TW201545871A - A surface enhanced transparent substrate and method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a transparent substrate having reinforced surfaces and a method for manufacturing same, and more specifically, to a transparent substrate having reinforced surfaces and a method for manufacturing same, which is capable of significantly improving surface hardness by treating the surfaces with a silsesquioxane complex polymer including, in a single polymer, a silsesquioxane ladder chain and a cage-type silsesquioxane which have a specific structure, and which has improved fingerprint resistance, scratch resistance, pollution resistance, heat resistance, light transmission, and haze characteristics.

Description

Surface-reinforced transparent substrate and method of manufacturing same Field of invention

The present invention relates to a surface-enhanced transparent substrate and a method of manufacturing the same, and to a surface-enhanced transparent substrate and a method for producing the same: the surface hardness is significantly improved by treating the surface with a sesquisesquioxane composite polymer, and at the same time To improve fingerprint resistance, scratch resistance, stain resistance, heat resistance, transmittance, and haze characteristics, the sesquisesquioxane composite polymer contains linear sesquioxanes of a specific structure in one polymer. Chain and cage sesquioxanes.

Background of the invention

Transparent substrates are used for various purposes. Especially in smart phones, tablet PCs, notebooks, AIO (All-In-One) PCs, liquid crystal displays (LCDs), TVs (TVs), advertising An electronic product such as a board or a touch panel is used as a window protection substrate or a protective film in various fields, or a transparent substrate is used for a protective sheet application for protecting an internal article.

As an example of a transparent substrate, glass is representative, but due to The brittleness (fragile nature) is strong, so a transparent substrate made of plastic material is widely used.

As a transparent substrate made of plastic material, PC (polycarbonate), PET (Polyethylene Terephthalate, polyethylene terephthalate), PE (Polyethylene, polyethylene) or PMMA (Polymethyl methacrylate, polymethyl methacrylate) is used. However, generally, a transparent substrate made of a plastic material has a problem of low surface hardness, reduced durability, fingerprint resistance, scratch resistance, stain resistance, heat resistance, transmittance, and haze characteristics.

In order to solve this problem, a polycarbonate laminate in which an acrylic resin is coated on a polycarbonate to increase the surface hardness is disclosed in Korean Patent Application No. 2009-7009932, but the surface hardness is improved by pencil hardness. Below 4H, the actual situation is still insufficient.

In addition, when a smart phone or the like is equipped with a touch function, Protectm Co., Ltd. forms various layers such as a hard coat layer - an auto-recovery layer - an impact diffusion layer - a self-cleaning layer - an anti-fingerprint layer - an external impact absorption layer. As a protective film for a mobile phone, it is desired to improve the surface characteristics of a transparent substrate, but there are problems in that the steps are very complicated and the productivity is lowered.

Summary of invention

In order to solve the above problems, an object of the present invention is to provide a surface-enhanced transparent substrate and a method of manufacturing the same, which can significantly improve the surface of a transparent substrate even by a single layer formed on a transparent substrate. Hardness, while improving fingerprint resistance, scratch resistance, Pollution resistance, heat resistance, transmittance and haze characteristics.

Moreover, the present invention provides a surface strengthening method for a transparent substrate, characterized in that a coating composition containing a specific structure of a sesquioxanes composite polymer is applied onto a transparent substrate and cured.

Still another object of the present invention is to provide an electronic article comprising the above surface-reinforced transparent substrate.

Further, it is an object of the present invention to provide a protective sheet comprising the above surface-reinforced transparent substrate.

In order to achieve the above object, the present invention provides a surface-strengthened transparent substrate characterized in that a cured product of a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is laminated on a transparent substrate:

[Chemical Formula 9]

In the above chemical formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], and at least one is [(SiO _3/2 R) _4+2n O], and X is independently R ²² or [ (SiO _3/2 R) _4+2n R], and at least one is [(SiO _3/2 R) _4+2n R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ -C ₄₀ aralkyl; C ₃ -C ₄₀ aryloxy; or C ₃ -C ₄₀ aryl thiol, preferably containing fluorene, halogen, amine, (A Acryl thiol, thiol, isocyanate, nitrile, nitro Phenyl, cyclohexyl epoxy groups of a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, the C ₂ ~ C ₄₀ alkenyl group, the amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylamide a mercapto group, a thiol group, a phenyl group or an isocyanate group, a and d are each independently an integer of from 1 to 100,000, preferably a is from 3 to 1,000, d is from 1 to 500, and even more preferably from 5 to 300. d is 2 to 100, and b is independently an integer of 1 to 500, and e is independently 1 or 2, preferably 1, and n is independently an integer of 1 to 20, preferably 3 to 10.

Moreover, the present invention provides a surface strengthening method for a transparent substrate, which is characterized in that a coating composition containing the sesquisesquioxane composite polymer shown in any one of the above Chemical Formulas 1 to 9 is applied onto a transparent substrate and cured.

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

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

The surface-enhanced transparent substrate of the present invention significantly improves the surface hardness of the transparent substrate by improving the surface hardness of the transparent substrate by using a hardened body containing a specific structure of the sesquioxanes composite polymer as a coating layer, and at the same time improving fingerprint resistance, scratch resistance, and stain resistance. Dyeability, heat resistance, transmittance and haze characteristics can be very useful for window protection substrates, protective films or protective sheets for electronic products.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

The surface-reinforced transparent substrate of the present invention is characterized in that a cured product of a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is laminated on a transparent substrate:

[Chemical Formula 4]

[Chemical Formula 9]

In the above chemical formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], and at least one is [(SiO _3/2 R) _4+2n O], and X is independently R ²² or [ (SiO _3/2 R) _4+2n R], and at least one is [(SiO _3/2 R) _4+2n R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ -C ₄₀ aralkyl; C ₃ -C ₄₀ aryloxy; or C ₃ -C ₄₀ aryl thiol, preferably containing fluorene, halogen, amine, (A Acryl thiol, thiol, isocyanate, nitrile, nitro Phenyl, cyclohexyl epoxy groups of a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, the C ₂ ~ C ₄₀ alkenyl group, the amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylamide a mercapto group, a thiol group, a phenyl group or an isocyanate group, a and d are each independently an integer of from 1 to 100,000, preferably a is from 3 to 1,000, d is from 1 to 500, and even more preferably from 5 to 300. d is 2 to 100, and b is independently an integer of 1 to 500, and e is independently 1 or 2, preferably 1, and n is independently an integer of 1 to 20, preferably 3 to 10.

Regarding the surface-enhanced transparent substrate of the present invention, a sesquisesquioxane having a specific structure having repeating units of [A]a and [D]d and optionally having repeating units of [B]b or [E]e The polymer is used as a surface treatment agent for a transparent substrate, and a transparent substrate which is suitable for a window protection substrate for an electronic product, a protective film, and is suitable for use as a protective sheet for protecting an internal article.

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

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

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

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

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

The sesquisesquioxane composite polymer of the above Chemical Formula 5 of the present invention may be produced by the following steps: In the first step, after mixing a basic catalyst and an organic solvent in a reactor, an organodecane compound is added and condensed. The above chemical formula 10 is produced; the second step, after the first step, adding an acidic catalyst to the reactor to adjust the reaction solution to be acidic, and then adding an excess of the organic decane compound and stirring to form the [B]b structure and [D]d(OR ⁸ ) ₂ , [D]d(OR ⁹ ) ₂ is introduced into the chemical formula 10; in the third step, after the second step, a basic catalyst is added to the reactor to transfer the reaction solution. Conversion to alkaline and carrying out the condensation reaction; and step 4, after the third step, removing the structure forming the individual cage by recrystallization and filtration.

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

Preferably, in the method of the above Chemical Formulas 1 to 6, the pH of the reaction liquid of the first step of the present invention is preferably from 9 to 11.5, and the pH of the reaction liquid of the second step is preferably from 2 to 4, The pH of the reaction liquid of the third step is preferably from 8 to 11.5, and the pH of the reaction liquid of the fourth step of introducing Ee is preferably from 1.5 to 4. In the case of the above range, not only the produced sesquisestamer compound is high. The yield of the molecule is high, and the mechanical properties of the produced sesquisquioxane composite polymer can be improved.

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

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

The sesquisesquioxane composite polymer of the above Chemical Formula 9 of the present invention may be produced by the following steps: a first step of mixing an alkali catalyst and an organic solvent in a reactor, and then adding an organic decane compound to produce a condensation The above chemical formula 10 of the two types of adjustment; the second step, wherein an acidic catalyst is added to the reactor to adjust the reaction solution to be acidic, and then the organic decane compound is added and stirred to introduce the [B]b structure into the above The chemical formula 10 obtained in the first step; the third step, after the above-mentioned individual two-step reaction, adding a basic catalyst to the reactor to convert the reaction liquid to basicity and performing a condensation reaction; The two or more compounds obtained by the above three steps are condensed and condensed under basic conditions; the fifth step, after the above four steps, in the reactor for introducing [D]d(OR ⁵ ) ₂ Adding an acidic catalyst to adjust the reaction solution to be acidic, and then adding the organodecane compound and stirring; in the sixth step, after the above five-step reaction, adding a basic catalyst to the reactor to convert the reaction solution to alkaline real The condensation reaction; and the seventh step of, after said introducing an acidic catalyst in step 6 in the reactor and the reaction solution was converted to an acidic environment, and the mixing and stirring of organosilane compounds, to [E] ₂ is introduced into the structure of eX The end of the composite polymer.

Preferably, in the method for producing the polymer of the above Chemical Formulas 7 to 9, the pH of the reaction liquid of the first step is preferably from 9 to 11.5, and the reverse of the second step. The pH of the solution is preferably 2 to 4, the pH of the reaction liquid of the third step is preferably 8 to 11.5, and the pH of the reaction liquid of the fourth step is preferably 9 to 11.5. The pH of the reaction liquid in the sixth step is preferably from 8 to 11.5, and the pH of the reaction liquid in the seventh step of introducing Ee is preferably from 1.5 to 4. When it is in the above range, not only the yield of the produced sesquisesquioxane composite polymer is high, but also the mechanical properties of the produced sesquisesquioxane composite polymer can be improved.

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

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

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

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

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

Further, as the above organic decane-based compound, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in} Chemical Formulas 1 to 9 containing the sesquisesquioxane composite polymer of the present invention can be used. Organic decanes of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² It is preferable to use an organic decane compound containing a phenyl group or an amine group having an effect of increasing the chemical resistance of the sesquioxane complex polymer to improve the non-swelling property, or to increase the hardening density of the composite polymer. An epoxy group or a (meth) acrylonitrile-based organic decane compound which enhances the mechanical strength and hardness of the hardened layer.

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

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

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

In the present invention, n in the [(SiO _3/2 R) _4+2n R] structure introduced in the repeating unit [B]b or [E]e of the above chemical formula may be replaced by an integer of 1 to 20, Preferably, it is from 3 to 10, and further preferably, the average n value is from 4 to 5. For example, if the above-mentioned structure in which n is 4 is substituted, it is as shown in the following Chemical Formula 12:

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

As a specific example, the sesquisquioxane polymer proposed by the present invention may be a polymer described in the following Tables 1 to 18. In the following Tables 1 to 9, ECHE means (epoxycyclohexyl)ethyl, GlyP means glycidyloxypropyl, and POMMA means (methacryloxy)propyl. In the case of the above, it means mixed use. n is independently 1 to 8.

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

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

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

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

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

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

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

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

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

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

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

In the present invention, a method of laminating a cured product of a sesquisesquioxane composite polymer represented by any one of Chemical Formulas 1 to 9 on a transparent substrate may be included in any one of Chemical Formulas 1 to 9 The coating composition of the sesquioxane hybrid polymer is applied to a transparent substrate and then cured. Two or more kinds of composite polymers may be used, and it is preferred to use a sesquisesquioxane composite polymer represented by any one of Chemical Formulas 3 to 9. In this case, the physical properties of the transparent substrate including the surface hardness can be further improved by including the repeating unit [B]b or [E]e.

When the sulfonium sesquioxane composite polymer is in a liquid state, the coating composition may be applied in a solvent-free manner alone, and when the sesquisesquioxane composite polymer is in a solid state, the coating composition may include It is composed of an organic solvent. Further, the coating composition may further comprise a starter or a hardener.

It is preferable that the coating composition is characterized by comprising a sesquisesquioxane composite polymer represented by any one of the above Chemical Formulas 1 to 9 and an organic solvent generally used in the art which is compatible with the above composite polymer. Further, an initiator such as a curing agent, a plasticizer, an ultraviolet ray blocking agent, or another functional additive may be selectively and additionally added to improve curability, heat resistance, ultraviolet blocking, plasticizing effect, and the like.

In the coating composition of the present invention, the above-mentioned sesquisesquioxane composite polymer preferably contains at least 5 parts by weight or more, preferably 5 parts by weight to 90 parts by weight, more preferably 100 parts by weight of the coating composition. It is contained in an amount of 10 to 50 parts by weight. When it is in the above range, the mechanical properties of the cured film of the coating composition can be further improved.

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

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

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

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

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

Further, when the organic functional group contains an epoxy group or the like, a lanthanide such as triphenylsulfonium or diphenyl-4-(phenylthio)phenylhydrazine can be used as the photopolymerization initiator (cation). , diphenyl hydrazine or bis(dodecylphenyl) fluorene, etc., diazonium such as phenyldiazonium, 1-benzyl-2-cyanopyridinium or 1-(naphthylmethyl)- Ammonium such as 2-cyanopyridinium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-phosphonium hexafluorophosphate, bis(4-t-butylphenyl)hexafluorophosphate Barium phosphate, barium diphenyl hexafluorophosphate, barium diphenyl trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolylsulfonium triflate, and (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe cation like Fe and _{^{BF 4 -, PF 6 -,}} SbF 6 - , etc. [BQ _4] ^- salt Combination (here, Q is a phenyl group substituted with at least 2 or more fluorine or trifluoromethyl groups).

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

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

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

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

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

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

Examples of the additive which can be used in the present invention include polyether-modified polydimethylsiloxane (for example, BYK-300, BYK-301, BYK-302, and BYK-331 which are BYK products). BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), Polyether modified hydroxyfunctional poly -dimethyl-siloxane, such as BYK-308, BYK-373, BYK, etc., Methylalkylpolysiloxane (such as BYK-077, BYK-085, etc.), polyether polymethylalkyl hydrazine Polyether modified methylalkylpolysiloxane (such as BYK-320, BYK-325, etc.), polyester polymethyl-alkyl-siloxane (Polyester modified poly-methyl-alkyl-siloxane (such as BYK-315, etc.), aralkyl Polyalkyl modified methylalkyl polysiloxane (such as BYK-322, BYK-323, etc.), polyester modified hydroxy functional polydimethylsiloxane (such as BYK-370, etc.) Polyester propylene fluorenyl polydimethyl methoxide (Acrylic functi) Onal polyester modified polydimethylsiloxane (such as BYK-371, BYK-UV3570, etc.), polyether-polyester modified hydroxy functional polydimethylsiloxane (such as BYK-375, etc.), polyether poly Polyether modified dimethylpolysiloxane (such as BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), non-ionic acrylic copolymer (Non-ionic acrylic copolymer, For example, BYK-380, etc.), ionic polyacrylic acid (Ionic Acrylic copolymer (such as BYK-381, etc.), polyacrylate (Polyacrylate, such as BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361N, BYK-357, BYK-358N, BYK-352, etc., polymethacrylate (such as BYK-390, etc.), polyether modified acrylic functional polydimethylsiloxane (such as BYK-UV3500, BYK-UV3530) Etc.), polyether siloxane (such as BYK-347, etc.), alcohol alkoxylates (such as BYK-DYNWET800, etc.), acrylate (Acrylate, such as BYK-392, etc.) And succinyl polyacrylate (OH-functional), such as BYK-Silclean 3700, etc.

Moreover, the transparent substrate used for the surface-enhanced transparent substrate of the present invention can be a plastic transparent substrate and glass, and the transparent substrate is a substrate having a transmittance of at least 80% or more under a light source having a wavelength of 500 nm, as a specific plastic transparent substrate. For example, it may be selected from COC (Cyclic olefin copolymer), PAc (Polyacrylate), PC (Polycarbonate), PE (Polyethylene), PEEK (Polyetheretherketone), PEI (Polyetherimide). , polyether phthalimide), PEN (Polyethylenenaphthalate, polyethylene naphthalate), PES (Polyethersulfone, polyether oxime), PET (Polyethylene terephate), PI (Polyimide, polyimine), PO (Polyolefin, poly Olefin), PMMA (Polymethylmethacrylate), PSF (Polysulfone, polyfluorene), PVA (Polyvinylalcohol, polyvinyl alcohol), PVCi (Polyvinylcinnamate, polyvinyl cinnamate), TAC (Triacetyl cellulose, cellulose triacetate), polysilicone, polyurethane, and epoxy resin (Epoxy Resin) The substrate of the raw material. The above-mentioned raw materials may be composed of a single layer or two or more layers of different characteristics of the same material, or may be a transparent substrate obtained by mixing two or more kinds of plastics by co-extrusion.

In the present invention, the method of applying the above coating composition onto a transparent substrate can of course be applied by spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating. A known method such as roll coating, spin coating, curtain coating, spray coating, or gravure coating is arbitrarily selected. In the curing method, it is of course possible to appropriately select the light according to the functional group of the composite polymer. Hardened or heat hardened. It is preferred that in the case of heat hardening, the hardening temperature is 80 to 120 °C.

In the present invention, the coating thickness of the above coating composition can be arbitrarily adjusted, preferably from 0.01 to 500 μm, more preferably from 0.1 to 300 μm, still more preferably from 1 to 100 μm. When it is in the above range, not only the surface hardness of 7H or more can be stably ensured, but also the physical properties of the substrate are excellent. In particular, when a coating layer is laminated in a thickness of 5 μm or more, since the surface hardness can stably exhibit 9H, it can also be used as a substitute for glass.

The present invention further provides an electronic product including the surface-enhanced transparent substrate. Preferably, the electronic product is a display device. As a specific example, the smart phone, the tablet PC, the notebook computer, AIO (All-In-One) PC, LCD display, TV, advertising board or touch panel, and can be a flexible and intelligent device (wearable smart device) that requires flexibility of the substrate.

The form of the surface-enhanced transparent substrate included in the electronic product is not particularly limited, and may be in the form of a window protective substrate or a protective film as an example. The electronic product of the present invention remarkably improves the surface hardness of the transparent substrate by only a single layer, and is excellent in fingerprint resistance, scratch resistance, stain resistance, heat resistance, transmittance, and haze characteristics.

Moreover, the present invention provides a protective sheet comprising the surface-enhanced transparent substrate, wherein the protective sheet is transparent or can be observed inside, and can be a substrate for protecting an internal electronic product (display device), and as an example, can be used to protect public facilities ( A transparent protective plate for the display device of the display device of the railway station building, airport, bus terminal, etc.).

In the following, the preferred embodiments are set forth to understand the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples. In the following examples of the invention, ECHETMS means 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, GPTMS means glycidoxypropyltrimethoxydecane, and MAPTMS means (methacryloxy) propyltrimethoxydecane, PTMS means phenyltrimethoxydecane, MTMS means methyltrimethoxydecane, and ECHETMDS means bis(epoxycyclohexylethyl)tetramethoxy Dioxazane, GPTMDS means bis(glycidoxypropyl)tetramethoxydioxane, MAPTMDS means bis(methacryloxy)propyl, and PTMDS means bis(phenyl) Tetramethoxydioxane, MTMDS means di(methyl)tetramethoxydioxane.

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

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

[Example 1-a] Manufacture of catalyst

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

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

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

[Example 1-c] Generation of continuous cage structure

To the mixed solution of the above Example 1-b, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise to obtain stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst produced in Example 1-a was again added. The pH of the mixed solution was adjusted to an alkaline state. At this time, an alkoxy-open D structure precursor is separately formed separately from the linear polymer. A small amount of the sample was dropped, and the residual ratio of methoxy was confirmed by H-NMR (Nuclear Magnetic Resonance) and IR analysis. When the residual ratio was 20%, 0.36 wt% was gradually added dropwise. The pH was adjusted to be acidic by 10 parts by weight of an aqueous HCl solution. Thereafter, 1 part by weight of phenyltrimethoxysilane (Phenyltrimethoxysilane) was added dropwise thereto and stirred for 15 minutes, and then 20 parts by weight of a catalyst produced in 1-a was added. After mixing and stirring for 4 hours, it was confirmed that a polymer having a cage form was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After mixing and stirring for 4 hours, a part of the solution was dropped and analyzed by ²⁹ Si-NMR. As a result, it was confirmed that two analytical peaks of a structure in which a phenyl group was introduced in a sharp form were used, and it was confirmed that 50% or more of the composition was produced. The AD polymer of Chemical Formula 1 has no other by-products remaining alone. Further, the molecular weight in terms of styrene was measured to be 11,000, and the average n value was 4.6. ²⁹ Si-NMR (CDCl ₃ ) δ

[Example 1-d] Production of Photocurable Resin Composition

30 g of the sesquisesquioxane composite polymer obtained in the above Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of chloro acetophenone, 1 part by weight of BYK-347 and 1 are added to 100 parts by weight of the coating composition, respectively. The photohardenable coating composition was produced by stirring in a portion of BYK-UV3500 for 10 minutes.

[Example 1-e] Production of thermosetting resin composition

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

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

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

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

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

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

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

To the mixed solution of the above Example 1-b, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 25 parts by weight of 5 times the diphenyltetramethoxydisiloxane used in Example 1-b was added dropwise to obtain stable hydrolysis, and the mixture was stirred for 1 hour and then added again. The pH of the mixed solution was adjusted to an alkaline state by 7 parts by weight of the catalyst produced in Example 1-a. At this time, an alkoxy-open D structure precursor is separately formed separately from the linear polymer. A small amount of the sample was dropped, and the residual ratio of the methoxy group was confirmed by H-NMR and IR analysis. When the residual ratio was 20%, 10 parts by weight of a 0.36% by weight aqueous HCl solution was gradually added dropwise to adjust the pH. The value is adjusted to be acidic. Thereafter, 1 part by weight of phenyltrimethoxysilane (Phenyltrimethoxysilane) was added dropwise thereto and stirred for 15 minutes, and then 20 parts by weight of a catalyst produced in 1-a was added. After mixing and stirring for 4 hours, it was confirmed that a polymer having a cage form was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After mixing and stirring for 4 hours, a part of the mixture was dropped and analyzed by ²⁹ Si-NMR. As a result, it was confirmed that two analytical peaks of a structure in which a phenyl group was introduced in a sharp form were used, and it was confirmed that AD of the chemical formula 1 was produced. The polymer does not have a separate by-product by-product. Further, the molecular weight in terms of styrene was measured to be 14,000, and the average n value was 4.6. Further, it was confirmed by Si-NMR analysis that, unlike the AD structure, the peak near -68 ppm which appeared at the end of the A structure disappeared, and all the ends of the A structure were converted into the D structure to form a DAD structure. ²⁹ Si-NMR (CDCl ₃ ) δ-72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

Further, a sesquisesquioxane composite polymer and a coating composition were produced using the monomers described in the following Table 20. At this time, the manufacturing method uses the method used in the above embodiment 2 in a peer-to-peer manner.

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

Using the following examples, a composite polymer of the E-A-D structure was produced, and a coating composition was produced by a method corresponding to the method described in the above Example 1. The production of the catalyst and the linear structure was carried out in the same manner as in Example 1, and thereafter, the production was carried out by the following method to produce an E-A-D structure.

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

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

[Example 3-b] Introduction of the end E structure into a cage

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

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

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

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

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

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

Example 4 : Synthesis of a composite sesquioxane polymer of ABD structure

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

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

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

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

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

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

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

To the mixed solution of Example 4-b in the reaction, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 5 parts by weight of diPhenyltetramethoxydisiloxane was added dropwise thereto, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was again added to mix the solution. The pH is adjusted to an alkaline state. In this case, it was confirmed that the structure of the cage form was separately formed from the linear structure and introduced into the polymer chain, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum, so that all The reactants are converted to an aqueous mixture. After the mixture was stirred for 4 hours, a part of the mixture was separated and analyzed by ²⁹ Si-NMR and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group present in the B structure was changed to 0.025 mmol/g. The repeating unit having B and D is introduced at a ratio of about 5:5. Further, the molecular weight in terms of styrene was measured to be 10,000. Further, although a cage structure was introduced, the molecular weight distribution of a separate cage material was not observed in the GPC form of the polymer, and it was confirmed that the cage structure was favorably introduced into the high state by continuous reaction. molecular chain.

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

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

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

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

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 4-d, and washed separately with distilled water. When the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. . Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and stored in a solvent of 30 parts by weight of tetrahydrofuran and an aqueous solution in a weight ratio of 9.5:0.5, and stored at -20 ° C for 2 days. . The object of the invention is to recrystallize a substance which is not introduced into a polymer and which is blocked by a cage structure, so that purification can be easily carried out.

Confirmed that the solid matter obtained by the end of the recrystallization process has passed After filtration, the polymer of Chemical Formula 4 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight was a value of 12,000 in terms of styrene, and the average value of n of n was 4.6, and the average value of n of 4.7 was 4.6, and the result of Chemical Formula 4 was 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)

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

Example 5 : Synthesis of a composite sesquioxane polymer of DABD structure

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

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

To the mixed solution of Example 4-b in the reaction, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, the amount of diPhenyltetramethoxydisiloxane was prepared in an amount of 5 times, that is, 25 parts by weight of Example 4-b, and added dropwise at a time. After stirring for 1 hour, Example 1 was again added. The pH of the mixed solution was adjusted to an alkaline state by 5 parts by weight of the catalyst produced in a. After the end of the reaction, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After mixing and stirring for 4 hours, a part of the mixture was dropped and analyzed by ²⁹ Si-NMR and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group present in the B structure was changed to 0.012 mmol/g. The repeating unit having B and D is introduced at a ratio of about 1:9. Further, the molecular weight in terms of styrene was measured to be 24,000. Further, although a cage structure was introduced, the molecular weight distribution of a separate cage material was not observed in the GPC form of the polymer, and it was confirmed that the cage structure was favorably introduced into the high state by continuous reaction. molecular chain.

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

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

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

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

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 5-b, and washed separately with distilled water. When the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. . its Thereafter, the unreacted monomers were removed by precipitation twice in methanol, and 30 parts by weight of a solvent in which tetrahydrofuran and an aqueous solution were mixed at a weight ratio of 9.5:0.5 were stored at -20 ° C for 2 days. The object of the invention is to recrystallize a substance which is not introduced into a polymer and which is blocked by a cage structure, so that purification can be easily carried out.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and then the polymer of Chemical Formula 5 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight was a value of 16,000 in terms of styrene, and the average value of n of n was 4.6, and the average value of n of 4.7 was 4.6. In particular, the result of Chemical Formula 5 was as follows.

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

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

Example 6 : Synthesis of a composite polymer of oxime sesquioxane EABD structure

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

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

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

[Example 6-b] Introduction of the B structure and the end E structure into the cage (cage)

After the organic layer of the result obtained in the above Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of methyl trimethoxysilane (Methyltrimethoxysilane) was added dropwise in the mixed solution of Example 6-a in the reaction to obtain stable hydrolysis, and after stirring for 24 hours, the product produced in Example 1-a was again added. The pH of the mixed solution was adjusted to an alkaline state by 3 parts by weight of the catalyst. At this time, a polymer in a cage form is introduced into the end of the E structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 6. However, since it is obtained together with other by-products, it must be separately refined. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

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

After the mixture of the above-mentioned Example 6-b was completed, it was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and stored in a solvent of 30 parts by weight of tetrahydrofuran and an aqueous solution in a weight ratio of 9.5:0.5, and stored at -20 ° C for 2 days. . The object of the invention is to refine the material which is not introduced into a polymer and which is blocked by a cage structure, and is simply purified.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and the polymer of the chemical formula 6 and various vices were obtained together by vacuum decompression. product. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight was 21,000 in terms of styrene, and the average value of n of n was 4.6, and the average value of n of 4.7 was 4.6, and the result of Chemical Formula 6 was as follows.

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

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

Example 7 : Synthesis of a composite polymer of hydrazine sesquioxane ABAD structure

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

[Example 7-a] Manufacture of catalyst

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

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

5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, and 1 part by weight of the catalyst prepared in the above Example 7-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and stirred at room temperature for 1 hour, followed by dropwise addition. 20 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and 15 parts by weight of tetrahydrofuran were further added dropwise thereto, and the mixture was further stirred for 5 hours. The mixed solution in the stirring was dropped, and after removing the catalyst and impurities by washing twice, the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group was confirmed by IR analysis, and the molecular weight was measured. It was confirmed that the linear heptasilane has a styrene-converted molecular weight of 6,000.

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

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

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

5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, and 10 parts by weight of the catalyst of Example 7-a produced were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and the mixture was stirred at room temperature for 1 hour, and then added dropwise. 20 parts by weight of each of the 7-b precursor and the 7-c precursor, and 10 parts by weight of tetrahydrofuran was further added dropwise thereto, and the mixture was further stirred for 24 hours. The mixed solution in the stirring was dropped, and after removing the catalyst and impurities by washing twice, the SI-OH functional group (3200 cm ^-1 ) formed at the terminal group was confirmed by IR analysis, and the molecular weight was measured. It was confirmed that the linear heptasilane has a molecular weight of styrene of 15,000.

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

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

To the mixed solution of the above Example 7-d, 5 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, 5 parts by weight of diPhenyltetramethoxydisiloxane was added dropwise in one portion to obtain stable hydrolysis, and after stirring for 1 hour, the catalyst 7 produced in Example 7-a was again added. The pH of the mixed solution was adjusted to an alkaline state. At this time, an alkoxy-open D structure precursor is separately formed separately from the linear polymer. A small amount of the sample was dropped, and the residual ratio of the methoxy group was confirmed by H-NMR and IR analysis. When the residual ratio was 10%, 10 parts by weight of a 0.36 wt% aqueous HCl solution was gradually added dropwise to adjust the pH. The value is adjusted to be acidic. Thereafter, 1 part by weight of phenyltrimethoxysilane (Phenyltrimethoxysilane) was added dropwise thereto and stirred for 15 minutes, and then 20 parts by weight of a catalyst produced in 1-a was added. After mixing and stirring for 4 hours, it was confirmed that a polymer having a cage form was formed in the polymer. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After stirring and stirring for 4 hours, a part of the mixture was dropped and analyzed by ²⁹ Si-NMR. As a result, it was confirmed that the analysis peak of the structure in which two phenyl (phenyl) were introduced in a sharp form was observed, and it was confirmed that the production was as high as Chemical Formula 7. Molecules without additional by-products. Further, the molecular weight in terms of styrene was measured to be 18,000.

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

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

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

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

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 7-f, and washed separately with distilled water. When the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. . Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and stored in a solvent of 30 parts by weight of tetrahydrofuran and an aqueous solution in a weight ratio of 9.5:0.5, and stored at -20 ° C for 2 days. . The object of the invention is to recrystallize a substance which is not introduced into a polymer and which is blocked by a cage structure, so that purification can be easily carried out.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and then the polymer of Chemical Formula 7 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight was 24,000 in terms of styrene, the average value of n of n was 4.6, and the average value of n of 4.7 was 4.6.

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

Example 8 : Synthesis of a composite sesquisilane polymer of DABAD structure

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

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

To the mixed solution of Example 7-d in the reaction, 15 parts by weight of a 0.36 wt% aqueous HCl solution was added dropwise very slowly, adjusted so that the pH was acidic, and stirred at a temperature of 4 ° C for 30 minutes. Thereafter, the amount of diPhenyltetramethoxydisiloxane was prepared in an amount of 5 times that of Example 7-e, that is, 25 parts by weight, and added dropwise at a time. After stirring for 1 hour, Example 7 was again added. The pH of the mixed solution was adjusted to an alkaline state by 20 parts by weight of the catalyst produced in a. After the end of the reaction, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to convert all the reactants into an aqueous mixture. After the mixture was stirred for 4 hours, a part of the mixture was separated and analyzed by ²⁹ Si-NMR and ¹ H-NMR. As a result, it was confirmed that the amount of the alkoxy group present in the B structure was changed to 0.006 mmol/g. The repeating unit having B and D is introduced at a ratio of about 5:5. Further, the molecular weight in terms of styrene was measured to be 32,000. Further, although a cage structure was introduced, the molecular weight distribution of a separate cage material was not observed in the GPC form of the polymer, and it was confirmed that the cage structure was favorably introduced into the high state by continuous reaction. molecular chain.

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

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

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

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

200 parts by weight of dichloromethane was added to the mixture after the completion of the reaction in the above Example 8-b, and washed separately with distilled water. When the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. . Thereafter, it was precipitated twice in methanol to remove unreacted monomers and dissolved in 30 parts by weight. The mixture was mixed with tetrahydrofuran and an aqueous solution at a weight ratio of 9.5:0.5, and stored at a temperature of -20 ° C for 2 days. The object of the invention is to recrystallize a substance which is not introduced into a polymer and which is blocked by a cage structure, so that purification can be easily carried out.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and then the polymer of Chemical Formula 1 was obtained by vacuum decompression without various by-products. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight was 36,000 in terms of styrene conversion value, the average value of n of n was 4.6, and the average value of n of 4.7 was 4.6, and the result of Chemical Formula 8 was as follows.

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

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

Example 9 : Synthesis of a composite polymer of a sesquioxane EABAD structure

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

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

To the mixture obtained in Example 7-g, 20 parts by weight of dichloromethane was added dropwise without further purification, and 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted so as to be acidic. Stir at a temperature of 4 ° C for 30 minutes. Thereafter, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, a portion which has not been hydrolyzed in the molecular structure is easily converted into a hydrolyzate by an acidic aqueous layer which has been separated from the solvent, and is condensed with the other reactant formed by the organic solvent layer at the end. The unit imports E. After stirring for 5 hours, The stirring of the reaction was stopped, and the temperature of the reactor was adjusted to normal temperature.

[Example 9-b] X-introduction of the B structure and the end E structure into a cage

After preparing the organic layer of the result obtained in the above Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in the reaction to obtain stable hydrolysis, and after stirring for 24 hours, the product produced in Example 7-a was again added. The pH of the mixed solution was adjusted to an alkaline state by 3 parts by weight of the catalyst. At this time, a polymer in a cage form is introduced into the end of the E structure, and the reaction is continuously carried out in the reactor to form a polymer of Chemical Formula 9. However, since it is obtained together with other by-products, it must be separately refined. Thereafter, the temperature was changed to normal temperature, and the tetrahydrofuran in the mixed solution was removed by vacuum to prepare for purification.

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

After the mixture of the above-mentioned Example 9-b was completed, it was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum decompression. Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and stored in a solvent of 30 parts by weight of tetrahydrofuran and an aqueous solution in a weight ratio of 9.5:0.5, and stored at -20 ° C for 2 days. . The object of the invention is to recrystallize a substance which is not introduced into a polymer and which is blocked by a cage structure, so that purification can be easily carried out.

It was confirmed that the solid matter obtained by the completion of the recrystallization process was filtered, and the polymer of the chemical formula 9 and various vices were obtained together by vacuum decompression. product. Further, when the GPC result is compared with the NMR result, the result is a cage form in which a sharp form is obtained without a low molecule obtained by polymer growth in each step, and it is inferred that no Problemly obtaining a composite polymer. At this time, the molecular weight was 28,000 in terms of styrene, and the average value of n of n was 4.6, and the average value of n of 4.7 was 4.6.

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

[experiment]

The coating compositions prepared in the above Examples 1 to 9 were applied to PC, PET, and PMMA transparent substrates and cured to measure surface characteristics.

- Surface hardness measurement: In general, the pencil hardness method (JIS 5600-5-4) is usually evaluated with a load of 500 g, and the pencil is placed at an angle of 45 degrees on the coated surface under a more severe condition, that is, a 1 kgf load. The speed of 0.5 mm was moved horizontally by 3 mm to scrape the coated film, and the scratch was evaluated. If the scratch marks are not confirmed twice or more in 5 experiments, the pencil of high hardness is selected. If there are scratch marks for 2 or more times, the pencil is selected, and the pencil hardness is one hardness lower than the hardness of the pencil. The pencil hardness of the coating film is shown in Table 28 below. Regarding the evaluation results, at a coating thickness of 10 μm or more, the glass level 9H hardness was confirmed regardless of the type of the substrate.

- Reliability evaluation: The bending characteristics were evaluated by storing in a reliability chamber of 85% and 85 ° C for 240 hours, and the results are shown in Table 29 below.

The bending evaluation criteria were within ±0.1 mm before the reliability evaluation and within ±0.3 mm after the reliability evaluation.

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

- Scratch test: using steel wool (Steel Wool) #0000 was evaluated 400 times at 1 kgf. The abrasion evaluation method (JIS K5600-5-9) by steel wool is used to wind the steel wool of #0000 at the tip of a hammer of about 1 kg and to rub the test piece 15 times. The haze value was measured, and the test piece was rubbed under a harsh condition, that is, rubbed 400 times, and visually evaluated by haze measurement and a microscope, and the result of the photocurable coating composition of Example 6 is shown. Table 30 below. Although it is not described in Table 30, the coating composition of another embodiment of the present invention has been found to have excellent resistance to scratches generated on the surface under application of a coating thickness of 5 μm or more.

- Subsequent force evaluation (JIS K5600-5-6): The coating film was cut at intervals of 1-5 mm by a blade, and a scotch tape was attached thereto to remove the number of tapes attached thereto. When the adhesion was determined, at this time, 100 grids were produced by a blade, and the adhesion was judged by the number of detachment of 100. The results of the photocurable coating composition of Example 6 are shown in Table 30 below. Regarding the description, the number of the 100 items that are not separated is described as "(the number of undivided/100)", and as an example, if 100 pieces are not separated, it is described as "(100/100)". It was confirmed that the adhesion was excellent. Although not shown in Table 30, the coating composition of another example of the present invention was evaluated, and as a result, it was confirmed that the adhesion was extremely excellent.

As shown in the above Table 30, it was confirmed that the surface-reinforced transparent substrate of the present invention exhibits not only excellent surface hardness and optical characteristics but also other physical properties.

Claims (17)

A surface-enhanced transparent substrate characterized in that a cured product of a sesquisesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is laminated on a transparent substrate: [Chemical Formula 5] In the above Chemical Formulas 1 to 9, A is , B is , D is , E is , Y is independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], and at least one is [(SiO _3/2 R) _4+2n O], and X is independently R ²² or [ (SiO _3/2 R) _4+2n R], and at least one is [(SiO _3/2 R) _4+2n R], R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently Is hydrogen; hydrazine; halogen; amine; epoxy; cyclohexyl epoxy; (meth) propylene sulfhydryl; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Alkyl group, epoxy group, (meth) propylene sulfhydryl group, thiol group, isocyanate group, nitrile group, nitro group, phenyl substituted or unsubstituted C ₁ -C ₄₀ alkyl group; C ₂ ~ C ₄₀ Alkenyl; C ₁ ~ C ₄₀ alkoxy; C ₃ ~ C ₄₀ cycloalkyl; C ₃ ~ C ₄₀ heterocycloalkyl; C ₆ ~ C ₄₀ aryl; C ₃ ~ C ₄₀ miscellaneous Aryl; C ₃ ~ C ₄₀ aralkyl; C ₃ ~ C ₄₀ aryloxy; or C ₃ ~ C ₄₀ aryl thiol, a and d are each independently an integer from 1 to 100,000, b respectively Independently an integer from 1 to 500, e is independently 1 or 2, n respectively Li is an integer of 1-20. The surface-reinforced transparent substrate of claim 1, wherein a is from 3 to 1000, b is from 1 to 500, and d is from 1 to 500. The surface-enhanced transparent substrate of claim 1 wherein d is from 2 to 100. The surface-enhanced transparent substrate of claim 1 wherein the average of n values is 4 to 5. The surface-reinforced transparent substrate of claim 1, wherein the above-mentioned sesquisesquioxane composite polymer has a weight average molecular weight of 1,000 to 1,000,000. The surface-enhanced transparent substrate of claim 1, wherein the transmittance of the transparent substrate is at least 80% or more under a light source having a wavelength of 500 nm. The surface-reinforced transparent substrate of claim 1, wherein the substrate is selected from the group consisting of COC (Cyclic olefin copolymer), PAc (Polyacrylate), PC (Polycarbonate, Polycarbonate), PE (Polyethylene) , Polyethylene), PEEK (polyetheretherketone, Polyetheretherketone), PEI (polyether phthalimide, Polyetherimide), PEN (polyethylene naphthalate), PES (polyether oxime, Polyethersulfone), PET ( Polyethylene terephtalate, PI (Polyimide), PO (Polyolefin, Polyolefin), PMMA (Polymethylmethacrylate), PSF (Polysulfone) , PVA (polyvinyl alcohol, Polyvinylalcohol), PVCi (polyvinyl cinnamate, Polyvinylcinnamate), TAC (cellulose triacetate, A substrate of a raw material in a group consisting of a triacetylcellulose, a polysilicone, a polyurethane, and an epoxy resin (Epoxy Resin). The surface-reinforced transparent substrate according to claim 7, wherein the substrate is formed by co-extruding two or more kinds of plastic materials. The surface-reinforced transparent substrate of claim 1, wherein the cured product has a thickness of 0.01 to 500 μm. A surface strengthening method for a transparent substrate, characterized in that a coating composition comprising a sesquisesquioxane composite polymer represented by any one of Chemical Formulas 1 to 9 is applied onto a transparent substrate and cured. A surface strengthening method of a transparent substrate according to claim 10, wherein the coating composition is a solventless type. The surface strengthening method of the transparent substrate of claim 10, comprising: the sesquisesquioxane composite polymer according to claim 1; an initiator; and an organic solvent. The surface strengthening method of the transparent substrate of claim 12, wherein the above-mentioned sesquisesquioxane composite polymer is 5 to 90 parts by weight with respect to 100 parts by weight of the coating composition. An electronic article comprising the surface-reinforced transparent substrate of claim 1. The electronic product of claim 14, wherein the electronic product is a smart phone, a tablet personal computer, a notebook computer, an all-in-one PC (AIO), a liquid crystal display, a television, an advertisement board. Or touch Control panel, flexible and intelligent device that requires the flexibility of the substrate. The electronic article of claim 14, wherein the surface-enhanced transparent substrate is used as a window protective substrate or a protective film. A protective sheet comprising the surface-reinforced transparent substrate of claim 1.