TWI669351B - A coating method for plastic using silsesquioxane composite polymer - Google Patents

Abstract

The present invention relates to a plastic coating method using a silsesquioxane composite polymer, and more specifically, it relates to a plastic coating method using a silsesquioxane composite polymer as follows: used in a polymer The silsesquioxane composite polymer containing a linear silsesquioxane chain of a specific structure and a silsesquioxane cage-type silsesquioxane is used to coat the plastic surface, thereby not only the coating step is easier, but also the formed The coating has a very high surface hardness, and has excellent transparency, scratch resistance, water resistance, antifouling properties, fingerprint resistance, thermal stability and gloss properties, and excellent adhesion to plastic substrates. High compatibility with pigments and easy coloring.

Description

Plastic coating method using silsesquioxane composite polymer Field of invention

The present invention relates to a plastic coating method using a silsesquioxane composite polymer, and more specifically, it relates to a plastic coating method using a silsesquioxane composite polymer as follows: used in a polymer The silsesquioxane composite polymer containing a linear silsesquioxane chain of a specific structure and a silsesquioxane cage-type silsesquioxane is used to coat the plastic surface, thereby not only the coating step is easier, but also the The coating has a very high surface hardness, and has excellent transparency, scratch resistance, water resistance, antifouling properties, fingerprint resistance, thermal stability and gloss properties, and excellent adhesion to plastic substrates. High compatibility with pigments and easy coloring.

Background of the invention

Generally speaking, plastic products are used in a large number of products due to their high processability and flexibility. However, due to the poor surface hardness, durability, pollution resistance, scratch resistance, gloss characteristics, and heat resistance of plastic materials, the following methods are used: Depending on the use of plastic products, the surface is coated with two or more layers of various coatings. Cloth to impart functionality.

As an example, in the Republic of Korea Patent Publication No. 10-2006-0121334, a surface coating method of a plastic molded product is disclosed. The plastic molded product forms an organic coating on the surface of the plastic, and forms an inorganic coating on the outside thereof. Then, after the physical forming of all plastics in the vacuum chamber, an organic film is formed on the surface, and an inorganic film is formed again on the outside, and various colors can be expressed in the vacuum chamber by physical and chemical evaporation. For metallic texture, the surface coating method of the plastic molded product is characterized by the following steps: a washing step, which uses compressed air or other solvents to clean and dry to remove the residue on the surface of the plastic molded product. Various foreign matter; organic film coating step, which uses surface spray hardening or dipping method to harden the surface and the organic material with excellent adhesion to the inorganic material on the plastic molded product whose surface is washed through the above washing step to form a film ; An inorganic coating step, which uses an inorganic coating on the pass through the use of spraying or dipping An organic film coating step to form a film on the surface-hardened plastic molded product to suppress gas dissolution suppression; and a vacuum evaporation step that performs physical and chemical evaporation in a vacuum chamber to form a metal film to After forming the above-mentioned organic / inorganic composite film, the plastic molded product gives physical and chemical characteristics and realizes the metal texture of various colors; however, the method has too complicated steps, and the durability and thermal stability of the formed coating are also The worse problem is disclosed in the Korean Patent Publication No. 10-2011-0014517 by the following method: using silicon dioxide particles containing urethane-based polymers and ethylenically unsaturated groups for surface coating to plastics For hard coating, the urethane-based polymer has an ethylenically unsaturated group in the molecule and penetrates through the gel The mass average molecular weight measured by permeation chromatography is 3,000-200,000, and the glass transition temperature is more than 30%; however, this method has problems that the surface hardness, pollution resistance and thermal stability are still at unsatisfactory levels.

Summary of invention

In order to solve the problems as described above, an object of the present invention is to provide a plastic coating method using a silsesquioxane composite polymer as follows: using a coating solution to coat on a plastic surface, thereby not only the coating step It is easy, and the coating formed has a very high surface hardness, and has excellent transparency, scratch resistance, water resistance, antifouling properties, fingerprint resistance, thermal stability and gloss properties, and plastic substrates It has excellent adhesion and is easy to color because of its high compatibility with pigments.

In addition, an object of the present invention is to provide a plastic coating composition which can impart high surface hardness to plastic surfaces and excellent transparency, scratch resistance, water resistance, antifouling properties, fingerprint resistance, and thermal stability. And gloss characteristics.

In addition, an object of the present invention is to provide a plastic having a coating layer having a very high surface hardness on the surface, and having excellent transparency, scratch resistance, waterproof properties, antifouling properties, fingerprint resistance, and heat. Stability and gloss characteristics, excellent adhesion to plastic substrates.

Another object of the present invention is to provide an article, which is characterized by including a plastic having the above coating.

In order to achieve the above object, the present invention provides a plastic coating method, which is characterized in that a plastic coating containing a silsesquioxane composite polymer represented by any one of the following chemical formulae 1 to 9 is coated on a plastic surface. Composition and hardening:

[Chemical Formula 5]

In the above Chemical Formulae 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 of them is [(SiO _3/2 R) _{4 + 2n} R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently Hydrogen; deuterium; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth) acrylfluorenyl group; thiol group; isocyanate group; nitrile group; nitro; phenyl group; deuterium, halogen, amine group , Epoxy, (meth) acrylfluorenyl, thiol, isocyanate, nitrile, nitro, phenyl substituted or unsubstituted C ₁ to C ₄₀ alkyl; C ₂ to C ₄₀ alkenes C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ heteroaryl C ₃ ~ C ₄₀ aralkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ arylthiol, preferably containing deuterium, halogen, amine, (methyl ) Acrylofluorenyl, thiol, isocyanate, nitrile, nitro, Groups, cyclohexyl epoxy groups of a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, the C ₂ ~ C ₄₀ alkenyl group, the amine group, an epoxy group, cyclohexyl epoxy groups, (meth) Bing Xixi Group, thiol group, phenyl group or isocyanate group, a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, and further preferably a is 5 to 300, d It is 2 to 100, b is independently an integer of 1 to 500, e is independently 1 or 2, preferably 1, and n is independently an integer of 1 to 20, preferably 3 to 10.

In addition, the present invention provides a plastic coating composition including the silsesquioxane composite polymer shown in any one of the above chemical formulas 1 to 9.

In addition, the present invention provides a silsesquioxane composite polymer coated plastic, which is characterized in that it comprises coating on the surface the silsesquioxane composite polymer containing any one of the above-mentioned chemical formulae 1 to 9. A hardened product obtained by curing a plastic coating composition.

In addition, the present invention provides an article including the above silsesquioxane composite polymer-coated plastic.

The plastic coating method of the present invention uses a silsesquioxane composite polymer containing a linear silsesquioxane chain with a specific structure and a cage silsesquioxane in a polymer to coat the surface of the plastic. Therefore, not only the coating step is relatively easy, but also the formed coating has a very high surface hardness, and has excellent transparency, scratch resistance, waterproof properties, and antifouling properties. Resistance, fingerprint resistance, thermal stability and gloss characteristics, excellent adhesion to plastic substrates, can be usefully used in optical films, protective films, plastics for electronic products, glasses, building exterior materials, building interior materials , Plastic piping, wire covering materials, optical lenses, sound insulation walls, plastic signage, plastic shapes, furniture, lighting, skylights, safety helmets and other products.

Forms used to implement the invention

Hereinafter, the present invention will be described in detail.

The plastic coating method of the present invention provides a plastic coating method, which is characterized in that a plastic coating including a silsesquioxane composite polymer shown in any one of the following chemical formulae 1 to 9 is coated on a plastic surface. Composition and hardening:

[Chemical Formula 3]

[Chemical Formula 8]

In the above Chemical Formulae 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 of them is [(SiO _3/2 R) _{4 + 2n} R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently Hydrogen; deuterium; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth) acrylfluorenyl group; thiol group; isocyanate group; nitrile group; nitro; phenyl group; deuterium, halogen, amine group , Epoxy, (meth) acrylfluorenyl, thiol, isocyanate, nitrile, nitro, phenyl substituted or unsubstituted C ₁ to C ₄₀ alkyl; C ₂ to C ₄₀ alkenes C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ heteroaryl C ₃ ~ C ₄₀ aralkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ arylthiol, preferably containing deuterium, halogen, amine, (methyl ) Acrylofluorenyl, thiol, isocyanate, nitrile, nitro, Groups, cyclohexyl epoxy groups of a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, the C ₂ ~ C ₄₀ alkenyl group, the amine group, an epoxy group, cyclohexyl epoxy groups, (meth) Bing Xixi Group, thiol group, phenyl group or isocyanate group, a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, and further preferably a is 5 to 300, d It is 2 to 100, b is independently an integer of 1 to 500, e is independently 1 or 2, preferably 1, and n is independently an integer of 1 to 20, preferably 3 to 10.

The plastic coating method of the present invention and the plastic coating composition used therefor will have the above-mentioned repeating units of [A] a and [D] d and optionally have the specificity of repeating units of [B] b or [E] e The structured silsesquioxane polymer is coated on the surface of the plastic and hardened, thereby forming it even through the solution step only. A single coating can also have excellent surface hardness, transparency, scratch resistance, water resistance, antifouling properties, fingerprint resistance, thermal stability and gloss properties compared to plastic.

In the present invention, the above-mentioned plastics to be coated are not particularly limited as long as they include plastics. As an example, they can be not only polyethylene (PE), polypropylene (PP), and polystyrene (polystyrene, PS), polyethylene terephthalate (PET), polyamides (PA, nylon), polyester (PES), polyvinyl chloride (PVC), polyurethane Polyurethanes (PU), polycarbonate (PC), high hardness polycarbonate (high hardness PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE) , Plastic ether, polyetheretherketone (PEEK), polyetherimide (PEI), acrylic resin, and other single plastic materials, can also be a mixture of two or more plastic materials, and can also be Composite plastics made of plastic and inorganic fibers such as glass fiber or carbon fiber. In terms of morphology, due to the use of solution steps, they can also include sheets, films, ejections, shapes, and beads. All plastic products.

The silsesquioxane composite polymer shown in the above Chemical Formula 1 of the present invention may be manufactured by the following steps. In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organic silane compound is added and condensed to The following chemical formula 10 is produced: a second step, after the above first step, an acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, and then an organic silane compound is added and stirred to make [D] d (OR ² ) ₂ structure is introduced into Chemical Formula 10; and a third step, after the above second step, a basic catalyst is added to the reactor to convert the reaction solution to basic and perform a condensation reaction.

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

The silsesquioxane composite polymer shown in 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 organic silane compound is added and condensed to Manufacture the above-mentioned chemical formula 10; the second step, after the above first step, add an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then add an excess of an organic silane compound and stir to make [D] d (OR ³ ) The structures of ₂ and [D] d (OR ⁴ ) ₂ are introduced into Chemical Formula 10 like Chemical Formula 2; the third step is to add a basic catalyst to the reactor after the second step to convert the reaction solution into Basic step and performing a condensation reaction; a fourth step, after the above third step, adding a basic catalyst to the reactor to convert the reaction solution to basic and perform a condensation reaction; and a refining step by recrystallization The cage structure, which is formed as a by-product by the reaction in the third step, is removed.

The silsesquioxane composite polymer shown in the above Chemical Formula 3 of the present invention may be manufactured by the following steps. In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organic silane compound is added and condensed to Manufacture the above-mentioned chemical formula 10; a second step, after the above first step, add an acidic catalyst to the reactor to adjust the reaction liquid to be acidic, and then add an organic silane compound and stir to [D] d (OR ⁵ ) _{2 The} structure is introduced into Chemical Formula 10; the third step is to add a basic catalyst to the reactor after the above second step to convert the reaction solution to basic and perform a condensation reaction; and the fourth step is to After 3 steps, an acidic catalyst is put into the reactor to convert the reaction solution into an acidic environment, and the organic silane compound is mixed and stirred to introduce the [E] eX ₂ structure to the end of the composite polymer.

The silsesquioxane composite polymer shown in the above Chemical Formula 4 of the present invention may be manufactured by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organic silane compound is added and the condensation is adjusted. The second step is to prepare the above-mentioned chemical formula 10; the second step is to add an acidic catalyst to the reactor to adjust the reaction solution to be acidic after the first step described above, and then add an organic silane compound and stir to change the [B] b structure and [D] d (OR ⁷ ) ₂ structure is introduced into Chemical Formula 10; and a third step, after the second step described above, a basic catalyst is added to the reactor to convert the reaction solution to basic and perform a condensation reaction.

The silsesquioxane composite polymer shown in the above Chemical Formula 5 of the present invention may be manufactured by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organic silane compound is added and condensed to Manufacture the above Chemical Formula 10; the second step, after the above first step, add an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then add an excess of an organic silane compound and stir to change the [B] b structure and [D] d (OR ⁸ ) ₂ and [D] d (OR ⁹ ) ₂ structures are introduced into Chemical Formula 10; the third step is to add a basic catalyst to the reactor after the second step to convert the reaction solution. It is converted to basicity and subjected to a condensation reaction; and a fourth step, after the third step, a separate cage-forming structure is removed by a recrystallization and filtration process.

The silsesquioxane composite polymer shown in 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 silane compound is added and condensed to The above-mentioned chemical formula 10 is produced; the second step is to add an acidic catalyst to the reactor to adjust the reaction solution to be acidic after the above first step, and then add an organic silane compound and stir to change the [B] b structure and [D ] d (OR ¹⁰ ) ₂ structure is introduced into Chemical Formula 10; the third step is to add a basic catalyst to the reactor after the above second step to convert the reaction solution to basic and perform a condensation reaction; and the fourth step Step: After the third step, an acid catalyst is introduced into the reactor to convert the reaction solution into an acidic environment, and the organic silane compound is mixed and stirred to introduce the [E] eX ₂ structure to the end of the composite polymer. .

In the method for manufacturing the above Chemical Formulas 1 to 6, the pH value of the reaction solution in the first step of the present invention is preferably 9 to 11.5, and the pH value of the reaction solution in the second step is preferably 2 to 4. 3-step reaction solution has better pH It is 8 to 11.5, and the pH value of the reaction solution in the fourth step of introducing Ee is preferably 1.5 to 4. In the case of the above range, not only the yield of the silsesquioxane composite polymer produced is high, but also the mechanical properties of the silsesquioxane composite polymer produced can be improved.

The silsesquioxane composite polymer shown in the above Chemical Formula 7 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 silane compound is added to produce a condensation. The above-mentioned chemical formula 10 of the adjusted two forms is added; in the second step, an acid catalyst is added to the reactor to adjust the reaction solution to be acidic, and then an organic silane compound is added and stirred to change the [B] b structure and [D ] d (OR ¹² ) ₂ structure is introduced into the chemical formula 10 obtained in the above first step; in the third step, after the reaction in each of the above second steps, an alkaline catalyst is added to the reactor to convert the reaction solution into It is basic and performs a condensation reaction; and a fourth step, in which two or more substances obtained in the third step described above are condensed and linked under basic conditions.

The silsesquioxane composite polymer represented by the above-mentioned chemical formula 8 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 silane compound is added to produce a condensation. The above-mentioned chemical formula 10 in two forms with adjusted degrees; in the second step, an acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, and then an organic silane compound is added and stirred to change the [B] b structure, [D ] d (OR ¹⁴ ) ₂ structure is introduced into the chemical formula 10 obtained in the first step; in the third step, after the reaction in each of the second steps, an alkaline catalyst is added to the reactor to convert the reaction solution into It is basic and performs a condensation reaction. In the fourth step, two or more substances obtained by the above third step are condensed and linked under basic conditions. In the fifth step, the fourth step is used after the fourth step. Add [D] d (OR ¹³ ) _{2 to} the reactor, add an acidic catalyst to adjust the reaction solution to be acidic, add an organic silane compound, and stir; and step 6: after the reaction in step 5 above, in the reactor Adding alkaline catalyst and The reaction solution is converted to a basic embodiment and condensation reaction.

The silsesquioxane composite polymer shown in the above Chemical Formula 9 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 silane compound is added to produce a condensation. The above-mentioned chemical formula 10 of the two adjusted forms; the second step, adding an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then adding an organic silane compound and stirring to introduce the [B] b structure into the above The chemical formula 10 obtained in the first step; the third step, after the reaction in each of the above second steps, adding a basic catalyst to the reactor to convert the reaction solution to basic and perform a condensation reaction; the fourth step, It condenses and links two or more compounds obtained in the third step under basic conditions; in the fifth step, it is used to introduce [D] d (OR ⁵ ) ₂ after the fourth step. An acid catalyst is added to the reactor to adjust the reaction solution to be acidic, and then an organic silane compound is added and stirred. In the sixth step, after the reaction in the fifth step, an alkaline catalyst is added to the reactor to convert the reaction solution into Alkali Embodiment and condensation reaction; and the seventh step, in which, after the sixth step, 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 The structure is introduced to the end of the composite polymer.

Preferably, in the method for manufacturing the polymer of the above Chemical Formulae 7 to 9, the pH value of the reaction solution in the first step is preferably 9 to 11.5, and the pH value of the reaction solution in the second step is preferably 2 to 4. The pH value of the reaction solution in step 3 is preferably 8 to 11.5, the pH value of the reaction solution in step 4 is preferably 9 to 11.5, the pH value of the reaction solution in step 5 is preferably 2 to 4, and the sixth step The pH value of the reaction solution is preferably 8 to 11.5, and the pH value of the reaction solution in the seventh step of introducing Ee is preferably 1.5 to 4. In the case of the above range, not only the yield of the silsesquioxane composite polymer produced is high, but also the mechanical properties of the silsesquioxane composite polymer produced can be improved.

When necessary, in order to further introduce the [B] b structure and the [D] d (OR) ₂ structure into each composite polymer, it is possible to further include [B] in the composite polymer through the following two steps. b repeating unit: adding an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then adding an organic silane compound and stirring; and after the above steps, adding a basic catalyst to the reactor to convert the reaction solution to alkaline And a condensation reaction is performed.

In addition, when necessary, in order to introduce the [E] eX ₂ structure at the end of each composite polymer, the following steps may be included to include a repeating unit of [E] e at the end of the composite polymer: put in the reactor An acidic catalyst converts the reaction solution into an acidic environment, and the organic silane compound is mixed and stirred.

In the above-mentioned method for producing a silsesquioxane composite polymer, as the basic catalyst, a mixed catalyst using two or more kinds of basic catalysts is preferred, and neutralization and acidification are performed by using an acidic catalyst. Initiate rehydrolysis, and By using a mixed catalyst of two or more basic catalysts again and performing condensation under alkalinity, the acidity and alkalinity can be continuously adjusted in one reactor.

In this case, the above-mentioned basic catalyst may be appropriately selected from two or more kinds of metal-based alkaline catalysts selected from the group consisting of Li, Na, K, Ca, and Ba and amine-based basic catalysts. And combined. Preferably, the amine-based alkaline catalyst may be tetramethylammonium hydroxide (TMAH), and the metal-based alkaline catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO ₃ ). In the above mixed catalyst, the content of each component is preferably a ratio of an amine-based alkaline catalyst to a metal-based alkaline catalyst, which can be arbitrarily adjusted within a ratio of 10 to 90: 10 to 90 parts by weight. When it is in the above range, it has the following advantages: it can minimize the reactivity of the functional group with the catalyst during hydrolysis, thereby significantly reducing the defects of organic functional groups such as Si-OH or Si-alkoxy, Thereby, the degree of condensation can be freely adjusted. The acidic catalyst may be used without limitation as long as it is an acidic substance generally used in the field. For example, ordinary acidic substances such as HCl, H ₂ SO ₄ , HNO ₃ , and CH ₃ COOH can be used. Organic acidic materials such as lactic acid, tartaric acid, maleic acid, and citric acid can also be used.

In the method for producing a silsesquioxane composite polymer of the present invention, as long as the organic solvent is an organic solvent generally used in the field, it can be used without limitation, for example, not only methanol, ethanol, and isopropanol can be used. Alcohols such as butanol and celestial, lactic acid, ketones such as acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan systems such as tetrahydrofuran, dimethylformamide Solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, dimethyl Benzene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, dichloromethane, stearylamine, aniline, diamine Various solvents such as methyl sulfene and benzyl alcohol.

In addition, as the above-mentioned organic silane compound, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² It is preferable to use an organic silane compound containing a phenyl group or an amine group having the effect of increasing the chemical resistance of the silsesquioxane composite polymer and improving the non-swelling property, or a compound having an increased hardening density of the composite polymer. An epoxy or (meth) acrylfluorene-based organosilane compound that enhances the mechanical strength and hardness of the hardened layer.

Specific examples of the organic silane-based compound include (3-glycidyloxypropyl) trimethoxysilane, (3-glycidyloxypropyl) triethoxysilane, and (3-glycidyloxypropyl) (Oxypropyl) methyldimethoxysilane, (3-glycidyloxypropyl) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriisobutoxysilane , Vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-amine Propyltrimethoxysilane, dimethyltetramethoxysilane, diphenyltetramethyl Oxysiloxanes, etc .; one of these may be used alone, or two or more of them may be used in combination. For the physical properties of the finally produced composition, it is more preferable to use a mixture of two or more kinds.

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 It is further preferred that the average n value is 4 to 5. For example, when the above n is 4, if it shows a substituted structure, it is shown in the following chemical formula 11:

In the above formula, R is the same as defined 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, which is more than It is preferably 3 to 10, and further preferably an average n value of 4 to 5. For example, if the substituted structure when n is 4 is expressed, it is represented by the following chemical formula 12: [Chemical formula 12]

In the above formula, R is the same as defined above.

As a specific example, the silsesquioxane polymer proposed in the present invention may be a polymer described in Tables 1 to 18 below. In the following Tables 1 to 9, ECHE means (epoxycyclohexyl) ethyl, GlyP means glycidyl etheroxypropyl, and POMMA means (methacryloxy) propyl. In the case of more than one kind, it means mixed use. n are independently 1 to 8.

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

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

As a specific example, the silsesquioxane composite polymer of the chemical formula 3 may be a polymer described in Tables 5 and 6 below.

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

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

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

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

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

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

Regarding the silsesquioxane composite polymer of the present invention, in order to ensure excellent storage stability, a wide range of applicability is obtained, and the degree of condensation can be adjusted to 1 to 99.9% or more. That is, the content of the alkoxy group of Si bonded to the terminal and center can be adjusted to 50% to 0.01% with respect to the bonding group of the polymer as a whole.

In addition, the weight average molecular weight of the silsesquioxane composite polymer proposed by the present invention may be 1,000 to 1,000,000, preferably 5,000 to 100,000, and even more preferably 7,000 to 50,000. In this case, the processability and physical properties of silsesquioxane can be improved at the same time.

In the present invention, the plastic coating composition containing the silsesquioxane composite polymer shown in any one of the above chemical formulas 1 to 9 may use two or more kinds of composite polymers, and it is preferable to use chemical formulas 3 to The silsesquioxane composite polymer shown in any one of 9. In this case, by including the repeating unit [B] b or [E] e, the physical properties of the transparent substrate including the surface hardness can be further improved.

In the present invention, when the silsesquioxane composite polymer is in a liquid state, the above plastic coating composition can be applied separately without a solvent, and when the silsesquioxane composite polymer is in a solid state The plastic coating composition is composed of an organic solvent. The coating composition may further contain an initiator or a hardener.

The coating composition is preferably characterized in that it comprises a silsesquioxane composite polymer represented by any one of the above chemical formulas 1 to 9, and an organic compound generally used in the field having compatibility with the composite polymer. Solvents and initiators, optionally containing hardeners and plasticizers Additives, UV blocking agents, and other functional additives to improve hardenability, heat resistance, UV blocking, and plasticizing effects.

In the coating composition of the present invention, the silicon silsesquioxane composite polymer preferably contains at least 5 parts by weight or more, more preferably 5 to 90 parts by weight relative to 100 parts by weight of the coating composition. It is preferably included in an amount of 10 to 50 parts by weight. When it is in the said range, the mechanical physical property of the hardened film of a coating composition can be improved further.

As the above-mentioned organic solvent, not only alcohols such as methanol, ethanol, isopropanol, butanol, and cyrus, alcohols such as lactic acid, ketones such as acetone, methyl (isobutyl) ethyl ketone, or ethylene glycol can be used. Diols, furans such as tetrahydrofuran, polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, cyclohexane, and cyclohexanone can also be used , Toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, dichloromethane, stearylamine Various solvents such as aniline, dimethylsulfinium, and benzyl alcohol are not limited thereto. The amount of the above-mentioned organic solvent is the balance after excluding the composite polymer, the starter, and the optionally added additives.

In the coating composition of the present invention, the above-mentioned initiator or hardener can be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.

As a specific example, when an organic hydrocarbon group capable of post-curing, such as an unsaturated hydrocarbon, a thiol system, an epoxy system, an amine system, or an isocyanate system, is introduced into the organic functional group, various types of curing using heat or light can be performed. At this time, although the change caused by heat or light can be sought in the polymer itself, it is preferable The hardening step can be performed by diluting in such an organic solvent.

In addition, in the present invention, in order to harden the composite polymer and subsequent reactions, various initiators may be used. The initiator is preferably contained in an amount of 0.1-20 parts by weight relative to 100 parts by weight of the total weight of the composition. When the content is within the above range, the transmittance and coating stability after curing can be satisfied at the same time.

When unsaturated hydrocarbons are introduced into the organic functional group, a radical initiator may be used. As the radical initiator, trichloroacetophenone, diethoxybenzene may be used. Diethoxy acetophenone, 1-phenyl-2-hydroxyl-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1- (4-methylthienyl) -2- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzobenzoyl diphenylphosphine oxide diphenylphosphine oxide), camphorquinone (camphorquinone), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylbutanoic acid) dimethyl ester, 3,3 -Dimethyl-4-methoxy-diphenyl ketone, p-methoxydiphenyl ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2- Photo radical initiators such as diphenylethane-1-one, tert-butylperoxymaleic acid, tert-butyl hydroperoxide, 2,4-dichlorobenzyl peroxide, 1,1-bis (third butylperoxy) -3,3,5-trimethylcyclohexane, N-4,4'-bis (third butylperoxy) butyl valerate and other thermal free Base initiators, and various mixtures of these.

When the organic functional group contains an epoxy group or the like, as the photopolymerization initiator (cation), a fluorene system such as triphenylsulfonium or diphenyl-4- (phenylthio) phenylsulfonium can be used. , Diphenylfluorene or bis (dodecylphenyl) fluorene and the like, 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-thirdbutylphenyl) hexafluoro Europium phosphate, europium diphenylhexafluorophosphate, europium diphenyltrifluoromethanesulfonate, triphenylphosphonium tetrafluoroborate, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolylphosphonium trifluoromethanesulfonate, and (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe cation like Fe and _{^{BF 4 -, PF 6 -,}} SbF 6 - , etc. [BQ _4] ^- salt A combination (here, Q is a phenyl substituted with at least two fluorine or trifluoromethyl groups).

In addition, as a cationic initiator that functions by heat, a cationic system such as trifluoromethanesulfonate, boron trifluoride ether complex, boron trifluoride, or a protonic acid can be used without limitation. Catalysts, various onium salts such as ammonium, phosphonium and phosphonium salts, as well as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide, etc. It can also be added in various mixed forms, and can also be mixed with various free radical initiators shown above.

Further, depending on the type of the organic functional group, ethylenediamine, triethylenetetraamine, tetraethylenetetraamine, 1,3-diaminopropane, and dipropylenetriamine can be used as amine hardeners. , 3- (2-aminoethyl) amino-propylamine, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadodecane-1, 12-diamine, 4,7,10-trioxatridecane-1,13-diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisamine methylcyclohexyl Alkane, bis (4-aminocyclohexyl) methane, Alkenyl diamine, 1,2-diamino cyclohexane and the like.

Furthermore, phthalic anhydride and trimellitic acid can be widely used. Formic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, Acid anhydride hardeners such as hydrogenated methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, dodecylsuccinic anhydride, and 2,4-diethylglutaric anhydride.

The hardener preferably contains 0.1 to 20 parts by weight relative to 100 parts by weight of the composition.

Ethylguanidine can also be used as a hardening accelerator for promoting the hardening effect. , Benzoguanamine, 2,4-diamino-6-vinyl-secondary Wait three Compounds, 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 phosphonium, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylhydrogen difluoride , Tetrabutylphosphonium dihydrotrifluoro and the like.

In the present invention, in order to improve the hardness, strength, durability, moldability, etc. after the hardening step or subsequent reaction, ultraviolet absorbers, antioxidants, antifoaming agents, leveling agents, and waterproofing agents may be additionally included. , Flame retardants, and additives such as improvers. Such additives are not particularly limited in their use, and can be appropriately added within a range that does not impair the properties of the substrate, that is, physical properties such as flexibility, light transmission, heat resistance, hardness, and strength. It is preferable that the above-mentioned additives contain 0.1 to 10 parts by weight, respectively, with respect to 100 parts by weight of the composition.

Examples of additives that can be used in the present invention include polyether-modified polydimethylsiloxane modified by polyether, such as BYK-300, BYK-301, BYK-302, BYK, which are products of BYK Company. -331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), hydroxy-functional polydimethylsiloxane modified with polyether Siloxane (Polyether modified hydroxyfunctional poly-dimethyl-siloxane, such as BYK-308, BYK-373, etc. of BYK), methyl alkyl polysiloxane (Methylalkylpolysiloxane, such as BYK-077, BYK-085, etc.), Polyether modified methylalkyl polysiloxane (such as BYK-320, BYK-325, etc.), polyester modified polymethyl alkyl polysiloxane (Polyester modified poly-methyl- alkyl-siloxane (such as BYK-315, etc.), aralkyl modified methylalkyl polysiloxane (such as BYK-322, BYK-323, etc.), polyester-modified hydroxyl groups Polyester modified hydroxy functional polydimethylsiloxane BYK-370, etc.) acrylic functional polyester modified polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV3570, etc.), polyether-polyester modified hydroxy function Polyeher-polyester modified hydroxy functional polydimethylsiloxane (such as BYK-375, etc.), polyether modified dimethylpolysiloxane (Polyether modified dimethylpolysiloxane, example Such as BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), non-ionic acrylic copolymers (Non-ionic acrylic copolymers, such as BYK-380, etc.), ionic polymers Ionic acrylic copolymer (such as BYK-381, etc.), polyacrylate (Polyacrylate, such as BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361N, BYK-357, BYK-358N, BYK-352, etc.), polymethacrylate (such as BYK-390, etc.), polyether modified acryl functional polydimethylsiloxane (Polyether modified acryl functional polydimethylsiloxane) , Such as BYK-UV3500, BYK-UV3530, etc.), polyether modified siloxane (Polyether modified siloxane, such as BYK-347, etc.), alcohol alkoxylates (Alcohol alkoxylates, such as BYK-DYNWET800, etc.), acrylic acid Ester (Acrylate, such as BYK-392, etc.), silicon modified polyacrylate (OH-functional) (Silicone modified polyacrylate (OH-functional), such as BYK-Silclean 3700, etc.) and the like.

In the present invention, as for the method for coating the plastic coating composition on the plastic surface, of course, the industry can perform spin coating, bar coating, slit coating, dip coating, natural coating, and reverse coating. It can be arbitrarily selected and used in known methods such as coating, roll coating, spin coating, curtain coating, spray coating, dipping method, impregnation method, and gravure coating. Of course, in the hardening method, it can also be based on the composite polymer. As the functional group, light curing or heat curing is appropriately selected and used. Preferably in the case of thermal curing, the curing temperature is 80 to 120 ° C.

In the present invention, the coating thickness of the coating composition can be arbitrarily adjusted, and is preferably 0.01 to 500 μm, more preferably 0.1 to 300 μm, and still more preferably 1 to 100 μm. In the case of the above range, not only the surface hardness of 7H or more can be stably ensured, but also the physical properties of the surface of the substrate are excellent. Especially when the coating is laminated with a thickness of 10 μm or more, the surface hardness can stably show 9H, so it can also be used as a substitute for glass.

Provided is a silsesquioxane composite polymer-coated plastic and a product containing the silsesquioxane composite polymer-coated plastic. The silsesquioxane composite polymer-coated plastic is characterized in that it includes a hardened material. The hardened material is obtained by coating and curing the silsesquioxane composite polymer plastic coating composition shown in any one of the above chemical formulas 1 to 9, and the silsesquioxane composite polymer coated plastic can be borrowed. Manufactured by the plastic coating method described above.

In the silsesquioxane composite polymer coated plastic of the present invention, the silsesquioxane composite polymer coating has excellent adhesion to the plastic, and the silsesquioxane composite polymer coating formed has a very high Surface hardness, and has excellent transparency, scratch resistance, waterproof properties, antifouling properties, fingerprint resistance, thermal stability and gloss properties, and excellent adhesion to plastic substrates, can be usefully applied to optical Film, protective film, plastic for electronic products, glasses, building exterior materials, building interior materials, plastic piping, wire covering materials, optical lenses, sound insulation walls, plastic signage, plastic shapes, furniture, lighting, skylights, security Hats and other products.

Hereinafter, in order to understand the present invention, a preferred embodiment is proposed. However, the following examples are merely examples of the present inventors, and the scope of the present invention is not limited to the following examples.

In the following examples of the present invention, ECHETMS means 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS means glycidyl etheroxypropyltrimethoxysilane, and MAPTMS means (Methacryloxy) propyltrimethoxysilane, PTMS means phenyltrimethoxysilane, MTMS means methyltrimethoxysilane, and ECHETMDS means bis (epoxycyclohexylethyl) tetramethoxy Dimethyl disiloxane, GPTMDS means bis (glycidyl etheroxypropyl) tetramethoxydisilazane, MAPTMDS means bis (methacryloxy) propyl, PTMDS means bis (phenyl ) Tetramethoxydisilazane, MTMDS means bis (methyl) tetramethoxydisilazane.

[Example]

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

As for the synthesis step, continuous hydrolysis and condensation are performed stepwise as described below.

[Example 1-a] Manufacturing of catalyst

In order to adjust the alkalinity, a catalyst 1a was prepared by mixing a 10% by weight aqueous solution of potassium hydroxide (KOH) in a 25% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).

[Example 1-b] Synthesis of linear silsesquioxane structure

In a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, and 1 part by weight of the catalyst produced in Example 1-a were added dropwise. After stirring at room temperature for 1 hour, the solution was added dropwise. 20 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise again to 15 parts by weight of tetrahydrofuran, and the mixture was stirred for an additional 5 hours. The mixed solution under stirring is removed by dripping, washed twice to remove the catalyst and impurities, and then the IR-infrared (IR) analysis can be used to confirm the SI-OH functional group (3200cm ^-1 ) generated at the terminal group. The molecular weight was measured, and as a result, it was confirmed that the silsesquioxane having a linear structure such as the structure of Chemical Formula 4 has a styrene conversion molecular weight of 8,000.

[Example 1-c] Generation of a continuous cage structure

To the mixed solution of Example 1-b, 5 parts by weight of a 0.36 wt% aqueous HCl solution was slowly added dropwise, the pH was adjusted to be acidic, and the mixture was stirred at 4 ° C for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time for stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst produced in Example 1-a was added again. And the pH value of the mixed solution is adjusted to an alkaline state. At this time, the precursor is separated from the linear polymer to form an alkoxy-open D structure precursor alone. A small amount of sample was dropped, and the residual rate of methoxy was confirmed by H-NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) and IR analysis. When the residual rate was 20%, 0.36% by weight was slowly added dropwise. The pH value was adjusted to be acidic by 10 parts by weight of an aqueous HCl solution. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise in one portion and stirred for 15 minutes, and then 20 parts by weight of the catalyst produced in 1-a was added. It was confirmed after 4 hours of mixing and stirring. As a result, it was confirmed that a cage-like polymer was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that all reactants were converted into an aqueous solution mixture. After 4 hours of mixing and stirring, a portion was dropped and analyzed by ²⁹ Si-NMR. As a result, two sharp peaks of the structure of the structure introduced by using phenyl were analyzed, and it was confirmed that more than 50% of the peaks were produced. The AD polymer of Chemical Formula 1 without any by-products remaining separately. The molecular weight in terms of styrene was measured at 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 silsesquioxane composite polymer obtained in the above Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to produce 100 g of a coating composition. Thereafter, 3 parts by weight of chloroacetophenone, 1 part by weight of BYK-347, and 1 part by weight of BYK-UV3500 were added to 100 parts by weight of the coating composition, and the mixture was stirred for 10 minutes to produce photohardening. Type coating composition.

[Example 1-e] Production of thermosetting resin composition

50 g of the silsesquioxane composite polymer obtained in Example 1-c described above was dissolved in methyl ethyl ketone at 50% by weight to produce 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of each of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to produce a thermosetting coating. combination.

[Example 1-f] A coating composition composed of a polymer itself

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

In addition, silicon halves were produced using the monomers described in Table 19 below. Oxane composite polymer, and manufacture coating composition. At this time, the manufacturing methods are equivalently using the methods used in the aforementioned Examples 1-b, 1-c, 1-d, 1-e, and 1-f.

Example 2 : Synthesis of silsesquioxane DAD-structured composite polymer

The following examples were used to produce a composite polymer having a D-A-D structure, and a coating composition was produced by a method corresponding to the method described in Example 1 above. The catalysts and linear structures were manufactured in the same manner as in Examples 1-a and 1-b, and then manufactured by the following methods to produce a continuous D-A-D structure.

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

To the mixed solution of Example 1-b, 5 parts by weight of a 0.36 wt% aqueous HCl solution was slowly added dropwise, the pH was adjusted to be acidic, and the mixture was stirred at 4 ° C for 30 minutes. Thereafter, 25 parts by weight of 5 times that of the diphenyltetramethoxydisiloxane used in Example 1-b was added dropwise at a time to obtain stable hydrolysis, and it was added again after stirring for 1 hour. 7 parts by weight of the catalyst produced in Example 1-a was used to adjust the pH of the mixed solution to an alkaline state. At this time, the precursor is separated from the linear polymer to form an alkoxy-open D structure precursor alone. A small amount of a sample was dropped, and the residual rate of methoxy was confirmed by analysis by H-NMR and IR. When the residual rate was 20%, 10% by weight of 0.36% by weight of HCl aqueous solution was slowly added dropwise to adjust the pH. The value is adjusted to be acidic. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise in one portion and stirred for 15 minutes, and then 20 parts by weight of the catalyst produced in 1-a was added. It was confirmed after 4 hours of mixing and stirring. As a result, it was confirmed that a cage-like polymer was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that all reactants were converted into an aqueous solution mixture. After 4 hours of mixing and stirring, a portion was dropped and analyzed by ²⁹ Si-NMR. As a result, two sharp peaks of the structure of the structure introduced using phenyl were analyzed, and it was confirmed that AD such as Chemical Formula 1 was produced. Polymer without any by-products remaining separately. The molecular weight in terms of styrene was measured at 14,000, and the n value was 4-6. In addition, it was confirmed by Si-NMR analysis that, unlike the AD structure, a peak near -68 ppm appearing at the end of the A structure disappeared, and all the ends of the A structure were converted into the D structure to generate a DAD structure.

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

In addition, a silsesquioxane composite polymer and a coating composition were produced using the monomers described in Table 20 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Embodiment 2.

Example 3 : Synthesis of a compound of silsesquioxane with EAD structure

The following examples were used to make the composite height of the E-A-D structure Molecules, and a coating composition is produced by a method corresponding to the method described in Example 1 above. The catalyst and the linear structure were manufactured in the same manner as in Example 1. Thereafter, manufacturing was performed by the following method to produce an E-A-D structure.

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

To the AD mixture obtained in Example 1-c, 20 parts by weight of dichloromethane was added dropwise without further purification, and 0.36% by weight of an aqueous solution of HCl was added dropwise to 5 parts by weight. The pH was adjusted to be acidic, and Stir at 4 ° C for 30 minutes. Thereafter, 1 part by weight of dimethyltetramethoxysilane was added dropwise at one time. At this time, the part that has not been hydrolyzed in the molecular structure is easily converted into a hydrolysate by the acidic aqueous solution layer that has been separated from the solvent, and is condensed with the other reactant generated at the end by the organic solvent layer. Unit import 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] A cage was introduced into the terminal E structure

After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. To the mixed solution of Example 3-a during the reaction, 3 parts by weight of Methyltrimethoxysilane was added dropwise at one time for stable hydrolysis. After stirring for 24 hours, the product produced in Example 1-a was added again. 3 parts by weight of the catalyst to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced at the end of the E structure, and a reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 3. But because it is obtained together with other by-products, it must be refined separately. its Then, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

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

After obtaining the mixture after completion of the reaction in Example 3-b, the mixture was 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 dissolved in a solvent prepared by mixing 30 parts by weight of 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 purpose is to recrystallize a substance which is not introduced into a polymer and is closed by a cage structure, so that purification can be easily performed.

It was confirmed that after filtering the solid matter obtained after the recrystallization process, the polymer of Chemical Formula 3 and various by-products were obtained together by vacuum decompression. In addition, when comparing the results of GPC (Gel Permeation Chromatography, gel permeation chromatography) with the results of NMR, the results were derived from the cage shape of the sharp shape without being obtained separately due to the polymer growth of each step. It is inferred from this that it is possible to confirm that a composite polymer can be obtained without any problem. At this time, the molecular weight was 17,000 in terms of styrene conversion, and the n value was 4-6. In particular, the results of Chemical Formula 3 are as follows.

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

In addition, a silsesquioxane composite polymer and a coating composition were produced using the monomers described in Table 21 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Embodiment 3.

Example 4 : Synthesis of composite silsesquioxane polymer with ABD structure

Regarding the synthesis steps, a composite polymer having an E-A-D structure was produced by performing continuous hydrolysis and condensation stepwise as described below, and a coating composition was produced by a method corresponding to the method described in Example 1 above.

[Example 4-a] Production of catalyst for hydrolysis and condensation reaction

To adjust the alkalinity, a catalyst 1a was prepared by mixing a 10 wt% aqueous solution of potassium hydroxide (KOH) in a 25 wt% aqueous solution of tetramethylammonium hydroxide (TMAH).

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

In a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, and 0.5 parts by weight of the catalyst produced in Example 4-a were added dropwise. After stirring at room temperature for 1 hour, the solution was added dropwise. 10 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise to 20 parts by weight of tetrahydrofuran again, and the mixture was stirred for an additional 2 hours. The mixed solution in agitation was dripped, and the catalyst and impurities were removed by washing twice, and the linear silsesquioxane was obtained. After ¹ H-NMR analysis, the residual alkoxy group was 0.1 mmol / g or less. It is used for subsequent introduction into the cage by continuous reaction. Regarding the morphological analysis of the linear structure, XRD (X-ray diffraction) analysis was performed to confirm that the overall structure was a linear structure. When the molecular weight was measured, it was confirmed that the silsesquioxane having a linear structure had a styrene-equivalent molecular weight of 6,000.

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 4-c] pH conversion reaction for generation of cage structure in chain (introduction of B and D structures)

To the mixed solution of Example 4-b during the reaction, 5 parts by weight of a 0.36 wt% aqueous HCl solution was slowly added dropwise, the pH was adjusted to be acidic, and the mixture was stirred at 4 ° C for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise at one time, and after stirring for 1 hour, 5 parts by weight of the catalyst produced in Example 4-a was added again to the mixed solution. The pH value is adjusted to an alkaline state. At this time, it can be confirmed that the cage-like structure is generated separately from the linear structure and is introduced into the polymer chain, the temperature is changed to normal temperature, and the tetrahydrofuran in the mixed solution is removed by vacuum, so that all The reaction was converted into an aqueous mixture. After mixing and stirring for 4 hours, a portion 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 existing in the B structure changed to 0.025 mmol / g, and Repeating units B and D were introduced at a ratio of about 5: 5. The molecular weight in terms of styrene was measured to be 10,000. In addition, although a cage structure was introduced, the molecular weight distribution of individual cage materials was not seen in the GPC form of the polymer. Therefore, it was confirmed that the cage structure was well introduced to a high level 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] Introducing X into the B structure (import of B and D structures)

After preparing the organic layer of the resultant obtained in 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 substance 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% HCl was added to the prepared mixed solution and stirred for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane was added dropwise at a time to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst produced in Example 4-a was added again to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced into the X part of the B structure, and the reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 4. But because it is obtained together with other by-products, it must be refined separately. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 4-e] Removal of by-products of precipitation and recrystallization, and obtaining of results

200 parts by weight of dichloromethane was added to the mixture after the reaction in Example 4-d above, and the mixture was 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 dissolved in a solvent prepared by mixing 30 parts by weight of 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 purpose is to recrystallize a substance which is not introduced into a polymer and is closed by a cage structure, so that purification can be easily performed.

It was confirmed that after filtering the solid matter obtained by completing the recrystallization process, the polymer of Chemical Formula 4 was obtained by vacuum decompression without various by-products. In addition, when comparing the GPC results with the NMR results, the results were derived from the cage shape of the sharp shape without the low molecules obtained separately due to the polymer growth in each step. Based on this, it can be confirmed that no Problematic access to composite polymers. At this time, the molecular weight can obtain a value of 12,000 in terms of styrene conversion, the n value of X is 4-6, and the n value of Y is 4-6. Especially, 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)

In addition, a silsesquioxane composite polymer and a coating composition were produced using the monomers described in Table 22 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Embodiment 4.

Example 5 : Synthesis of composite silsesquioxane polymer with DABD structure

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

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

To the mixed solution of Example 4-b during the reaction, 5 parts by weight of a 0.36 wt% aqueous HCl solution was slowly added dropwise, the pH was adjusted to be acidic, and the mixture was stirred at 4 ° C for 30 minutes. Thereafter, an amount of DiPhenyltetramethoxydisiloxane was prepared in an amount of 5 times that of Example 4-b, that is, 25 parts by weight and added dropwise in one portion. After stirring for 1 hour, Example 1- was added again. 5 parts by weight of the catalyst produced in a adjusts the pH of the mixed solution to an alkaline state. After the reaction is completed, the temperature is changed to normal temperature, and tetrahydrofuran in the mixed solution is removed by vacuum, so that all reactants are converted into an aqueous solution mixture. After 4 hours of mixing and stirring, a portion 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 existing in the B structure was changed to 0.012 mmol / g, and Repeating units B and D were introduced at a ratio of about 1: 9. The molecular weight in terms of styrene was measured to be 24,000. In addition, although a cage structure was introduced, the molecular weight distribution of individual cage materials was not seen in the GPC form of the polymer. Therefore, it was confirmed that the cage structure was well introduced to a high level 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] Introducing X into the B structure (import of B and D structures)

After preparing the organic layer of the product obtained in the above-mentioned 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 substance 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% HCl was added to the prepared mixed solution and stirred for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane was added dropwise at a time to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst produced in Example 4-a was added again to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced into the X part of the B structure, and the reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 5. But because it is obtained together with other by-products, it must be refined separately. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 5-c] Removal of by-products by precipitation and recrystallization Gain

200 parts by weight of dichloromethane was added to the mixture after completion of the reaction in Example 5-b, and the mixture was separately 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 dissolved in a solvent prepared by mixing 30 parts by weight of 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 purpose is to recrystallize a substance which is not introduced into a polymer and is closed by a cage structure, so that purification can be easily performed.

It was confirmed that after filtering the solid matter obtained after the recrystallization process, the polymer of Chemical Formula 5 was obtained by vacuum decompression without various by-products. In addition, when comparing the GPC results with the NMR results, the results were derived from the cage shape of the sharp shape without the low molecules obtained separately due to the polymer growth in each step. Based on this, it can be confirmed that no Problematic access to composite polymers. At this time, the molecular weight can be converted to a value of 16,000 in terms of styrene, the n value of X is 4-6, and the n value of Y is 4-6. In particular, the result of 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)

In addition, a silsesquioxane composite polymer and a coating composition were produced using the monomers described in Table 23 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Example 5.

[TABLE 23]

Example 6 : Synthesis of a compound of silsesquioxane EABD structure

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

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

20 parts by weight of dichloromethane was added dropwise to the mixture obtained in Example 4-c without further purification, and 0.36% by weight of an aqueous solution of HCl 5 was added dropwise. Parts by weight are adjusted so that the pH value is acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 1 part by weight of dimethyltetramethoxysilane was added dropwise at one time. At this time, the part that has not been hydrolyzed in the molecular structure is easily converted into a hydrolysate by the acidic aqueous solution layer that has been separated from the solvent, and is condensed with the other reactant generated at the end by the organic solvent layer. Unit import 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] X introduction of cage to B structure and terminal E structure

After preparing the organic layer of the resultant obtained in Example 6-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. To the mixed solution of Example 6-a during the reaction, 3 parts by weight of Methyltrimethoxysilane was added dropwise at one time for stable hydrolysis. After stirring for 24 hours, the product produced in Example 1-a was added again. 3 parts by weight of the catalyst to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced at the end of the E structure, and a reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 6. But because it is obtained together with other by-products, it must be refined separately. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 6-c] Removal of by-products from precipitation and recrystallization, and obtaining of results

After obtaining the mixture after completion of the reaction in Example 6-b, the mixture was 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 and removed. Remove unreacted monomers, and dissolve 30 parts by weight in a solvent prepared by mixing tetrahydrofuran with an aqueous solution at a weight ratio of 9.5: 0.5, and store at a temperature of -20 ° C for 2 days. The purpose is to simply recrystallize a substance that is not introduced into a polymer and is closed by a cage structure, and to simply purify it.

It was confirmed that after filtering the solid matter obtained after the recrystallization process, the polymer of Chemical Formula 6 and various by-products were obtained together by vacuum decompression. In addition, when comparing the GPC results with the NMR results, the results were derived from the cage shape of the sharp shape without the low molecules obtained separately due to the polymer growth in each step. Based on this, it can be confirmed that no Problematic access to composite polymers. At this time, the molecular weight can be converted to a value of 21,000 in terms of styrene, the n value of X is 4-6, and the n value of Y is 4-6. In particular, the results of Chemical Formula 6 are as follows.

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

In addition, a silsesquioxane composite polymer was produced using the monomers described in Table 24 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Example 6.

Example 7 : Synthesis of a compound of silsesquioxane ABAD structure

Regarding the synthesis steps, continuous hydrolysis and condensation were performed stepwise as described below, and a coating composition was produced by the same method as in Example 1 described above.

[Example 7-a] Production of catalyst

In order to adjust the alkalinity, a catalyst 1a was prepared by mixing a 10% by weight aqueous solution of potassium hydroxide (KOH) in a 25% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).

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

In a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, and 1 part by weight of the catalyst manufactured in Example 7-a were added dropwise. After stirring at room temperature for 1 hour, the solution was dropped 20 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise again to 15 parts by weight of tetrahydrofuran, and the mixture was stirred for an additional 5 hours. The mixed solution under stirring was dripped, washed twice to remove the catalyst and impurities, and then IR analysis was performed to confirm the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group. The molecular weight was measured. Results It was confirmed that the silsesquioxane having a linear structure had a styrene conversion molecular weight of 6,000.

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

5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, and 0.5 parts by weight of the catalyst produced in the above-mentioned Example 7-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer. After stirring at room temperature for 1 hour, the solution was added dropwise. 10 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise to 20 parts by weight of tetrahydrofuran, and the mixture was stirred for an additional 2 hours. The mixed solution in agitation was dripped, and the catalyst and impurities were removed by washing twice, and the linear silsesquioxane was obtained. After ¹ H-NMR analysis, the residual alkoxy group was 0.1 mmol / g or less. It is used for subsequent introduction into the cage by continuous reaction. Regarding the morphological analysis of the linear structure, it was confirmed by XRD analysis that the overall structure was a linear structure. When the molecular weight was measured, it was confirmed that the silsesquioxane having a linear structure had a styrene-equivalent molecular weight of 8,000.

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

In a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, and 10 parts by weight of the manufactured Example 7-a catalyst were added dropwise. After stirring at room temperature for 1 hour, the addition was performed dropwise. Example 7-b precursor and 7-c precursor were each 20 parts by weight, and 10 parts by weight of tetrahydrofuran was added dropwise again, and the mixture was stirred for additional 24 hours. The mixed solution under stirring was dripped, washed twice to remove the catalyst and impurities, and then IR analysis was performed to confirm the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group. The molecular weight was measured. Results It was confirmed that the silsesquioxane having a linear structure had a styrene-equivalent molecular weight 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 Example 7-d described above, 5 parts by weight of a 0.36% by weight aqueous solution of HCl was added very slowly, the pH was adjusted to be acidic, and the mixture was stirred at 4 ° C for 30 minutes. After that, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise at one time for stable hydrolysis, and after stirring for 1 hour, the weight of the catalyst 7 produced in Example 7-a was added again. The pH value of the mixed solution is adjusted to an alkaline state. At this time, the precursor is separated from the linear polymer to form an alkoxy-open D structure precursor alone. A small amount of the sample was dropped, and the residual rate of methoxy was confirmed by analysis by H-NMR and IR. When the residual rate was 10%, 10% by weight of 0.36% by weight of HCl aqueous solution was slowly added dropwise to adjust the pH. The value is adjusted to be acidic. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise in one portion and stirred for 15 minutes, and then 20 parts by weight of the catalyst produced in 1-a was added. It was confirmed after 4 hours of mixing and stirring. As a result, it was confirmed that a cage-like polymer was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that all reactants were converted into an aqueous solution mixture. After 4 hours of mixing and stirring, a portion was dropped and analyzed by ²⁹ Si-NMR. As a result, two sharp peaks of the structure of the structure introduced by using phenyl were analyzed, and it was confirmed that the peak was as high as chemical formula 7 Molecule without additional residual by-products. The styrene-equivalent molecular weight 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 (Completion of A-B-A-D structure)

After preparing the organic layer of the resultant obtained in 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 substance 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% HCl was added to the prepared mixed solution and stirred for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane was added dropwise at a time to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst produced in Example 7-a was added again to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced into the X part of the B structure, and the reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 7. But because it is obtained together with other by-products, it must be refined separately. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 7-g] Removal of by-products from precipitation and recrystallization, and obtaining of results

200 parts by weight of dichloromethane was added to the mixture after completion of the reaction in Example 7-f above, and the mixture was separately 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 dissolved in a solvent prepared by mixing 30 parts by weight of 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. . Its purpose is to seek the restructuring of substances that have not been introduced into polymers and are closed by cage structures. Crystal, making refining easy.

It was confirmed that after filtering the solid matter obtained after the recrystallization process, the polymer of Chemical Formula 7 was obtained by vacuum decompression without various by-products. In addition, when comparing the GPC results with the NMR results, the results were derived from the cage shape of the sharp shape without the low molecules obtained separately due to the polymer growth in each step. Based on this, it can be confirmed that no Problematic access to composite polymers. At this time, the molecular weight was a value of 24,000 in terms of styrene conversion, the average value of n in X was 4-6, and the n value of Y was 4-6.

In addition, a silsesquioxane composite polymer was produced using the monomers described in Table 25 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Example 7.

Example 8 : Synthesis of composite silsesquioxane polymer with DABAD structure

The following examples were used to produce a composite polymer having a D-A-B-D structure, and a coating composition was produced by the same method as in Example 1 above.

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

To the mixed solution of Example 7-d during the reaction, 15 parts by weight of 0.36 wt% aqueous HCl solution was added very slowly dropwise, the pH was adjusted to be acidic, and the mixture was stirred at 4 ° C for 30 minutes. Thereafter, 5 times of Example 7-e, that is, 25 parts by weight, was prepared in an amount of DiPhenyltetramethoxydisiloxane and added dropwise at one time. After stirring for 1 hour, Example 7- was added again. 20 parts by weight of the catalyst produced in a adjusts the pH of the mixed solution to an alkaline state. After the reaction is completed, the temperature is changed to normal temperature, and tetrahydrofuran in the mixed solution is removed by vacuum, so that all reactants are converted into an aqueous solution mixture. After mixing and stirring for 4 hours, a portion was taken dropwise and analyzed by ²⁹ Si-NMR and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group existing in the B structure changed to 0.006 mmol / g, and Repeating units B and D were introduced at a ratio of about 5: 5. The styrene-reduced molecular weight was measured to be 32,000. In addition, although a cage structure was introduced, the molecular weight distribution of individual cage materials was not seen in the GPC form of the polymer. Therefore, it was confirmed that the cage structure was well introduced to a high level 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] X was introduced into the B structure

After preparing the organic layer of the resultant obtained in 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 substance 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% HCl was added to the prepared mixed solution and stirred for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane was added dropwise at a time to obtain stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst produced in Example 7-a was added again to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced into the X part of the B structure, and the reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 8. But because it is obtained together with other by-products, it must be refined separately. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 8-c] Removal of by-products of precipitation and recrystallization, and obtaining of results

200 parts by weight of dichloromethane was added to the mixture after completion of the reaction in Example 8-b, which was washed separately with distilled water, When the pH of the distilled water layer is neutral, the solvent is completely removed by vacuum decompression. Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and dissolved in a solvent prepared by mixing 30 parts by weight of 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 purpose is to recrystallize a substance which is not introduced into a polymer and is closed by a cage structure, so that purification can be easily performed.

It was confirmed that after filtering the solid matter obtained by completing the recrystallization process, the polymer of Chemical Formula 1 was obtained by vacuum decompression without various by-products. In addition, when comparing the GPC results with the NMR results, the results were derived from the cage shape of the sharp shape without the low molecules obtained separately due to the polymer growth in each step. Based on this, it can be confirmed that no Problematic access to composite polymers. At this time, the molecular weight can be converted to a value of 36,000 in terms of styrene, the n value of X is 4-6, and the n value of Y is 4-6. The results of Chemical Formula 8 are 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)

In addition, a silsesquioxane composite polymer and a coating composition were produced using the monomers described in Table 26 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Example 8.

Example 9 : Synthesis of a compound of silsesquioxane EABAD structure

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

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

In the mixture obtained in Example 7-g, 20 parts by weight of dichloromethane was added dropwise without further purification, and 0.36 percent by weight of an aqueous solution of HCl was added dropwise to 5 parts by weight. The pH was adjusted to be acidic, and Stir at 4 ° C for 30 minutes. Thereafter, 1 part by weight of dimethyltetramethoxysilane was added dropwise at one time. At this time, the part that has not been hydrolyzed in the molecular structure is easily converted into a hydrolysate by the acidic aqueous solution layer that has been separated from the solvent, and is generated by the organic solvent layer. The resulting other reactants are condensed and E is introduced into the terminal unit. 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] The cage structure (X) of the B structure and the terminal E structure was introduced into cage

After preparing the organic layer of the product obtained in the above Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. To the mixed solution of Example 9-a during the reaction, 3 parts by weight of Methyltrimethoxysilane was added dropwise at one time for stable hydrolysis. After stirring for 24 hours, the product produced in Example 7-a was added again. 3 parts by weight of the catalyst to adjust the pH of the mixed solution to an alkaline state. At this time, a cage-shaped polymer is introduced at the end of the E structure, and a reaction is continuously performed in the reactor to form a polymer such as Chemical Formula 9. But because it is obtained together with other by-products, it must be refined separately. Thereafter, the temperature was changed to normal temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

[Example 9-c] Removal of by-products from precipitation and recrystallization, and obtaining of results

After obtaining the mixture after completion of the reaction in Example 9-b, the mixture was 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 dissolved in a solvent prepared by mixing 30 parts by weight of 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 purpose is to recrystallize a substance which is not introduced into a polymer and is closed by a cage structure, so that purification can be easily performed.

It was confirmed that the solid material obtained by the end of the recrystallization process After filtration, the polymer of Chemical Formula 9 and various by-products are obtained together by vacuum decompression. In addition, when comparing the GPC results with the NMR results, the results were derived from the cage shape of the sharp shape without the low molecules obtained separately due to the polymer growth in each step. Based on this, it can be confirmed that no Problematic access to composite polymers. At this time, the molecular weight can obtain a value of 28,000 in terms of styrene conversion, the n value of X is 4-6, and the n value of Y is 4-6.

In addition, a silsesquioxane composite polymer was produced using the monomers described in Table 27 below. At this time, the manufacturing method is equivalent to the method used in the above-mentioned Example 9.

[experiment]

In PC (i-components, Glastic 0.5 T), PET (SKC, V5400), PMMA (EVONIK, Plexiglas OF058), PVC (New East Asia Synthesis Co., Ltd., transparent PVC film 1mm) and PU (via SONG-STOMER P-7100 film), the coating composition produced in the above Examples 1 to 9 was applied and cured, and the surface characteristics were measured.

-Surface hardness measurement: Generally speaking, the pencil hardness method (JIS 5600-5-4) is usually evaluated with a load of 750g, and the pencil is subjected to a leap second at a 45-degree angle on the coating surface under more severe conditions, namely, a 1kgf load. The coating film was scratched by moving at a speed of 0.5 mm at a level of 10 mm, and evaluated by the scratched marks. If scratches of 3mm or more are not confirmed in more than 2 times in 5 experiments, choose a pencil with a high level of hardness for evaluation. If scratches are confirmed in more than 2 times, choose a pencil that is one level lower than the hardness of the pencil The pencil hardness suitable for the coating film was evaluated and shown in Tables 28 and 29 below. Regarding the evaluation results, at a coating thickness of 10 μm or more, regardless of the type of substrate, a 9H hardness of glass level was confirmed.

-Reliability evaluation: The storage was stored in a 85%, 85 ° C reliability chamber for 240 hours, and the bending characteristics (YI (ASTMD1925)) were evaluated. The results are shown in Tables 30 and 31 below.

The bending evaluation criteria are within ± 0.1 mm: ◎, ± 0.2 mm: ○, -0.3 mm or less, or 0.3 mm or more: X. The evaluation result was excellent among all substrates.

-Scratch test measurement (JIS K5600-5-9): The abrasion evaluation method using steel wool is based on a steel wool of # 0000 wound on the top of a hammer with a weight of about 1 kg (Steel wool) and rub the test piece back and forth 15 times to measure the haze value, and the evaluation this time is to rub the test piece under more severe conditions, that is, rub 400 times, and perform visual evaluation by haze measurement and microscope . As a result, when the haze increased by 0.05% or more, it was judged as a failure. It was confirmed that the resistance to scratches generated on the surface was excellent when the coating thickness was 5 μm or more.

-Adhesive force evaluation (JIS K5600-5-6): The coating film is cut with a blade at an interval of 1-5 mm, and a transparent tape is affixed thereon, so that the number of detached tapes can be removed when the attached tape is pulled. The adhesiveness was judged. At this time, 100 grids were made with the blade, and the adhesiveness was judged by the number of detachment among the 100. The results of the photocurable coating composition of Example 6 are shown in Table 32 and below. Table 33. Regarding the records, the number of 100 that has not left is described as "(the number of that that does not leave / 100)". As an example, if the number is not 100, it is described as "(100/100)". It was confirmed that the adhesiveness was very excellent. Although not shown in Tables 32 and 33, the coating compositions of other examples of the present invention were evaluated, and as a result, it was confirmed that the adhesiveness was very excellent.

As shown in the above Tables 32 and 33, it can be confirmed that the plastic coating composition of the present invention not only exhibits very excellent surface hardness, but is also excellent in other physical properties.

Claims (14)

A plastic coating method, characterized in that a plastic coating composition containing a silsesquioxane composite polymer shown in any one of the following chemical formulae 1 to 9 is coated on a plastic surface and hardened: [Chemical Formula 5] In the above Chemical Formulae 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 of them is [(SiO _3/2 R) _{4 + 2n} R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independent Is hydrogen; deuterium; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth) acrylfluorenyl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; deuterium, halogen, amine Group, epoxy group, (meth) acryl 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 hetero Aryl; C ₃ ~ C ₄₀ arylalkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ arylthiol group, a and d are each independently an integer of 1 to 100,000 b are independently Is an integer from 1 to 500, e is independently 1 or 2, n is independently It is an integer of from 1 to 20. For example, the plastic coating method of claim 1, wherein the plastic is selected from the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (polyethylene terephthalate). terephthalate (PET), polyamides (PA, nylon), polyester (PES), polyvinyl chloride (PVC), polyurethanes (PU), polycarbonate ( polycarbonate (PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), and polyetherimide (PEI) One or more of the group. The plastic coating method according to claim 1, wherein the coating thickness is 0.01 to 500um. A plastic coating composition comprising a silsesquioxane composite polymer shown in any one of the following chemical formulae 1 to 9: [Chemical Formula 2] [Chemical Formula 7] In the above Chemical Formulae 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 of them is [(SiO _3/2 R) _{4 + 2n} R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independent Is hydrogen; deuterium; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth) acrylfluorenyl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; deuterium, halogen, amine Group, epoxy group, (meth) acryl 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 hetero Aryl; C ₃ ~ C ₄₀ arylalkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ arylthiol group, a and d are each independently an integer of 1 to 100,000 b are independently Is an integer from 1 to 500, e is independently 1 or 2, n is independently It is an integer of from 1 to 20. For example, the plastic coating composition of claim 4, wherein a is 3 to 1000, b is 1 to 500, and d is 1 to 500. The plastic coating composition of claim 4, wherein the average value of n is 4 to 5. For example, the plastic coating composition of claim 4, wherein the weight-average molecular weight of the silsesquioxane composite polymer is 1,000 to 1,000,000. The plastic coating composition according to claim 4, wherein the coating composition is a solvent-free type. The plastic coating composition according to claim 4, wherein the coating composition comprises: the above silsesquioxane composite polymer; an initiator; and an organic solvent. The plastic coating composition according to claim 4, wherein the coating composition further comprises a pigment. A silsesquioxane composite polymer coated plastic, characterized in that it comprises a plastic coating composition containing a silsesquioxane composite polymer shown in any one of the above chemical formulas 1 to 9 coated on a surface. And hardened products. For example, the silsesquioxane composite polymer-coated plastic according to claim 11, wherein the silsesquioxane composite polymer-coated plastic is formed by the plastic coating method according to claim 1. An article comprising the silsesquioxane composite polymer-coated plastic according to claim 11. The article of claim 13, wherein the above-mentioned articles are optical films, protective films, plastics for electronic products, glasses, building exterior materials, building interior materials, plastic piping, wire covering materials, optical lenses, sound insulation walls, and plastic signboards , Plastic shapes, furniture, lighting, skylights or hard hats.