TW201602264A - A coating method for ceramics using silsesquioxane composite polymer - Google Patents

Abstract

The present invention relates to a method for coating ceramic using a silsesquioxane composite polymer, and more specifically, by coating the ceramic surface by means of a silsesquioxane composite polymer comprising, within a single polymer, a linear silsesquioxane chain of a particular structure and cage-type silsesquioxane, the method for coating ceramic using a silsesquioxane composite polymer facilitates the coating process, and the formed coating layer has superb crack resistance, resistance to the pin-hole phenomena, water repellency, moisture resistance, and soil resistance, as well as excellent adhesiveness.

Description

Ceramic coating method using sesquisesquioxane composite polymer Field of invention

The present invention relates to a ceramic coating method using a sesquisesquioxane composite polymer, and more particularly to a ceramic coating method using a sesquisesquioxane composite polymer as follows: for use in a polymer The surface of the ceramic is coated on the surface of the ceramic by a linear sesquioxane chain containing a specific structure and a caged sesquioxanes, whereby not only the coating step is easy but also formed The coating is excellent in crack resistance, pinhole resistance, water repellency, water repellency and antifouling properties, and is excellent in adhesion.

Background of the invention

In general, ceramic products can be used not only for buildings, structures such as wall materials, flooring materials, tiles, roofing materials, but also for household items such as cups, plates, containers, etc., or for industries such as semiconductor manufacturing equipment. In particular, glass systems are widely used in windows for buildings, glass for automobiles, optical products, glasses, and electronic products.

Moreover, since ceramic products form a unique lattice structure of ceramics, It exhibits excellent properties physically in various fields. In particular, the close-packed lattice structure has excellent barrier properties for blocking the passage of gas and moisture, and thus can be widely applied to the gas barrier field of recently emerging LED displays.

However, the ceramic product has the following disadvantages: in terms of the characteristics of the inorganic substance, even a weak deformation due to the weak soft characteristic causes a significant decrease in barrier properties such as cracking and pinhole phenomenon, and has been studied on the surface in order to fill the disadvantage. Attempts to form a coating film to complement the barrier properties.

As an example, a gas barrier film in which an inorganic layer containing ruthenium having a thickness of 10 to 1000 nm and a crosslinked resin layer having a pencil hardness of H or more is laminated is disclosed in Korean Patent Publication No. 10-2014-0018911. The result of using the excellent characteristics of the inorganic layer to drastically improve the gas barrier properties is derived. However, in this case, there are also problems in that the steps are complicated, and the inorganic layer is detached, and cracking and pinhole phenomenon are insufficiently prevented.

Summary of invention

In order to solve the problems as described above, it is an object of the present invention to provide a ceramic coating method which coats a ceramic surface using a coating solution, whereby not only the coating step is relatively easy, but also the formed coating layer It is excellent in crack resistance, pinhole resistance, water repellency, water repellency and antifouling properties, and has excellent adhesion.

Moreover, it is an object of the present invention to provide a ceramic coating composition The material imparts excellent crack resistance, pinhole resistance, water repellency, water repellency and antifouling properties to the ceramic.

Further, an object of the present invention is to provide a ceramic having a coating layer on the surface which is excellent in anti-crack property, pinhole prevention property, water-repellent property, water-repellent property and anti-fouling property, and excellent in adhesion.

Further, it is an object of the present invention to provide an article characterized by comprising a ceramic having the above coating.

In order to achieve the above object, the present invention provides a ceramic coating method characterized by coating a ceramic coating comprising a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 on a ceramic surface. Composition and hardening:

In the above Chemical Formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ 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 ²² 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 And R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ -C ₄₀ aralkyl; C ₃ -C ₄₀ aryloxy; or C ₃ -C ₄₀ aryl thiol, preferably containing fluorene, halogen, amine, (A Acryl thiol, thiol, isocyanate, nitrile, nitro , phenyl, cyclohexyl epoxy-substituted or unsubstituted C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, amine, epoxy, cyclohexyl epoxy, (methyl) Acryl thiol, thiol, phenyl or isocyanate group, a and d are each independently an integer of from 1 to 100,000, preferably a from 3 to 1000, d from 1 to 500, and even more preferably from 5 to 300. d is 2 to 100, and b is independently an integer of 1 to 500, and e is independently 1 or 2, preferably 1, and n is independently an integer of 1 to 20, preferably 3 to 10.

Moreover, the present invention provides a ceramic coating composition comprising the sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 9.

Moreover, the present invention provides a sesquisesquioxane composite polymer coated ceramic characterized by comprising coating a ruthenium sesquioxane composite polymer comprising any one of the above Chemical Formulas 1 to 9 on a surface thereof. A cured product obtained by coating a ceramic and hardening the ceramic.

Further, the present invention provides an article comprising the above-described sesquisesquioxane composite polymer coated ceramic.

The ceramic coating method of the present invention coats the surface of the ceramic using a coating solution, whereby not only the coating step is relatively easy, but also the crack-preventing property, the pinhole prevention property of the formed coating layer, and the water-repellent property Excellent in properties, waterproof and anti-fouling properties, excellent in adhesion, and useful for wall materials (including cement wall materials), flooring materials (including cement flooring), bricks, tiles, roofing materials, windows, etc. Objects or structures; household items such as cups, plates, containers; semiconductor manufacturing equipment; glass for automobiles, optical products, glasses, electronic products, solar cells themselves, and glass for protection.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

The ceramic coating method of the present invention provides a ceramic coating method characterized by coating a ceramic coating comprising a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 on a ceramic surface. Composition and hardening:

[Chemical Formula 2]

[Chemical Formula 7]

In the above Chemical Formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ 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 ²² 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 And R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ -C ₄₀ aralkyl; C ₃ -C ₄₀ aryloxy; or C ₃ -C ₄₀ aryl thiol, preferably containing fluorene, halogen, amine, (A Acryl thiol, thiol, isocyanate, nitrile, nitro Phenyl, cyclohexyl epoxy groups of a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, the C ₂ ~ C ₄₀ alkenyl group, the amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylamide a mercapto 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 from 1 to 500, and even more preferably from 5 to 300. d is 2 to 100, and b is independently an integer of 1 to 500, and e is independently 1 or 2, preferably 1, and n is independently an integer of 1 to 20, preferably 3 to 10.

The ceramic coating method of the present invention and the ceramic coating composition used therefor will have the above repeating units of [A]a and [D]d and optionally have the specific unit of [B]b or [E]e The structure of the sesquioxane polymer is applied to the surface of the ceramic and hardened, whereby even a single coating layer can be formed by the solution step, and the crack resistance and pinhole prevention phenomenon can be excellent with respect to the ceramic. Characteristics, water-repellent properties, waterproof properties and anti-fouling properties.

In the present invention, the ceramic to be coated includes not only a product produced by processing a non-metallic or inorganic material but also a glass.

The sesquisesquioxane composite polymer of the above Chemical Formula 1 of the present invention may be produced by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organodecane compound is added and condensed. The following chemical formula 10 is produced; in the 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 [D]d (OR ² The structure ₂ is introduced into the chemical formula 10; 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.

[Chemical Formula 10]

In the above formula, R ¹ , R ² , R ¹⁶ , D, a and d are identical to those defined in Chemical Formulas 1 to 9.

The sesquisesquioxane composite polymer represented by the above Chemical Formula 2 of the present invention can be produced by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organodecane compound is added and condensed. The above chemical formula 10 is produced; in the 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 to [D]d (OR) ³ ) ₂ and [D]d(OR ⁴ ) ₂ are introduced into the chemical formula 10 as in the chemical formula 2; in the third step, after the above two steps, a basic catalyst is added to the reactor to convert the reaction liquid into a base. a condensation reaction; a fourth step, after the third step, adding a basic catalyst to the reactor to convert the reaction solution to basicity and performing a condensation reaction; and a purification step by recrystallization A cage structure which is separately produced as a by-product through the three-step reaction is removed.

The sesquisesquioxane composite polymer of the above Chemical Formula 3 of the present invention may be produced by the following steps: a first step of adding an organic decane compound and condensing after mixing a basic catalyst and an organic solvent in a reactor The above chemical formula 10 is produced; in the 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 [D]d(OR ⁵ ) ₂ is introduced into the chemical formula 10; a third step, after the above two steps, adding a basic catalyst to the reactor to convert the reaction liquid to basic and performing a condensation reaction; and a fourth step, which is the third step After the step, an acidic 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 [E]eX ₂ structure to the end of the composite polymer.

The sesquisesquioxane composite polymer of the above Chemical Formula 4 of the present invention may be produced by the following steps: a first step of adding an organic decane compound and adjusting the condensation after mixing the basic catalyst and the organic solvent in the reactor The above chemical formula 10 is produced in 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 organic decane compound is added and stirred to form the [B]b structure and The [D]d(OR ⁷ ) ₂ structure is introduced to the chemical formula 10; and the third step, after the above two steps, a basic catalyst is added to the reactor to convert the reaction liquid to basicity and a condensation reaction is carried out.

The sesquisesquioxane composite polymer of the above Chemical Formula 5 of the present invention may be produced by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organodecane compound is added and condensed. The above chemical formula 10 is produced; after the first step, after the acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, an excess of the organic decane compound is added and stirred to form the [B]b structure and [D]d(OR ⁸ ) ₂ , [D]d(OR ⁹ ) ₂ structure is introduced into the chemical formula 10; in the third step, after the above two steps, a basic catalyst is added to the reactor to convert the reaction liquid It is basic and performs a condensation reaction; and a fourth step, after the third step, removes a separate cage generating structure by a recrystallization and filtration process.

The sesquisesquioxane composite polymer represented by the above Chemical Formula 6 of the present invention may be produced by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organic decane compound is added and condensed. The above chemical formula 10 is produced; in the 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 organic decane compound is added and stirred to form the [B]b structure and [D a structure of d(OR ¹⁰ ) ₂ is introduced into Chemical Formula 10; a third step, after the second step, a basic catalyst is added to the reactor to convert the reaction solution to basicity and a condensation reaction is carried out; After the third step, the acidic 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 [E]eX ₂ structure into the composite polymer. End.

Preferably, in the method of the above Chemical Formulas 1 to 6, the pH of the reaction liquid of the first step of the present invention is preferably from 9 to 11.5, and the pH of the reaction liquid of the second step is preferably from 2 to 4, The pH of the reaction liquid of the third step is preferably from 8 to 11.5, and the pH of the reaction liquid of the fourth step of introducing Ee 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.

The sesquisesquioxane composite polymer represented by the above Chemical Formula 7 of the present invention may be produced by the following steps: a first step of mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic decane compound to produce a condensation The above chemical formula 10 is adjusted in two forms; in the second step, after adding an acidic catalyst to the reactor to adjust the reaction solution to be acidic, the organic decane compound is added and stirred to form the [B]b structure and [D ]d(OR ¹² ) ₂ structure is introduced into the chemical formula 10 obtained in the above first step; and in the third step, after the respective two-step reaction, a basic catalyst is added to the reactor to convert the reaction liquid into The condensation reaction is carried out by alkaline reaction, and the fourth step is carried out by condensing two or more kinds of substances obtained by the above three steps under basic conditions.

The sesquisesquioxane composite polymer represented by the above Chemical Formula 8 of the present invention may be produced by the following steps: a first step of mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic decane compound to produce a condensation The above chemical formula 10 is adjusted in two forms; the second step is to add an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then add the organodecane compound and stir to form the [B]b structure, [D ]d(OR ¹⁴ ) ₂ structure is introduced into the chemical formula 10 obtained in the above first step; and in the third step, after the respective two-step reaction, a basic catalyst is added to the reactor to convert the reaction liquid into Basically, the condensation reaction is carried out; in the fourth step, the two or more substances obtained by the above three steps are condensed and condensed under alkaline conditions; and the fifth step is carried out after the above four steps. An acid catalyst is added to the reactor of D]d(OR ¹³ ) _{2 to} adjust the reaction liquid to be acidic, and then the organic decane compound is added and stirred; and in the sixth step, after the above 5-step reaction, a base is added to the reactor. Sexual catalyst will reverse And was converted to a basic embodiment of the condensation reaction.

The sesquisesquioxane composite polymer of the above Chemical Formula 9 of the present invention may be produced by the following steps: a first step of mixing an alkali catalyst and an organic solvent in a reactor, and then adding an organic decane compound to produce a condensation The above chemical formula 10 of the two types of adjustment; the second step, wherein an acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, and then the organic decane compound is added and stirred to introduce the [B]b structure into the above The chemical formula 10 obtained in the first step; the third step, after the reaction in each of the second steps, adding a basic catalyst to the reactor to convert the reaction liquid to basicity and performing a condensation reaction; It is obtained by condensing two or more kinds of compounds obtained by the above third step under alkaline conditions; and in the fifth step, after the fourth step, for introducing [D]d(OR ⁵ ) ₂ After the acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, the organodecane compound is added and stirred. In the sixth step, after the reaction in the fifth step, a basic catalyst is added to the reactor to convert the reaction solution into Alkali Embodiment and condensation reaction; and the seventh step, in which, after the sixth step, and converted into acidic catalytic reaction liquid acidic atmosphere, and the mixture was stirred and organosilane compounds in a reactor, to [E] eX _{2 The} structure is introduced to the end of the composite polymer.

Preferably, in the method for producing the polymer of the above Chemical Formulas 7 to 9, the pH of the reaction liquid of the first step is preferably from 9 to 11.5, and the pH of the reaction liquid of the second step is preferably from 2 to 4, The pH of the reaction liquid in the third step is preferably from 8 to 11.5, the pH of the reaction liquid in the fourth step is preferably from 9 to 11.5, and the pH of the reaction liquid in the fifth step is preferably from 2 to 4, the sixth step. The pH of the reaction solution is higher than The pH of the reaction liquid of the seventh step of introducing Ee is preferably from 1.5 to 4, preferably from 8 to 11.5. 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.

Further, in the case where it is necessary, in order to further introduce the [B]b structure and the [D]d(OR) ₂ structure into each of the composite polymers, the composite polymer may be further included in the following two steps [B]. b repeating unit: adding an acidic catalyst to the reactor to adjust the reaction liquid to be acidic, adding an organodecane compound and stirring; and after the above steps, adding a basic catalyst to the reactor to convert the reaction liquid to alkaline And the condensation reaction is carried out.

Further, in the case where it is necessary, in order to introduce the [E]eX ₂ structure at the end of each of the composite polymers, the following steps may be included to further comprise a repeating unit of [E]e at the end of the hybrid polymer: The reaction solution was converted into an acidic ambient gas by an acidic catalyst, and the organic decane compound was mixed and stirred.

In the method for producing the above-mentioned sesquisquioxane composite polymer, it is preferred to use a mixed catalyst of two or more kinds of basic catalysts as an alkaline catalyst, and to neutralize and acidify them by using an acidic catalyst. The re-hydrolysis is initiated, and the mixed catalyst of two or more kinds of basic catalysts is used again to carry out condensation under alkaline conditions, and the acidity and alkalinity can be continuously adjusted in one reactor.

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, or hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform or dichlorobenzene. Various solvents such as dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, 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 9 containing the sesquisesquioxane composite polymer of the present invention can be used. Organic decanes of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² It is preferable to use an organic decane compound containing a phenyl group or an amine group having an effect of increasing the chemical resistance of the sesquioxane complex polymer to improve the non-swelling property, or to increase the hardening density of the composite polymer. An epoxy group or a (meth) acrylonitrile-based organic decane compound which enhances 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 The propyl trimethoxy decane, the dimethyltetramethoxy decane, the diphenyltetramethoxy decane, etc. 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.

In the present invention, n in the [(SiO _3/2 R) _4+2n O] structure introduced in the repeating unit [D]d of the above chemical formula may be replaced by an integer of 1 to 20, preferably 3 to 10 Further preferably, the average n value is 4 to 5. For example, when the above n is 4, if the substituted structure is represented, it is as shown in the following Chemical Formula 11:

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 [B]b or [E]e of the above chemical formula may be replaced by an integer of 1 to 20, Preferably, it is from 3 to 10, and further preferably, the average n value is from 4 to 5. For example, if the above-mentioned structure in which n is 4 is substituted, it is as shown in the following Chemical Formula 12:

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

As a specific example, the sesquisquioxane polymer of the present invention may be a polymer described in the following Tables 1 to 18. In the following Tables 1 to 9, ECHE means (epoxycyclohexyl)ethyl, and GlyP means glycidoxypropyl propyl group. POMMA means (methacryloxy) propyl group, and when two or more cases are described, it means mixed use. n is independently 1 to 8.

The sesquisesquioxane composite polymer of the above Chemical Formula 1 may be a polymer described in the following Table 1 or 2.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 2 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.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 4 may be a polymer described in the following Tables 7 and 8.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 5 may be a polymer described in the following Tables 9 and 10.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 6 may be a polymer described in the following Tables 11 and 12.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 7 may be a polymer described in the following Tables 13 and 14.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 8 may be a polymer described in the following Tables 15 and 16.

As a specific example, the sesquisesquioxane composite polymer of the above Chemical Formula 9 may be a polymer described in the following Tables 17 and 18.

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 polysilsesquioxane composite polymer of the present invention may have a weight average molecular weight of 1,000 to 1,000,000, preferably 5,000 to 100,000, and still more preferably 7,000 to 50,000. In this case, the processability and physical properties of the sesquioxanes can be simultaneously improved.

In the present invention, two or more kinds of composite polymers may be used as the ceramic coating composition containing the sesquisesquioxane composite polymer shown in any one of the above Chemical Formulas 1 to 9, and it is preferred to use Chemical Formula 3 A sesquioxane complex polymer as shown in any one of 9. In this case, the physical properties of the transparent substrate including the surface hardness can be further improved by including the repeating unit [B]b or [E]e.

In the present invention, when the sesquisesquioxane composite polymer is in the form of a liquid, the ceramic coating composition can be applied alone without a solvent, and when the sesquisesquioxane composite polymer is in a solid state. The ceramic coating composition may be composed of an organic solvent. Further, the coating composition may further comprise an initiator 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 9 and having compatibility with the above-mentioned composite polymer, which is generally used in the art. a solvent and a starter, and optionally and additionally containing a hardener, a plasticizer, Additives such as ultraviolet blocking agents and other functional additives improve hardenability, heat resistance, ultraviolet blocking, and plasticizing effects.

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. When it is in the above range, the mechanical properties of the cured film of the coating composition can be further improved.

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 the change in heat or light can be sought in the polymer itself, it is preferably The hardening step can be achieved by diluting in such an organic solvent.

Further, in the present invention, for the curing of the hybrid 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 20 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-methylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1-(4-methylthienyl)-2- 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- Photoactive radical initiator such as diphenylethyl-1-one, tert-butylperoxy maleic acid, tert-butyl hydroperoxide, 2,4-dichlorobenzhydryl peroxide, 1 Thermal radicals such as 1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, N-4,4'-di(t-butylperoxy)pentanoate Starting agent, and various mixtures of these, 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 (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe cation like Fe and _{^{BF 4 -, PF 6 -,}} SbF 6 - , etc. [BQ _4] ^- salt 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, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, and the like, can also be widely used. Methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl dimer An acid anhydride hardener such as an acid anhydride or 2,4-diethylglutaric anhydride.

The hardener is preferably contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition.

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, 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.

As an additive which can be used in the present invention, polyether II can be cited. Polyether-modified polydimethylsiloxane (for example, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341 as BYK products) Polyether modified hydroxyfunctional poly-dimethyl-siloxane (BYK-344, BYK-307 373, 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 modified methylalkyl polysiloxane (Aralkyl modified methylalkyl polysiloxane) For example, BYK-322, BYK-323, etc., Polyester modified hydroxy functional polydimethylsiloxane (such as BYK-370, etc.), polyester acrylonitrile-based polydimethyl siloxane ( Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV3570, etc., polyether-polyester modified hydroxy functional polydimethylsiloxane (such as BYK-375, etc.), polyether polydimethylsiloxane (Polyether modified dimethylpolysiloxane) , for example, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), non-ionic acrylic copolymer (such as BYK-380, etc.), ionic Polyacrylic acid (Ionic 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 modified acrylic functional polydimethylsiloxane (such as BYK- UV3500, BYK-UV3530, etc., polyether modified siloxane (such as BYK-347, etc.), alcohol alkoxylates (such as BYK-DYNWET800, etc.), acrylate (Acrylate, for example) BYK-392, etc., fluorinated polyacrylate (OH-functional), such as BYK-Silclean 3700, etc.

In the present invention, the method of applying the above ceramic coating composition to a ceramic surface may of course be applied by spin coating, bar coating, slit coating, dip coating, natural coating, and reverse. Any of known methods such as coating, roll coating, spin coating, curtain coating, spray coating, dipping, impregnation, gravure coating, etc., may be optionally used in the curing method, and of course, according to the composite polymer. The functional group is appropriately selected to use photo hardening or thermal hardening. It is preferred that in the case of heat hardening, the hardening temperature is 80 to 120 °C.

In the present invention, the coating thickness of the above coating composition can be arbitrarily adjusted, preferably from 0.01 to 500 μm, more preferably from 0.1 to 300 μm, still more preferably from 1 to 100 μm. When it is in the above range, not only the surface hardness of 7H or more can be stably ensured, but also the physical properties of the substrate are excellent. Especially above 10μm When the thickness of the laminate is coated, since the surface hardness can stably exhibit 9H, it can also be used as a substitute for glass.

Moreover, the present invention provides a sesquisesquioxane composite polymer coated ceramic and a product comprising the above sesquisesquioxane composite polymer coated ceramic, the sesquisesquioxane composite polymer coated ceramic characterized by comprising a cured product obtained by coating and hardening a ceramic coating composition comprising the sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 9 on the surface, the above-mentioned sesquioxalic acid The hybrid polymer coated ceramic can be produced by the above ceramic coating method.

In the sesquisesquioxane composite polymer coated ceramic of the present invention, the ruthenium sesquioxane composite polymer coating and the ceramic have excellent adhesion, and the formed sesquioxanes composite polymer coating on the ceramic surface Provides excellent anti-crack properties, anti-pinhole properties, water-repellent properties, waterproof properties and anti-fouling properties. The article comprising the sesquisesquioxane composite polymer coated ceramic of the present invention can be usefully used in various fields as a product comprising the above-described sesquisesquioxane composite polymer coated ceramic, and is particularly useful for wall materials. (including cement wall materials), flooring (including cement flooring), bricks, tiles, roofing materials, windows and other buildings or structures; household items such as cups, plates, containers; semiconductor manufacturing equipment; automotive glass, optical Products, glasses, electronic products, solar cells themselves, and glass for protection.

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.

In the embodiments of the invention described below, ECHETMS means 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, GPTMS means glycidoxypropyltrimethoxydecane, and MAPTMS means (methacryloxy)propyltrimethoxy Decane, PTMS means phenyltrimethoxydecane, MTMS means methyltrimethoxydecane, ECHETMDS means bis(epoxycyclohexylethyl)tetramethoxydioxane, GPTMDS means bis(glycidol) Etheroxypropyl)tetramethoxydioxane, MAPTMDS means bis(methacryloxy)propyl, PTMDS means di(phenyl)tetramethoxydioxane, MTMDS means Di(methyl)tetramethoxydioxane.

Example 1: Manufacture of a coating composition comprising copolymers 1 and 9

Regarding the synthesis step, continuous hydrolysis and condensation were carried out stepwise as follows.

[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 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 had 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. 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 other by-products remaining alone. Further, the molecular weight in terms of styrene was measured to be 11,000, and the n value was 4-6.

²⁹ Si-NMR (CDCl ₃ ) δ

[Example 1-d] Production of Photocurable Resin Composition

30 g of the sesquisesquioxane composite polymer obtained in the above Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of chloroacetophenone, 1 part by weight of BYK-347, and 1 part by weight of BYK-UV3500 were added to 100 parts by weight of the coating composition, and the mixture was stirred for 10 minutes to produce photohardening. Type coating composition.

[Example 1-e] Production of thermosetting resin composition

50 g of the sesquisesquioxane composite polymer obtained in the above Example 1-c was dissolved in methyl ethyl ketone at 50% by weight 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 produce thermosetting coating. Composition.

[Example 1-f] Coating composition composed of the polymer itself

The coating composition was constituted by only Example 1-c without other composition.

Further, a sesquisesquioxane composite polymer was produced using the monomers described in the following Table 19, and a coating composition was produced. At this time, the manufacturing method used the methods used in the above Examples 1-b, 1-c, 1-d, 1-e, and 1-f in a peer-to-peer manner.

[Table 19]

Example 2: Synthesis of a composite polymer of a sesquioxane D-A-D structure

Using the following examples, a composite polymer of the D-A-D structure was produced, and a coating composition was produced by a method corresponding to the method described in the above Example 1. 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 the methoxy group was confirmed by H-NMR and IR analysis. When the residual ratio was 20%, 10 parts by weight of a 0.36% by weight aqueous HCl solution was gradually added dropwise to adjust the pH. The value 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 does not have a separate by-product by-product. Further, the molecular weight in terms of styrene was measured to be 14,000, and the 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 all the ends of the A structure were 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 and a coating composition were produced using the monomers described in Table 20 below. At this time, the manufacturing method uses the method used in the above embodiment 2 in a peer-to-peer manner.

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

The composite polymer of the E-A-D structure was produced by the following examples, and was produced by the method corresponding to the method described in the above Example 1. Coating the composition. 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 dropwise 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] Introduction of the end E structure into a cage

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 was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for 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 n value was 4 to 6, and in particular, the result of Chemical Formula 3 was 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)

Further, a sesquisesquioxane composite polymer and a coating composition were produced using the monomers described in the following Table 21. At this time, the manufacturing method uses the method used in the above-described Embodiment 3 in a peer-to-peer manner.

Example 4: Synthesis of a composite sesquioxane polymer of A-B-D structure

In the synthesis step, a composite polymer having an E-A-D structure was produced by successively hydrolyzing and condensing as follows, and a coating composition was produced by a method corresponding to the method described in the above Example 1.

[Example 4-a] Manufacture of Catalyst for Hydrolysis and Condensation Reaction

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

[Example 4-b] Synthesis of linear sesquioxanes structure (synthesis of A-B precursor)

5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, and 0.5 part by weight of the catalyst prepared in the above Example 4-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and stirred at room temperature for 1 hour, followed by dropwise addition. 10 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and 20 parts by weight of tetrahydrofuran was further added dropwise thereto, and the mixture was further stirred for 2 hours. The mixed solution in the stirring was dripped, and the catalyst and the impurities were removed by washing twice to obtain a linear sesquisesquioxane. The residual alkoxy group was analyzed by ¹ H-NMR. 0.1 mmol/g or less. It is used to introduce a portion of the cage after continuous reaction. Regarding the morphological analysis of the linear structure, it was confirmed by XRD (X-ray diffraction) analysis that the integral structure was a linear structure. When the molecular weight was measured, it was confirmed that the linear structure of the sesquisesquioxane had a molecular weight of 6,000 in terms of styrene.

¹ H-NMR (CDCl ₃ ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.

[Example 4-c] pH conversion reaction for the formation of a cage structure in the chain (introduction of B and D structures)

To the mixed solution of Example 4-b in the reaction, 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 thereto, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was again added to mix the solution. The pH is adjusted to an alkaline state. In this case, it was confirmed that the structure of the cage form was separately formed from the linear structure and introduced into the polymer chain, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum, so that all The reactants are converted to an aqueous mixture. After the mixture was stirred for 4 hours, a part of the mixture was separated and analyzed by ²⁹ Si-NMR and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group present in the B structure was changed to 0.025 mmol/g. The repeating unit having B and D is introduced at a ratio of about 5:5. Further, the molecular weight in terms of styrene was measured to be 10,000. Further, although a cage structure was introduced, the molecular weight distribution of a separate cage material was not observed in the GPC form of the polymer, and it was confirmed that the cage structure was favorably introduced into the high state by continuous reaction. molecular chain.

¹ H-NMR (CDCl ₃ ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. ²⁹ Si-NMR (CDCl ₃ ) δ-72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)

[Example 4-d] Introduction of X into the B structure (introduction of B and D structures)

After preparing the organic layer of the result obtained in the above Example 4-c without further purification, the terminal was converted into a cage structure using a trifunctional monomer. After 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% of HCl was added to the produced mixed solution and stirred for 10 minutes, and then 3 parts by weight of methyltrimethoxysilane (Methyltrimethoxysilane) was added dropwise to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was again added to adjust the pH of the mixed solution to an alkaline state. At this time, a polymer in a cage form is introduced into the X portion of the B structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 4. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 4-e] Removal by by-product of precipitation and recrystallization, obtaining of the result

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 4-d, and washed separately 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.

Confirmed that the solid matter obtained by the end of the recrystallization process has passed After filtration, the polymer of Chemical Formula 4 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight is 12,000 in terms of styrene, the n value of X is 4-6, and the n value of Y is 4-6, and the result of Chemical Formula 4 is as follows.

²⁹ Si-NMR (CDCl ₃ ) δ-72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)

Further, a sesquisesquioxane composite polymer and a coating composition were produced using the monomers described in Table 22 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 4 in a peer-to-peer manner.

Example 5: Synthesis of a composite sesquioxane polymer of D-A-B-D structure

The composite polymer of the D-A-B-D structure was produced by the following method, and the coating composition was produced by the method equivalent to the above Example 1.

[Example 5-a] pH conversion reaction for excessive formation of D structure (introduction of B and D structures)

To the mixed solution of Example 4-b in the reaction, 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, the amount of diPhenyltetramethoxydisiloxane was prepared in an amount of 5 times, that is, 25 parts by weight of Example 4-b, and added dropwise at a time. After stirring for 1 hour, Example 1 was again added. The pH of the mixed solution was adjusted to an alkaline state by 5 parts by weight of the catalyst produced in a. After the end of the reaction, 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 and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group present in the B structure was changed to 0.012 mmol/g. The repeating unit having B and D is introduced at a ratio of about 1:9. Further, the molecular weight in terms of styrene was measured to be 24,000. Further, although a cage structure was introduced, the molecular weight distribution of a separate cage material was not observed in the GPC form of the polymer, and it was confirmed that the cage structure was favorably introduced into the high state by continuous reaction. molecular chain.

¹ H-NMR (CDCl ₃ ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. ²⁹ Si-NMR (CDCl ₃ ) δ-72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)

[Example 5-b] Introduction of X into the B structure (introduction of B and D structures)

After preparing the organic layer of the result obtained in the above Example 5-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. After 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% of HCl was added to the produced mixed solution and stirred for 10 minutes, and then 3 parts by weight of methyltrimethoxysilane (Methyltrimethoxysilane) was added dropwise to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was again added to adjust the pH of the mixed solution to an alkaline state. At this time, a polymer in a cage form is introduced into the X portion of the B structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 5. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 5-c] Removal by by-product of precipitation and recrystallization, obtaining of the result

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 5-b, and washed separately with distilled water. When the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. . its Thereafter, the unreacted monomers were removed by precipitation twice in methanol, and 30 parts by weight of a solvent in which tetrahydrofuran and an aqueous solution were mixed at a weight ratio of 9.5:0.5, and stored at a temperature of -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 5 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight is a value of 16,000 in terms of styrene, and the n value of X is 4-6, and the n value of Y is 4-6, and the result of the chemical formula 5 is as follows.

²⁹ Si-NMR (CDCl ₃ ) δ-72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)

Further, a sesquisesquioxane composite polymer and a coating composition were produced using the monomers described in Table 23 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 5 in a peer-to-peer manner.

Example 6: Synthesis of a composite polymer of oxime sesquioxane E-A-B-D structure

The composite polymer of the E-A-B-D structure was produced by the following method, and the coating composition was produced by the method equivalent to the above Example 1.

[Example 6-a] Generation of chain end E structure

20 parts by weight of dichloromethane was added dropwise to the mixture obtained in Example 4-c without further purification, and 5 parts by weight of a 0.36% by weight aqueous solution of HCl 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 6-b] Introduction of the B structure and the end E structure into the cage (cage)

After preparing the organic layer of the result obtained in the above Example 6-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 in the mixed solution of Example 6-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 6. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 6-c] Removal by by-product of precipitation and recrystallization, obtaining of the result

After the mixture of the above-mentioned Example 6-b was completed, it 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, 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 carry out purification by simply recrystallizing a substance which has not been introduced into a polymer and which is blocked by a cage structure.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and the polymer of Chemical Formula 6 and various by-products were obtained together by vacuum reduction. Also, when comparing the GPC results with the NMR results, the results are The cage form of the sharp form was obtained without the low molecular weight obtained by the growth of the polymer in each step. From this, it was confirmed that the composite polymer was obtained without problems. At this time, the molecular weight is 21,000 in terms of styrene conversion value, X has an n value of 4-6, and Y has an n value of 4-6, and particularly the result of Chemical Formula 6 is as follows.

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

Further, a sesquisesquioxane composite polymer was produced using the monomers described in Table 24 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 6 in a peer-to-peer manner.

Example 7: Synthesis of a composite polymer of a sesquioxanes A-B-A-D structure

In the synthesis step, continuous hydrolysis and condensation were carried out in stages, and a coating composition was produced in the same manner as in the above Example 1.

[Example 7-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 7-b] Synthesis of linear sesquioxanes (A precursor)

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 7-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and stirred at room temperature for 1 hour, followed by dropwise addition. 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 dropped, and after removing the catalyst and impurities by washing twice, the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group was confirmed by IR analysis, and the molecular weight was measured. It was confirmed that the linear heptasilane has a styrene-converted molecular weight of 6,000.

[Example 7-c] Synthesis of linear sesquisesquioxane structure (synthesis of A-B precursor)

5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, and 0.5 part by weight of the catalyst prepared in the above Example 7-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. 10 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and 20 parts by weight of tetrahydrofuran was further added dropwise thereto, and the mixture was further stirred for 2 hours. The mixed solution in the stirring was dripped, and the catalyst and the impurities were removed by washing twice to obtain a linear sesquisesquioxane. The residual alkoxy group was analyzed by ¹ H-NMR. 0.1 mmol/g or less. It is used to introduce a portion of the cage after continuous reaction. Regarding the morphological analysis of the linear structure, it was confirmed by XRD analysis that the integral structure was a linear structure. When the molecular weight was measured, it was confirmed that the linear structure of the sesquisestamer has a molecular weight of 8,000 in terms of styrene.

[Example 7-d] Synthesis of linear sesquioxanes structure (synthesis of A-B-A precursor)

5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, and 10 parts by weight of the catalyst of Example 7-a produced 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 each of the 7-b precursor and the 7-c precursor, and 10 parts by weight of tetrahydrofuran was further added dropwise thereto, and the mixture was further stirred for 24 hours. The mixed solution in the stirring was dropped, and after removing the catalyst and impurities by washing twice, the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group was confirmed by IR analysis, and the molecular weight was measured. It was confirmed that the linear heptasilane has a molecular weight of styrene of 15,000.

¹ H-NMR (CDCl ₃ ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.

[Example 7-e] Generation of continuous cage structure (introduction of D structure)

To the mixed solution of the above Example 7-d, 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 in one portion to obtain stable hydrolysis, and after stirring for 1 hour, the catalyst 7 produced in Example 7-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 the methoxy group was confirmed by H-NMR and IR analysis. When the residual ratio was 10%, 10 parts by weight of a 0.36 wt% aqueous HCl solution was gradually added dropwise to adjust the pH. The value 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 stirring 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 the analysis peak of the structure in which two phenyl (phenyl) were introduced in a sharp form was observed, and it was confirmed that the production was as high as Chemical Formula 7. Molecules without additional by-products. Further, the molecular weight in terms of styrene was measured to be ²²² 8,000.

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

[Example 7-f] Introduction of X into the B structure (completed of the A-B-A-D structure)

After preparing the organic layer of the result obtained in the above Example 7-e without further purification, the terminal was converted into a cage structure using a trifunctional monomer. After 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% of HCl was added to the produced mixed solution and stirred for 10 minutes, and then 3 parts by weight of methyltrimethoxysilane (Methyltrimethoxysilane) was added dropwise to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was again added to adjust the pH of the mixed solution to an alkaline state. At this time, a polymer in a cage form is introduced into the X portion of the B structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 7. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 7-g] Removal by by-product of precipitation and recrystallization, obtaining of the result

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 7-f, and washed separately 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.

Confirmed that the solid matter obtained by the end of the recrystallization process has passed After filtration, the polymer of Chemical Formula 7 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight is a value of 24,000 in terms of styrene, the average value of n of n is 4-6, and the value of n of Y is 4-6.

Further, a sesquisesquioxane composite polymer was produced using the monomers described in Table 25 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 7 in a peer-to-peer manner.

Example 8: Synthesis of a composite sesquioxane polymer of D-A-B-A-D structure

Using the following examples, a composite polymer of the D-A-B-D structure was produced, and a coating composition was produced by the same method as in the above Example 1.

[Example 8-a] pH conversion reaction for excessive formation of D structure

To the mixed solution of Example 7-d in the reaction, 15 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, the amount of diPhenyltetramethoxydisiloxane was prepared in an amount of 5 times that of Example 7-e, that is, 25 parts by weight, and added dropwise at a time. After stirring for 1 hour, Example 7 was again added. The pH of the mixed solution was adjusted to an alkaline state by 20 parts by weight of the catalyst produced in a. After the end of the reaction, 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 the mixture was stirred for 4 hours, a part of the mixture was separated and analyzed by ²⁹ Si-NMR and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group present in the B structure was changed to 0.006 mmol/g. The repeating unit having B and D is introduced at a ratio of about 5:5. Further, the molecular weight in terms of styrene was measured to be 32,000. Further, although a cage structure was introduced, the molecular weight distribution of a separate cage material was not observed in the GPC form of the polymer, and it was confirmed that the cage structure was favorably introduced into the high state by continuous reaction. molecular chain.

¹ H-NMR (CDCl ₃ ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. ²⁹ Si-NMR (CDCl ₃ ) δ-72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)

[Example 8-b] Introducing X into the B structure

After preparing the organic layer of the result obtained in the above Example 8-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. After 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% of HCl was added to the produced mixed solution and stirred for 10 minutes, and then 3 parts by weight of methyltrimethoxysilane (Methyltrimethoxysilane) was added dropwise to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was again added to adjust the pH of the mixed solution to an alkaline state. At this time, a polymer in a cage form is introduced into the X portion of the B structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 8. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 8-c] Removal by by-product of precipitation and recrystallization, obtaining of the result

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 8-b, and washed separately 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. . Its purpose is to seek not to import Recrystallization of a polymer and a substance blocked by a cage structure facilitates purification.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and then the polymer of Chemical Formula 1 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight is 36,000 in terms of styrene, the n value of X is 4-6, and the n value of Y is 4-6, especially the result of Chemical Formula 8 is as follows.

²⁹ Si-NMR (CDCl ₃ ) δ-72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)

Further, a sesquisesquioxane composite polymer and a coating composition were produced using the monomers described in Table 26 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 8 in a peer-to-peer manner.

Example 9: Synthesis of a composite polymer of oxime sesquioxane E-A-B-A-D structure

The composite polymer of the E-A-B-A-D structure was produced by the following examples, and a coating composition was produced by the method equivalent to the above Example 1.

[Example 9-a] Generation of chain end E structure

20 parts by weight of dichloromethane was added dropwise to the mixture obtained in Example 7-g without further purification, and 5 parts by weight of a 0.36% by weight aqueous solution of HCl 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 9-b] X-introduction of the B structure and the end E structure into a cage

The knot obtained in the above Example 9-a was prepared without further purification. After the organic layer of the fruit, the terminal is converted to a cage structure using a trifunctional monomer. 3 parts by weight of methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in the reaction to obtain stable hydrolysis, and after stirring for 24 hours, the product produced in Example 7-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 9. However, since it is obtained together with other by-products, it must be separately purified. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 9-c] Removal by by-product of precipitation and recrystallization, obtaining of the result

After the mixture of the above-mentioned Example 9-b was completed, it 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, 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 9 and various by-products were obtained together by vacuum reduction. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problem ground A composite polymer is obtained. At this time, the molecular weight is a value of 28,000 in terms of styrene, and the n value of X is 4-6, and the n value of Y is 4-6.

Further, a sesquisesquioxane composite polymer was produced using the monomers described in Table 27 below. At this time, the manufacturing method uses the method used in the above-described Embodiment 9 in a peer-to-peer manner.

[experiment]

In glass (Asahi Glass, soda lime 0.5T), tile (Daelim Bath / Dalin Sanitary Ware (share), PF wall tile), cement structure (Dongyang Cement (share), Portland 1 (general) cement and Sand is produced by mixing at a weight ratio of 1:3) and Sputtering a PET film having SiO ₂ (sprayed by itself, PET film = SKC, V5400, hereinafter referred to as "SiO ₂ sputtering"). The ceramic coating composition produced in the above Examples 1 to 9 was applied and hardened to measure surface characteristics.

- Surface hardness measurement: In general, the pencil hardness method (JIS 5600-5-4) is usually evaluated at a load of 750 g, but the pencil is placed at an angle of 45 degrees on the coated surface under a harsh condition, that is, a 1 kgf load. The speed of 0.5 mm was moved horizontally by 10 mm to scratch the coating film, and the scratches were evaluated. If the scratch marks of 3 mm or more are not confirmed in 2 or more times in 5 experiments, the pencil of high grade hardness is selected, and if the scratch marks are confirmed 2 times or more, the pencil which is one grade lower than the pencil hardness is selected and evaluated. To meet the pencil hardness of the coated film, it is shown in Table 28 below. Regarding the evaluation results, the 9H hardness was confirmed regardless of the type of the substrate at a coating thickness of 10 μm or more. Further, although not described in Table 28, the coating composition of another example of the present invention was confirmed to have a hardness of 9H under coating having a coating thickness of 10 μm or more.

- Contact angle: The contact angle was measured for glass, tile, SiO ₂ sputtering. For the measurement method, after dropping water droplets on the surface of the sample using a contact angle measuring device (DSA100 of KRUSS Co., Ltd.), the contact angle with respect to the water droplets was measured after 1 minute, and the contact angle was measured 5 times for each sample and the average value thereof was used. . The evaluation result is expressed as ◎ when the contact angle exceeds 100 degrees, ○ when the contact angle is 90-100 degrees, and X when the contact angle is less than 90 degrees.

- Reliability evaluation: Evaluation of reliability of glass, tile, and SiO ₂ sputtering. The evaluation method was stored in a reliability chamber of 85% and 85 ° C for 240 hours, and the bending property (YI (ASTMD 1925)) was evaluated, and the results are shown in Table 30 below.

The bending evaluation standard is within ±0.1 mm: ◎, within ±0.2 mm: ○, -0.3 mm or less, or 0.3 mm or more: X. The evaluation results were excellent in all the substrates.

- Scratch test: 400 wool was evaluated by steel wool # 0000 at 1 kgf, and the abrasion evaluation method (JIS K5600-5-9) by steel wool was used for about 1 kg. The weight of the hammer is wound at the top of the #0000 steel wool and rubbed the test piece 15 times, and the test piece is measured. The haze value is measured, and the test piece is rubbed under the harsh conditions, that is, rubbing 400 times, and by Haze measurement and microscopic evaluation The results of the photocurable coating composition of Example 6 are shown in Table 31 below. Although it is not described in Table 31, the coating composition of the other embodiment of the present invention has been confirmed to have excellent resistance to scratches generated on the surface under application of a coating thickness of 5 μm or more.

- 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. In the case of the adhesion, the results were as follows. The results of the photocurable coating composition of Example 6 are shown in Table 31 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)". It was confirmed that the adhesion was excellent. Although not shown in Table 31, the coating composition of another example of the present invention was evaluated, and as a result, it was confirmed that the adhesion was extremely excellent.

As shown in the above Tables 28 to 31, in the case where the ceramic coating composition of the present invention is applied, it exhibits extremely excellent anti-crack property and pinhole prevention characteristics as compared with the case of uncoated. The water-repellent property, the water-repellent property, and the anti-fouling property, and exhibit excellent characteristics that do not impair the transmittance and optical properties of the substrate.

Claims (15)

A ceramic coating method characterized by coating a ceramic coating composition comprising a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 on a ceramic surface and hardening: [Chemical Formula 5] In the above Chemical Formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ 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 ²² 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, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21 and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ ~ C ₄₀ aralkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ aryl thiol, a and d are each independently an integer from 1 to 100,000, b respectively Independently an integer from 1 to 500, e is independently 1 or 2, n respectively Li is an integer of 1-20. The ceramic coating method according to claim 1, wherein the ceramic is produced by processing a non-metal or inorganic material. The ceramic coating method of claim 1, wherein the ceramic is glass, wall material (including cement wall material), ground material (including cement floor material) or brick. The ceramic coating method of claim 1, wherein the coating has a thickness of 0.01 to 500 um. A ceramic coating composition comprising the sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9: [Chemical Formula 4] [Chemical Formula 9] In the above Chemical Formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ 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 ²² 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 And R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ ~ C ₄₀ aralkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ aryl thiol, a and d are each independently an integer from 1 to 100,000, b respectively Independently an integer from 1 to 500, e is independently 1 or 2, n respectively Li is an integer of 1-20. The ceramic coating composition of claim 5, wherein a is from 3 to 1,000, b is from 1 to 500, and d is from 1 to 500. The ceramic coating composition of claim 5, wherein the average of n values is 4 to 5. The ceramic coating composition of claim 5, wherein the above-mentioned sesquisesquioxane composite polymer has a weight average molecular weight of 1,000 to 1,000,000. The ceramic coating composition of claim 5, wherein the coating composition is a solventless type. The ceramic coating composition according to claim 5, wherein the coating composition comprises: the above-mentioned sesquisesquioxane composite polymer; an initiator; and an organic solvent. The ceramic coating composition of claim 5, wherein the coating composition further comprises a hardener, an ultraviolet absorber, an antioxidant, an antifoaming agent, a leveling agent, a water repellent, a flame retardant, or a subsequent improving agent. A sesquisesquioxane composite polymer coated ceramic characterized by being coated on a surface and coated as shown in any one of the above Chemical Formulas 1 to 9 A cured product obtained by coating a ceramic coating of a sesquisquioxane composite polymer and hardening it. The sesquisesquioxane composite polymer coated ceramic according to claim 12, wherein the sesquisesquioxane composite polymer coated ceramic is formed by the ceramic coating method of claim 1. An article comprising the sesquisesquioxane composite polymer coated ceramic of claim 12. The article of claim 14, wherein the article is a wall material (including cement wall material) of a building or structure, a ground material (including cement flooring), a brick, a tile, a roofing material, a window; a cup, a tray, a container Semiconductor manufacturing equipment; automotive glass, optical products, glasses, electronic products, solar cells themselves, and glass for protection.