TW201546205A - A coating method for metal using silsesquioxane composite polymer - Google Patents

Abstract

The present invention relates to a method for coating metal using a silsesquioxane composite polymer, and more specifically, by coating the metal 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 metal using silsesquioxane composite polymer facilitates the coating process and the formed coating layer has superb characteristics for sustained rust resistance, scratch resistance, water repellency, moisture blocking, soil resistance, glossiness, surface strength, and thermal stability, and additionally has an excellent adhesive property.

Description

Metal coating method using sesquioxane composite polymer Field of invention

The present invention relates to a metal coating method using a sesquisesquioxane composite polymer, and more particularly to a metal coating method using a sesquisesquioxane composite polymer as follows: for use in a polymer The sulfonium sesquioxane chain containing a specific structure of a linear sesquioxane chain and a cage sesquioxanes is coated on the metal surface, thereby not only making the coating step easier but also forming The coating has excellent rust resistance, scratch resistance, water repellency, water repellency, antifouling property, gloss, surface strength and thermal stability, and is excellent in adhesion.

Background of the invention

In general, there is a phenomenon in which metal or plating metal is immediately rusted by moisture and oxygen in the air when it is exposed to the air. The existence of such a rot to reduce the luster of the metal is not good in terms of aesthetics, and seriously affects the quality of the product. In order to delay or prevent such rot, the methods of coating, plating, oxide film, cathodic corrosion, alloy, etc. have been tried since, but the previous method has the ability to resist rot (rust) depending on the situation. In the case of poor force, a number of steps must be carried out, and the cost is also high. Therefore, the actual situation is still required to study the following methods: in practical applications, the coating solution can be used to easily apply to metal, and the rust-proof ability Excellent.

In order to impart a rust-preventing property to a metal by coating the raw material by such a solution type, it is physically required to have adhesion to a metal, flatness of coating, other water repellency or water repellency. In particular, it is desirable to chemically design the coating composition such that the coating has a stronger adhesion to the metal and imparts flow characteristics during the coating formation step.

In the prior Korean Patent Publication No. 10-2011-0054009, there is disclosed a method for preventing the surface of zinc or zinc alloy from using a blackening chemical treatment solution containing a phosphate ion, an iron ion, a manganese ion or a nitrate ion on a metal surface. In the method of rust treatment, in the Korean Patent Publication No. 10-2014-0013265, an attempt was made to achieve a rust prevention effect by coating a bismuth compound on a galvanized steel sheet, but the rust-preventing ability is still insufficient to satisfy At the same time, there are still many difficulties in meeting the requirements of the demander such as scratch resistance, antifouling property or glossiness.

Summary of invention

In order to solve the problems as described above, it is an object of the present invention to provide a metal coating method which coats a metal surface using a coating solution, whereby not only the coating step is relatively easy, but also the formed coating layer Anti-rust durability, scratch resistance, water-repellent properties, waterproof properties, anti-fouling Excellent in properties, gloss, surface strength and thermal stability, and excellent in adhesion.

Further, it is an object of the present invention to provide a metal coating composition which imparts rust-resistance, scratch resistance, water repellency, water repellency, antifouling property, gloss, surface strength and thermal stability to a metal. .

Further, it is an object of the present invention to provide a metal which has excellent rust-preventing ability, scratch resistance, water repellency, water repellency, antifouling property, gloss, surface strength and thermal stability on the surface, and at the same time Excellent coating.

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

In order to achieve the above object, the present invention provides a metal coating method characterized in that a metal coating composition comprising a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is coated on a metal surface. And harden:

[Chemical Formula 3]

[Chemical Formula 8]

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 metal 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 sesquioxalic oxide composite polymer coated metal, which comprises coating a metal comprising a sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 9 on a surface thereof. A cured product which is coated with a composition and hardened.

Moreover, the present invention provides an article comprising the above-mentioned sesquicibrane The alkane composite polymer coats the metal.

The metal coating method of the present invention coats a metal surface using a coating solution, whereby not only the coating step is relatively easy, but also the rust-preventing ability, scratch resistance, water-repellent property of the formed coating layer Excellent in water resistance, antifouling properties, gloss, surface strength and thermal stability, and excellent in adhesion, so it can be used not only in automobiles, kitchen supplies, metal pipes (including water supply pipes), metal shapes, street lamps, Traffic sign boards, solar cell appearance frames, road separation strips, buildings, etc., and can also be used effectively in the field of semiconductors and displays using metal wiring.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

The metal coating method of the present invention provides a metal coating method characterized in that a metal coating composition comprising a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is coated on a metal surface. And harden:

[Chemical Formula 2]

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 ¹ , 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.

The metal coating method of the present invention and the metal 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 metal and hardened, whereby even if a single coating layer is formed only by the solution step, it has excellent rust-preventing ability and scratch resistance with respect to the metal. , water-repellent characteristics, waterproof characteristics, anti-fouling properties, gloss, table Surface strength and thermal stability.

In the present invention, the metal to be coated is not particularly limited as long as it contains a metal. As an example, all of ordinary metals such as iron, copper, aluminum, and stainless steel can be used, and all metal plating layers and alloys can be used. In addition, if it is a steel plate, a steel material, a structure, a pipe (a water supply pipe, a sewage pipe, a gas pipe, etc.), a jewelry, etc., it is contained in a coating object, and it can also be used for metal wiring (semiconductor, display, etc. product).

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.

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 second step, a basic catalyst is added to the reactor to convert the reaction liquid into Basically, performing a condensation reaction; in the 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 refining step by recrystallization On the other hand, a cage structure which is separately produced as a by-product by the reaction of the third step 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 was introduced into the reactor to convert the reaction liquid into an acidic environment, and the organic decane compound was 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 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.

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; a step, after the third step, introducing an acid catalyst into the reactor to convert the reaction liquid into an acidic environment, and mixing the organic decane compound and stirring to introduce the [E]eX ₂ structure to the end of the composite polymer .

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 alkaline; and the fourth step is carried out by condensing two or more kinds of substances obtained by the above third step 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 is introduced into the chemical formula 10 obtained in the above first step; and in the third step, after the reaction in each of the second steps, a basic catalyst is added to the reactor to convert the reaction liquid into a basic step of performing a condensation reaction; a fourth step of condensing two or more substances obtained by the above third step under basic conditions; and a fifth step, after the fourth step, Adding an acid catalyst to the reactor into which [D]d(OR ¹³ ) ₂ is introduced, adjusting the reaction solution to be acidic, adding an organodecane compound and stirring; and a sixth step, after reacting in the above fifth step, in the reactor Adding alkaline catalyst The reaction solution is converted to a basic embodiment and 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 respective two-step reaction, adding a basic catalyst to the reactor to convert the reaction liquid to basicity and performing a condensation reaction; The two or more compounds obtained by the above three steps are condensed and condensed under basic conditions; and the fifth step, after the fourth step, is used to introduce [D]d(OR ⁵ ) ₂ Adding an acidic catalyst to the reactor to adjust the acid to acidic, and then adding the organodecane compound and stirring; in the sixth step, after the above five-step reaction, adding a basic catalyst to the reactor to convert the reaction solution to alkaline Condensation embodiment; 7 and a second step, in which, after the sixth step, by introducing an acidic catalyst in the reactor and the reaction solution was converted to an acidic environment, and the mixing and stirring of organosilane compounds, to [E] eX ₂ structure 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 liquid is preferably from 8 to 11.5, and the pH of the reaction liquid introduced in the seventh step of 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.

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 switched to an acidic environment with 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. Moreover, as the acidic catalyst, an acidic substance which is generally used in the art can be used without limitation, 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 and (3-glycidoxypropyl). Triethoxy decane, (3-glycidoxypropyl) methyl dimethoxy decane, (3-glycidoxypropyl) dimethyl ethoxy decane, 3-(methacryl oxime) Propyltrimethoxydecane, 3,4-epoxybutyltrimethoxydecane, 3,4-epoxybutyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, aminopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethylbutoxide Base decane, vinyl triisobutoxy decane, vinyl triisopropoxy decane, vinyl triphenyloxy decane, phenyl triethoxy decane, phenyl trimethoxy decane, aminopropyl trimethoxy Pyridinium, N-phenyl-3-aminopropyltrimethoxydecane, dimethyltetramethoxyoxirane, diphenyltetramethoxyanthracene, etc.; One type or two or more types are used in combination. 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, it is preferable that 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, ie, epoxycyclohexyl)ethyl; GlyP means Glycidoxypropyl, glycidoxypropyl; POMMA means (methacryloyloxy)propyl, ie Methyl propylene oxime) propyl; 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 sesquisesquioxane 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 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, the metal coating composition containing the sesquisesquioxane composite polymer shown in any one of the above Chemical Formulas 1 to 9 may be used in combination of two or more kinds, 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 coating 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 above metal coating composition can be applied alone without a solvent, and when the sesquisesquioxane composite polymer is in a solid state. The above metal coating composition may be composed of an organic solvent. Also, 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 an initiator, and optionally, additives such as a curing agent, a plasticizer, an ultraviolet blocking agent, and other functional additives are added to improve the hardenability. Heat resistance, UV blocking, plasticizing effect, etc.

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 it is possible to change the heat or light in the polymer itself, it is preferred to obtain a curing step by diluting it in such an organic solvent.

Further, in the present invention, for the curing of the 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 and the coating stability after hardening can be simultaneously satisfied.

Further, when introducing an unsaturated hydrocarbon or the like into the above organic functional group, a radical initiator may be used, and as the radical initiator, trichloroacetophenone or diethoxybenzene may be used. Diethoxy acetophenone, 1-phenyl-2-hydroxyl-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1-(4-methylthienyl)-2- Benzyl-1-propan-1-one 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- Photoradical initiators such as diphenylethane-1-one, tert-butylperoxy maleic acid, tert-butyl hydroperoxide, 2,4-dichlorobenzhydryl peroxide, Thermal freedom such as 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, N-4,4'-di(t-butylperoxy)pentanoic acid butyl ester a base initiator, and various mixtures of the foregoing, and the like.

Further, when the organic functional group contains an epoxy group or the like, a lanthanide such as triphenylsulfonium or diphenyl-4-(phenylthio)phenylhydrazine can be used as the photopolymerization initiator (cation). , diphenyl hydrazine or bis(dodecylphenyl) fluorene, etc., diazonium such as phenyldiazonium, 1-benzyl-2-cyanopyridinium or 1-(naphthylmethyl)- Ammonium such as 2-cyanopyridinium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-phosphonium hexafluorophosphate, bis(4-t-butylphenyl)hexafluorophosphate Barium phosphate, barium diphenyl hexafluorophosphate, barium diphenyl trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolylsulfonium triflate, and (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, as a hardening accelerator for promoting the above hardening action, acetamidine may also be used. Benzoguanamine, 2,4-diamino-6-vinyl-second three Wait three a compound, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-benzimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, 1-methylimidazole, etc. Compound, 1,5-diazabicyclo[4.3.0]nonene-5,1,8-diazabicyclo[5.4.0]undecene-7, triphenylphosphine, diphenyl (p-toluene) Phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogen fluoride , tetrabutylphosphonium dihydrotrifluoride, and the like.

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

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

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

As an additive which can be used in the present invention, a polyether-modified polydimethylsiloxane (Polyether-modified polydimethylsiloxane) can be cited. For example, as BYK company's BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc., polyether modified hydroxyfunctional poly-dimethyl-siloxane (such as BYK-308, BYK-373 from BYK, etc.), polymethyl alkyl decane series (Methylalkylpolysiloxane, such as BYK-077, BYK-085, etc.), polyether modified methylalkylpolysiloxane (such as BYK-320, BYK-325, etc.), polyester polymethylalkyl oxime Polyester modified poly-methyl-alkyl-siloxane (such as BYK-315, etc.), aralkyl modified methylalkyl polysiloxane (such as BYK-322, BYK-323, etc.), poly Polyester modified hydroxy functional polydimethylsiloxane (such as BYK-370, etc.) Acrylic functional polyester modified polydimethylsiloxane (such as BYK-371, BYK-) UV3570, etc.), polyether-polyester hydroxypolydimethyloxane (Pol Yeher-polyester modified hydroxy functional polydimethylsiloxane (such as BYK-375, etc.), polyether polydimethylsiloxane (Polyether modified dimethylpolysiloxane, such as 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, For example, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361N, BYK-357, BYK-358N, BYK-352, etc.), polymethacrylate (Polymethacrylate, such as BYK-390, etc.), polyether propylene fluorenyl polydimethyl decane (Polyether modified acryl functional polydimethylsiloxane (such as BYK-UV3500, BYK-UV3530, etc.), polyether modified siloxane (such as BYK-347, etc.), alcohol alkoxylates (Alcohol alkoxylates, such as BYK- DYNWET800 or the like), an acrylate type (Acrylate, for example, BYK-392, etc.), a thiol modified polyacrylate (OH-functional), such as BYK-Silclean 3700, etc.

In the present invention, as for the method of applying the above metal coating composition to a metal surface, it is of course possible for spin coating, bar coating, slit coating, dip coating, natural coating, reverse Any of the 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 may 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. In particular, when a coating layer is laminated in a thickness of 10 μm or more, 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 metal and a product comprising the above-described sesquisesquioxane composite polymer coated metal, the sesquisesquioxane composite polymer coated metal characterized by comprising a cured product obtained by coating a metal coating composition comprising the sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 9 on a surface and hardening the above-mentioned sesquisesquioxane The composite polymer coated metal can be produced by the above metal coating method.

In the sesquioxane composite polymer coated metal of the present invention, the sulfonium sesquioxane composite polymer coating has excellent adhesion to the metal, and the formed sesquioxane composite polymer coating is applied to the metal surface. It imparts excellent rust-resistance, scratch resistance, water-repellent properties, water-repellent properties, anti-fouling properties, gloss, surface strength and thermal stability. The article comprising the sesquisesquioxane composite polymer coated metal of the present invention comprises the above-mentioned sesquisesquioxane composite polymer coated metal article, which can be usefully used in various fields, in particular, not only usefully For automobiles, kitchen supplies, metal pipes (including water pipes), metal shapes, street lamps, traffic signs, solar cell appearance frames, road separation belts, buildings, etc., and can also be used efficiently for semiconductors using metal wiring. , display field.

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 following examples of the invention, ECHETMS means 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, GPTMS means glycidoxypropyltrimethoxydecane, and MAPTMS means (methacryloxy) propyltrimethoxydecane, PTMS means phenyltrimethoxydecane, MTMS means methyltrimethoxydecane, ECHETMDS means bis(epoxycyclohexylethyl)tetramethoxydioxane, and GPTMDS means bis(glycidoxypropyl)tetramethoxydioxane Oxytomane, MAPTMDS means bis(methacryloxy)propyl, PTMDS means di(phenyl)tetramethoxydioxane, MTMDS means di(methyl)tetramethoxydioxine alkyl.

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 the 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 the coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of each of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, and the mixture was stirred for 10 minutes to prepare a thermosetting coating. combination.

[Example 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.

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

The following examples were used to make a composite high score for the E-A-D structure The coating composition was produced by a method corresponding to the method described in the above Example 1. 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

To the AD mixture obtained in Example 1-c, 20 parts by weight of dichloromethane was added dropwise 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 refined. Thereafter, the temperature is changed to normal temperature, and the tetrahydrofuran in the mixed solution is removed by vacuum to prepare refined.

[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 ABD 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 refined. 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 DABD structure

The composite polymer of the D-A-B-D structure was produced by the following method, and a 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 refined. 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 were 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 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 EABD structure

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

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

To the mixture obtained in Example 4-c, 20 parts by weight of dichloromethane was added dropwise 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 6-b] Introduction of the B structure and the end E structure into the cage (cage)

After the organic layer of the result obtained in the above Example 6-a was prepared 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 refined. 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 refine the material which is not introduced into a polymer and which is blocked by a cage structure, and is simply purified.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and the polymer of the chemical formula 6 and various vices were obtained together by vacuum decompression. product. 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 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 hydrazine sesquioxane ABAD structure

With respect to the synthesis step, continuous hydrolysis and condensation were carried out in stages as follows, 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 (guide of D structure) In)

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 18,000.

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 refined. 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.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and then 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 24,000 in terms of styrene, 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 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 sesquisilane polymer of DABAD 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 refined. 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 dissolved in 30 parts by weight. The mixture was mixed with tetrahydrofuran and an aqueous solution 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 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 a sesquioxane EABAD structure

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

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

To the mixture obtained in Example 7-g, 20 parts by weight of dichloromethane was added dropwise 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 9-b] X-introduction of the B structure and the end E structure into a cage

After preparing the organic layer of the result obtained in the above Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of methyltrimethoxysilane was added dropwise to the mixed solution of Example 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 refined. 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 the polymer of the chemical formula 9 and various vices were obtained together by vacuum decompression. product. 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 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]

The coating compositions prepared in the above Examples 1 to 9 were applied to galvanized steel sheets, stainless steel, and copper wirings 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 more severe condition, that is, a 1 kgf load. The film was scratched by moving the film at a speed of 0.5 mm per second at a speed of 10 mm, and evaluated by scratching. 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; if the scratch marks are confirmed more than 2 times, the pencil is selected and the pencil hardness is lower by one grade. The pencil hardness was evaluated to match the pencil hardness of the coated film and is shown in Table 28 below.

- Saline spray test: It was placed in a sodium chloride solution for 96 hours in accordance with JIS-K5621 and evaluated, and the results are shown in Table 29. With respect to the evaluation criteria, the coated film after the evaluation was dried at normal temperature for 48 hours, and then observed by the naked eye, and the portion which was not peeled off due to swelling or cracking of the coating film and the absence of discoloration and gloss of the steel sheet was expressed as good. It is not the case that this is not the case.

- Pollution resistance: 0.5% carbon black solution was sprayed and dropped on the surface of the coating film in the form of a spot. After being exposed to the film at 80 ° C for 24 hours, the water was wiped with water. The stain change on the surface was evaluated, and the results are shown in Table 30. Regarding the evaluation criteria, the case where the water was removed without the black stain was expressed as good, and the case where the trace of the spot form was not the case was indicated as defective.

As shown in the above Tables 28 to 30, in the case of coating using the metal coating composition of the present invention, it exhibited both excellent rust prevention properties, antifouling properties, surface strength and scratch resistance. Although not shown in Tables 28 to 30, the coating compositions of other embodiments of the present invention also exhibited results comparable to those of the coating compositions described in Tables 28 to 30 above.

Claims (17)

A metal coating method characterized by coating a metal coating composition comprising a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 on a metal 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 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 Independently an integer from 1 to 20. The metal coating method of claim 1, wherein the metal is a metal plating layer or an alloy metal. The metal coating method of claim 1, wherein the metal is stainless steel. The metal coating method of claim 1, wherein the metal is a wiring of an electronic product. The metal coating method of claim 1, wherein the coating thickness is from 0.01 to 500 um. A metal 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 Independently an integer from 1 to 20. The metal coating composition of claim 6, wherein a is from 3 to 1,000, b is from 1 to 500, and d is from 1 to 500. The metal coating composition of claim 6, wherein the average of n values is from 4 to 5. The metal coating composition of claim 6, wherein the above-mentioned sesquisesquioxane composite polymer has a weight average molecular weight of 1,000 to 1,000,000. The metal coating composition of claim 6, wherein the coating composition is a solventless type. The metal coating composition of claim 6, wherein the coating composition comprises: the above-mentioned sesquisesquioxane composite polymer; an initiator; and an organic solvent. The metal coating composition of claim 6, 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 an adhesion improver. A sesquioxane composite polymer coated metal, characterized in that the coating on the surface comprises coating any one of the above Chemical Formulas 1 to 9 A hardened material obtained by hardening a metal coating composition of a sesquisquioxane composite polymer. The sesquimethoxane composite polymer coated metal according to claim 13, wherein the above sesquisesquioxane composite polymer coated metal is formed by the metal coating method of claim 1. An article comprising the sesquisesquioxane composite polymer coated metal of claim 13. The article of claim 15 wherein the item is a car, a kitchen article, a metal pipe (including a water supply pipe), a metal shape, a street light, a traffic signage panel, a solar cell exterior frame, a road separation belt, or a building. The article of claim 15 wherein the item is a semiconductor or an electronic product.