyltrimethoxydecane, and MAPTMS means (methacryl)醯oxy)propyltrimethoxydecane, PTMS means phenyltrimethoxydecane, MTMS means methyltrimethoxydecane, and ECHETMDS means bis(epoxycyclohexylethyl)tetramethoxydioxane Alkane, GPTMDS means bis(glycidoxypropyl)tetramethoxydioxane, MAPTMDS means bis(methacryloxy)propyl, and PTMDS means di(phenyl)tetramethoxy Dioxazane, MTMDS means di(methyl)tetramethoxydioxane.

Example 2 : Synthesis of a composite polymer of a sesquioxane DAD structure

The following examples were used to produce a composite polymer of the D-A-D structure. The manufacture of the catalyst and the linear structure was carried out in the same manner as in the methods of Examples 1-a and 1-b, and then produced by the following method to produce a continuous D-A-D structure.

[Example 2-a] Generation of excess continuous cage structure

To the mixed solution of the above Example 1-b, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 25 parts by weight of 5 times the diphenyltetramethoxydisiloxane used in Example 1-b was added dropwise to obtain stable hydrolysis, and the mixture was stirred for 1 hour and then added again. The pH of the mixed solution was adjusted to an alkaline state by 7 parts by weight of the catalyst produced in Example 1-a. At this time, an alkoxy-open D structure precursor is separately formed separately from the linear polymer. A small amount of the sample was dropped, and the residual ratio of methoxy was confirmed by H-NMR and IR analysis. Then, when the residual ratio was 20%, 10 parts by weight of a 0.36% by weight aqueous HCl solution was gradually added dropwise. The pH is adjusted to be acidic. Thereafter, 1 part by weight of phenyltrimethoxysilane (Phenyltrimethoxysilane) was added dropwise thereto and stirred for 15 minutes, and then 20 parts by weight of a catalyst produced in 1-a was added. After mixing and stirring for 4 hours, it was confirmed that a polymer having a cage form was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After mixing and stirring for 4 hours, a part of the mixture was dropped and analyzed by ²⁹ Si-NMR. As a result, it was confirmed that two analytical peaks of a structure in which a phenyl group was introduced in a sharp form were used, and it was confirmed that AD of the chemical formula 1 was produced. The polymer has no additional by-products. Further, the molecular weight in terms of styrene was measured to be 14,000, and the average n value was 4.6. Further, it was confirmed by Si-NMR analysis that, unlike the AD structure, the peak near -68 ppm which appeared at the end of the A structure disappeared, and the end of the A structure was converted into the D structure to form a DAD structure.

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

Further, a sesquisesquioxane composite polymer was produced using the monomers described in Table 8 below. At this time, the manufacturing method uses the method used in the above embodiment 2 in a peer-to-peer manner.

In the above Table 8, ECHETMS means 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, GPTMS means glycidoxypropyltrimethoxydecane, and MAPTMS means (methacryl)醯oxy)propyltrimethoxydecane, PTMS means phenyltrimethoxydecane, MTMS means methyltrimethoxydecane, and ECHETMDS means bis(epoxycyclohexylethyl)tetramethoxydioxane Alkane, GPTMDS means bis(glycidoxypropyl)tetramethoxydioxane, MAPTMDS means bis(methacryloxy)propyl, and PTMDS means di(phenyl)tetramethoxy Dioxazane, MTMDS means di(methyl)tetramethoxydioxane.

Example 3 : Synthesis of a composite polymer of a sesquioxane EAD structure

The following examples were used to produce a composite polymer of the E-A-D structure. The production of the catalyst and the linear structure was carried out in the same manner as in Example 1, and thereafter, the production was carried out by the following method to produce an E-A-D structure.

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

20 parts by weight of dichloromethane was added to the AD mixture obtained in Example 1-c without further purification, and 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted so as to be acidic. Stir at a temperature of 4 ° C for 30 minutes. Thereafter, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, a portion which has not been hydrolyzed in the molecular structure is easily converted into a hydrolyzate by an acidic aqueous layer which has been separated from the solvent, and is condensed with the other reactant formed by the organic solvent layer at the end. The unit imports E. After stirring for 5 hours, the stirring of the reaction was stopped, and the temperature of the reactor was adjusted to normal temperature.

[Example 3-b] Introducing a cage in the end E structure

After preparing the organic layer of the result obtained in the above Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of methyl trimethoxysilane (Methyltrimethoxysilane) was added dropwise to the mixed solution of Example 3-a in the reaction to obtain stable hydrolysis, and after stirring for 24 hours, the product produced in Example 1-a was again added. The pH of the mixed solution was adjusted to an alkaline state by 3 parts by weight of the catalyst. At this time, a polymer in a cage form is introduced into the end of the E structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 3. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature is changed to normal temperature, and the tetrahydrofuran in the mixed solution is removed by vacuum to prepare purification.

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

The mixture after completion of the reaction in the above Example 3-b was obtained, and then washed with distilled water. When the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and stored in a solvent of 30 parts by weight of tetrahydrofuran and an aqueous solution in a weight ratio of 9.5:0.5, and stored at -20 ° C for 2 days. . The object of the invention is to recrystallize a substance which is not introduced into a polymer and which is blocked by a cage structure, so that purification can be easily carried out.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and then the polymer of Chemical Formula 3 and various by-products were obtained together by vacuum reduction. Further, when the results of GPC (Gel Permeation Chromatography) were compared with the NMR results, the results were obtained in a sharp Cage form without being obtained by polymer growth in each step. From the viewpoint of the low molecular weight, it was confirmed that the composite polymer was obtained without problems. At this time, the molecular weight was 17,000 in terms of styrene, and the average value of n was 4.6. In particular, the results of Chemical Formula 3 were as follows.

²⁹ Si-NMR (CDCl ₃ ) δ - 68.2, -11.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

Further, a sesquisesquioxane composite polymer and a coating composition were produced using the monomers described in Table 9 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 3 in a peer-to-peer manner.

[Table 9]

In the above Table 9, ECHETMS means 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, GPTMS means glycidoxypropyltrimethoxydecane, and MAPTMS means (methacryl)醯oxy)propyltrimethoxydecane, PTMS means phenyltrimethoxydecane, MTMS means methyltrimethoxydecane, and ECHETMDS means bis(epoxycyclohexylethyl)tetramethoxydioxane Alkane, GPTMDS means bis(glycidoxypropyl)tetramethoxydioxane, MAPTMDS means bis(methacryloxy)propyl, and PTMDS means di(phenyl)tetramethoxy Dioxazane, MTMDS means di(methyl)tetramethoxydioxane.

Example 4 : Manufacture and procedure of coating composition using sesquisesquioxane composite polymer

The coating composition was produced by initiating a hardening step by itself using the sesquioxane complex polymer obtained in Examples 1, 2 and 3.

[Example 4-1] Production of Photocurable Coating Composition

20 g of the sesquisesquioxane composite polymer of Chemical Formula 1 produced in the above Example 1 was dissolved in methyl ethyl ketone at 20% by weight. 100 g of the coating composition was made. Thereafter, 5 parts by weight of diphenylanthracene and 1 part by weight of BYK-347 were added to 100 parts by weight of the coating composition, and the mixture was stirred for 10 minutes to prepare a photocurable coating composition.

[Example 4-2] Hardening of photocurable coating composition

The coating composition prepared in Example 4-1 was applied onto a SKC-SG00L 250 um film as a PET (Polyethylene Terephthalate) film of SKC Corporation, and No. 30- Mayer coating was carried out by dividing 50 rods into 5 units. Thereafter, solvent removal was carried out at a temperature of 80 ° C for 10 minutes, and UV-irradiation was carried out for 10 seconds using a UV (Ultraviolet) machine using a 100 mW/cm ² lamp to obtain a resultant product.

[Example 4-3] Production of thermosetting coating composition

50 g of the sesquisesquioxane composite polymer represented by Chemical Formula 3-1 produced in the Example was dissolved by 50% by weight of 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 each of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, and the mixture was stirred for 10 minutes to prepare a thermosetting coating. combination.

[Example 4-4] Hardening of thermosetting coating composition

The coating composition prepared in Example 4-3 was applied onto a SKC-SG00L 250 um film as a PET film of SKC Co., Ltd., and a rod of No. 30 to 50 was divided into five units and implemented. Mayer coating. After coating, the resultant was obtained by hardening in a drying oven at 80 ° C for 10 minutes.

[Example 4-5] Self-curing of Chemical Formulas 1, 2, and 3 obtained using the examples

The results obtained by Examples 1, 2 and 3 were hardened via heat without other compositions. A rod of No. 30 to 50 was divided into five units, and Mayer coating was applied to a SKC-SG00L 250 um film as a PET film of SKC, and hardened in a drying oven at 100 ° C. The result was obtained after 2 hours.

[Experimental Example 1]

The sesquisesquioxane resin produced by Example 1 was measured using 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). Weight average molecular weight and molecular weight distribution. THF (Tetrahydrofuran, tetrahydrofuran) was used for the flow rate 1 at 40 ° C, and the sample was separated by 4 columns (Shodex-GPC KF-802, KF-803, KF-804, and KF-805). As a result, it was confirmed by SEC (Size-exclusion chromatography) analysis that the obtained sesquisesquioxane had a weight average molecular weight of 12,000 and a molecular weight distribution of 1.8.

[Experimental Example 2]

IR was determined using the ATR mode of Perkin-Elmer FT-IR system Spectrum-GX. As a result of FT-IR (Fourier Transform Infrared Radiation) analysis, a broad double peak was observed at 950 to 1200 cm ^-1 in a small amount of the structure suitable in the process of Example 1-b. Sex (two consecutive junmo ( The amount of absorption peaks, which are the stretching vibrations of the decane bonds in the vertical (-Si-O-Si-R) and level (-Si-O-Si-) directions in the sesquioxane chain ( Stretching Vibration). Thereafter, the composition of the structure obtained in 1-c was analyzed, and as a result, a peak shown at 1200 cm ^-1 was further grown, whereby the substitution of the cage structure was confirmed. Regarding this case, in the joint analysis with the results of the GPC analysis analyzed in Experimental Example 1, regardless of the growth of the basket-shaped characteristic peak, the actual molecular weight was not observed as a low-order cage (usually the molecular weight was 1,000~). 5,000 or so), in this respect, it can also be confirmed that the structure is introduced into the chain.

[Experimental Example 3]

The thermal stability of the structure produced by Examples 1, 2, and 3 was confirmed using a TGA (thermal gravimetric analyzer), and in particular, the composite polymer obtained by Chemical Formula 3-1 was measured. The measurement was carried out by TGA at a scanning speed of 10 ° C/min of 50-800 ° C under a nitrogen atmosphere. According to the measurement results, it was confirmed that the decomposition amount of Si-OH and Si-OR which were decomposed between 100 and 200 ° C was remarkably reduced by the terminal substitution of the cage structure.

[Experimental Example 4]

For the transparent substrate of PC (Polycarbonate, polycarbonate) (Glastic polycarbonate product of i-Components) SKC and PMMA (Polymethyl methacrylate) (COPA OAS-800) transparent substrate, use the above table. The polymer resin described in 7 to 9 was applied and cured by the same method as that described in Example 4, and the surface characteristics were measured. The results of the following experimental results are the results of using the polymer resin produced in Example 3, and are not described in the Table, but the coating composition using the polymer resin described in Tables 7 to 9 is expressed as in Example 3. The result of the equivalent of the polymer resin.

- Surface hardness measurement: In general, the pencil hardness method (JIS 5600-5-4) is usually evaluated with a load of 500 g, and the pencil is placed at an angle of 45 degrees on the coated surface under a more severe condition, that is, a 1 kgf load. The speed of 0.5 mm was moved horizontally by 3 mm to scrape the coated film, and the scratch was evaluated. If the scratch marks are not confirmed twice or more in 5 experiments, the pencil of high hardness is selected. If there are scratch marks for 2 or more times, the pencil is selected, and the pencil hardness is one hardness lower than the hardness of the pencil. The pencil hardness of the coated film. Regarding the evaluation results, the 9H hardness of the glass level was confirmed regardless of the type of the substrate at a coating thickness of 10 μm or more.

- Scratch test: 400 times with 1 kgf using Steel wool #0000. The abrasion evaluation method (JIS K5600-5-9) by steel wool is used to wind the steel wool of #0000 at the tip of a hammer of about 1 kg and to rub the test piece 15 times. The haze value was measured, and the test piece was rubbed under a harsh condition, that is, rubbed 400 times, and visually evaluated by haze measurement and a microscope. It was confirmed that the coating having a coating thickness of 5 μm or more was excellent in resistance to scratches generated on the surface.

- Subsequent force evaluation (JIS K5600-5-6): The coating film was cut at intervals of 1-5 mm by a blade, and a scotch tape was attached thereto to remove the number of tapes attached thereto. When the adhesion was judged, at this time, 100 grids were produced by a blade, and the adhesion was judged by the number of detachment among 100. The results are shown in Table 10 below. Regarding the description, the number of the 100 items that are not separated is described as "(the number of undivided/100)", and as an example, if 100 pieces are not separated, it is described as "(100/100)".

- Reliability evaluation: The bending characteristics were evaluated by storing in a reliability chamber of 85% and 85 ° C for 240 hours. The bending evaluation criteria were within ±0.1 mm before the reliability evaluation and within ±0.3 mm after the reliability evaluation.

The evaluation results were excellent in all substrates of PET, PC and PMMA.

As shown in the above Table 10, it was confirmed that the coating composition of the present invention exhibited not only excellent surface hardness and optical properties but also other physical properties.

Claims (17)

A sesquioxane complex polymer as shown in any one of Chemical Formulas 1 to 3: In the above Chemical Formulas 1 to 3, A is , B is , E is Y is independently O, NR ⁹ or [(SiO _3/2 R) _4+2n O], and at least one is [(SiO _3/2 R) _4+2n O], and X is independently R ¹⁰ or [( SiO _3/2 R) _4+2n R], and at least one of 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; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) acrylonitrile; thiol; isocyanate; Nitro; phenyl; C ₁ substituted or unsubstituted with hydrazine, halogen, amine, epoxy, (meth) acryl thiol, thiol, isocyanate, nitrile, nitro, phenyl ~C ₄₀ alkyl; C ₂ ~ C ₄₀ alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ An aryl group of C ₄₀ ; a heteroaryl group of C ₃ to C ₄₀ ; an aralkyl group of C ₃ to C ₄₀ ; an aryloxy group of C ₃ to C ₄₀ ; or an arylthiol group of C ₃ to C ₄₀ , a And d are each independently an integer from 1 to 100,000, preferably a is from 3 to 1000, d is from 1 to 500, e is 1 or 2, and n is an integer from 1 to 20. The sesquisesquioxane composite polymer of claim 1, wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently comprise C ₁ -C ₄₀ alkane substituted by halo, halogen, amine, (meth) propylene sulfhydryl, thiol, isocyanate, nitrile, nitro, phenyl, cyclohexyl epoxy or unsubstituted A group, an alkenyl group of C ₂ to C ₄₀ , an amine group, an epoxy group, a cyclohexyl epoxy group, a (meth)acrylinyl group, a thiol group, a phenyl group or an isocyanate group. The sesquioxane complex polymer of claim 1, wherein a is from 3 to 1,000 and d is from 1 to 500. The sesquimethoxane complex polymer of claim 1, wherein d is from 2 to 100. The sesquioxane complex polymer of claim 1, wherein the average value of n is 4 to 5. The sesquioxalic acid complex polymer of claim 1, wherein the linear sesquisesquioxane composite polymer of the above Chemical Formula 1 has a degree of condensation of from 1 to 99.9%. The linear sesquioxanes composite polymer of claim 1, wherein the linear sesquioxane complex polymer of the above Chemical Formula 1 has a weight average molecular weight of 1,000 to 1,000,000. A method for producing a sesqui! sesquioxane composite polymer, which is characterized by the chemical formula 1, wherein the method for producing a sesquisesquioxane composite polymer comprises the steps of: In the first step, after mixing the basic catalyst and the organic solvent in the reactor, the organodecane compound is added and condensed to produce the following chemical formula 4; and the second step, after the first step, the acid is added to the reactor. After the reaction solution is adjusted to be acidic, the organodecane compound is added and stirred to introduce the Dd(OR ² ) ₂ structure to the chemical formula 4; and the third step, after the second step, the base is added to the reactor. Converting the reaction solution to basicity by a catalytic catalyst and performing a condensation reaction; In the above formula, R ¹ , R ² , R ⁶ , D, a and d are identical to those defined in Chemical Formulas 1 to 3. A method for producing a sesquisesquioxane composite polymer, which is represented by Chemical Formula 2, wherein the method for producing a sesquisesquioxane composite polymer comprises the steps of: In the first step, after mixing the basic catalyst and the organic solvent in the reactor, the organodecane compound is added and condensed to produce the above chemical formula 4; and the second step, after the first step, the acidic contact is added to the reactor. After the reaction liquid is adjusted to be acidic, an excess of the organic decane compound is added and stirred to introduce the Dd(OR ³ ) ₂ and Dd(OR ⁴ ) ₂ structures to the chemical formula 4 as in the chemical formula 2; After the second step, a basic catalyst is added to the reactor to convert the reaction liquid to alkaline and a condensation reaction is carried out; and a fourth step, after the third step, is subjected to recrystallization and filtration to remove the individual cage. Shape generation structure; [Chemical Formula 4] In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , a, D and d are identical to those defined in Chemical Formulas 1 to 3. A method for producing a sesqui! sesquioxane composite polymer, wherein the sesquisesquioxane composite polymer is represented by Chemical Formula 3, and the method for producing the sesquisesquioxane composite polymer comprises the steps of: Step 1 After mixing the basic catalyst and the organic solvent in the reactor, the organodecane compound is added and condensed to produce the chemical formula 4; the second step, after the first step, the acid catalyst is added to the reactor to react After the liquid is adjusted to be acidic, the organodecane compound is added and stirred to introduce the structure of Dd(OR ⁵ ) ₂ in Chemical Formula 4; and in the third step, after the second step, the basic catalyst is added to the reactor to react the reaction. The liquid is converted to alkaline and subjected to a condensation reaction; and in the fourth step, after the third step, the acid catalyst is introduced into the reactor to convert the reaction liquid into an acidic ambient gas, and the organic decane compound is mixed and stirred. Introducing the EeX ₂ structure to the end of the composite polymer; [Chemical Formula 4] In the above formula, R ¹ , R ² , R ⁵ , R ⁶ , a, D, E, X, d and e are identical to those defined in Chemical Formulas 1 to 3. The method for producing a sesquisesquioxane composite polymer 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. The method for producing a sesquisesquioxane composite polymer according to claim 11, wherein the ratio of the amine-based basic catalyst to the metal-based basic catalyst is 10 to 90:10 to 90 parts by weight. A coating composition comprising the sesquisesquioxane composite polymer of claim 1. The coating composition of claim 13, wherein the coating composition is a solventless type. The coating composition of claim 13, which comprises: the sesquisesquioxane complex polymer of claim 1; an initiator; and an organic solvent. The coating composition of claim 15, wherein the above-mentioned sesquisesquioxane composite polymer is from 5 to 90 parts by weight based on 100 parts by weight of the coating composition. The coating composition of claim 15, wherein the above coating composition is further Contains hardeners, plasticizers or sunscreens.