KR102414700B1 - A coating method for plastic using silsesquioxane composite polymer - Google Patents

Abstract

The present invention relates to a plastic coating method using a silsesquioxane composite polymer, and more particularly, a silsesquioxane composite comprising a linear silsesquioxane chain of a specific structure and a cage-type silsesquioxane in one polymer. By coating the plastic surface using a polymer, the coating process is easy, and the formed coating layer has very high surface hardness, and has excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties. It relates to a plastic coating method using a silsesquioxane composite polymer that has excellent adhesion to plastic substrates and is easy to color due to high compatibility with pigments.

Description

Plastic coating method using silsesquioxane composite polymer {A COATING METHOD FOR PLASTIC USING SILSESQUIOXANE COMPOSITE POLYMER}

The present invention relates to a plastic coating method using a silsesquioxane composite polymer, and more particularly, to a silsesquioxane composite comprising a linear silsesquioxane chain of a specific structure and a cage-type silsesquioxane in one polymer. By coating the plastic surface using a polymer, the coating process is easy, and the formed coating layer has very high surface hardness, and has excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties. It relates to a plastic coating method using a silsesquioxane composite polymer that has excellent adhesion to plastic substrates and is easy to color due to high compatibility with pigments.

In general, plastic products have been applied and used in many products due to their high processability and flexibility. However, the plastic material has poor surface hardness, durability, stain resistance, scratch resistance, gloss properties and heat resistance, so a method of double or multiple coating of various coatings is used to give functionality to the surface depending on the use of the plastic product.

For example, in Korean Patent Laid-Open No. 10-2006-0121334 No. 10-2006-0121334, an organic film is formed on the surface of a plastic, an inorganic film is again formed on the outside, and an organic film is formed on the surface after physical and all plastics are molded in a vacuum chamber. After forming an inorganic film on the outside, it is possible to produce metal textures of various colors through physical and chemical vapor deposition in a vacuum chamber. Compressed to remove various foreign substances remaining on the surface of plastic molded products a washing process of washing and drying using air or other solvents; an organic coating process of forming a film by spraying or immersing an organic substance having excellent surface hardening and inorganic substances and adhesion to the plastic molded article whose surface has been cleaned through the washing process; An inorganic coating process for forming a film by applying an inorganic substance by spraying or immersing the plastic molded article having a surface hardened through the organic coating process to suppress gas elution; In order to impart physical and chemical properties to the plastic molded article cross-formed with the composite film of the organic/inorganic film and to realize the metal texture of various colors, physical and chemical vapor deposition is performed in a vacuum chamber to form a metal film. Although a method for surface coating a plastic molded article has been disclosed, the process is too complicated and the formed coating layer also has a problem in that durability and thermal stability are poor. A method of hard coating a plastic by surface coating using silica particles having a group, a mass average molecular weight of 3,000-200,000 measured by gel permeation chromatography, and a urethane-based polymer having a glass transition temperature of 30% or more and an ethylenically unsaturated group Although this has been disclosed, there is a problem in that the surface hardness, stain resistance and thermal stability are still at an unsatisfactory level.

In order to solve the above problems, in the present invention, the coating process is easy by coating the plastic surface using a coating solution, and the formed coating layer has very high surface hardness, and excellent transparency, scratch resistance, water repellency, and antifouling properties. To provide a plastic coating method using a silsesquioxane composite polymer that has properties, fingerprint resistance, thermal stability and gloss properties, has excellent adhesion to plastic substrates, and is easy to color due to high compatibility with pigments. do.

Another object of the present invention is to provide a plastic coating composition capable of imparting high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties to the plastic surface.

In addition, the present invention has a very high surface hardness on the surface, has excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties, and provides a plastic having a coating layer having excellent adhesion to a plastic substrate. aim to do

Another object of the present invention is to provide an article comprising a plastic having the coating layer.

In order to achieve the above object, the present invention provides a plastic coating method comprising coating and curing a plastic coating composition comprising a silsesquioxane composite polymer represented by any one of the following formulas 1 to 9 on a plastic surface:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 1 to 9,

이고, B는

이고, D는

이고, E는

이며,A is

and B is

and D is

and E is

is,

Y is each independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],

each X is independently R ²² or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acrylic group, thiol group, isocyanate group, nitrile group, nitro group, phenyl group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₁ ~ C ₄₀ Alkoxy group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ Heterocycloalkyl group, C ₆ ~ C ₄₀ Aryl group, C ₃ ~ C ₄₀ Heteroaryl group, C ₃ ~ C ₄₀ aralkyl group, C ₃ ~ C ₄₀ aryloxy group, or C ₃ ~ C ₄₀ aryl thiol group, preferably deuterium, halogen, amine group, (meth) acryl group, thiol group, isocyanate group , nitrile group, nitro group, phenyl group, cyclohexyl epoxy group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, amine group, epoxy group, cyclohexyl epoxy group, (meth) acryl group, It contains a thiol group, a phenyl group or an isocyanate group,

a and d are each independently an integer from 1 to 100,000, preferably a is from 3 to 1000, d is from 1 to 500, more preferably a is from 5 to 300, and d is from 2 to 100,

b is each independently an integer from 1 to 500,

e is each independently 1 or 2, preferably 1,

n is each independently an integer of 1 to 20, preferably 3 to 10.

The present invention also provides a plastic coating composition comprising the silsesquioxane composite polymer represented by any one of Formulas 1 to 9.

In addition, the present invention is a silsesquioxane composite polymer-coated plastic comprising a cured product coated with a plastic coating composition comprising a silsesquioxane composite polymer represented by any one of Formulas 1 to 9 on the surface and cured. to provide.

The present invention also provides an article comprising the silsesquioxane composite polymer coated plastic.

The plastic coating method according to the present invention uses a silsesquioxane composite polymer containing a linear silsesquioxane chain of a specific structure and a cage-type silsesquioxane in one polymer to coat the plastic surface, thereby making the coating process easy. In addition, the formed coating layer has very high surface hardness, has excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties, and has excellent adhesion to plastic substrates, so that optical films, protective films, It can be usefully applied to a variety of products such as plastics for electronic products, glasses, building exteriors, building interiors, plastic piping, wire coverings, optical lenses, soundproof walls, plastic signs, plastic sculptures, furniture, lighting, sunroofs, helmets, etc. have.

Hereinafter, the present invention will be described in detail.

The plastic coating method of the present invention provides a plastic coating method comprising coating and curing a plastic coating composition comprising a silsesquioxane composite polymer represented by any one of the following formulas 1 to 9 on a plastic surface:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 1 to 9,

이고, B는

이고, D는

이고, E는

이며,A is

and B is

and D is

and E is

is,

Y is each independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],

each X is independently R ²² or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acrylic group, thiol group, isocyanate group, nitrile group, nitro group, phenyl group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₁ ~ C ₄₀ Alkoxy group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ Heterocycloalkyl group, C ₆ ~ C ₄₀ Aryl group, C ₃ ~ C ₄₀ Heteroaryl group, C ₃ ~ C ₄₀ aralkyl group, C ₃ ~ C ₄₀ aryloxy group, or C ₃ ~ C ₄₀ aryl thiol group, preferably deuterium, halogen, amine group, (meth) acryl group, thiol group, isocyanate group , nitrile group, nitro group, phenyl group, cyclohexyl epoxy group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, amine group, epoxy group, cyclohexyl epoxy group, (meth) acryl group, It contains a thiol group, a phenyl group or an isocyanate group,

a and d are each independently an integer from 1 to 100,000, preferably a is from 3 to 1000, d is from 1 to 500, more preferably a is from 5 to 300, and d is from 2 to 100,

b is each independently an integer from 1 to 500,

e is each independently 1 or 2, preferably 1,

n is each independently an integer of 1 to 20, preferably 3 to 10.

The plastic coating method of the present invention and the plastic coating composition used therein have a specific structure having repeating units of [A]a and [D]d, and optionally having repeating units [B]b or [E]e By coating and curing the quioxane polymer on the surface of the plastic, excellent surface hardness, transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties for plastics are achieved only by forming a single coating layer through a solution process. can have it

The plastic to be coated in the present invention is not particularly limited as long as it is composed of plastic, for example, polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (polyethylene) terephthalate, PET, PET), polyamides (polyamides, PA, nylon), polyester (PES), polyvinyl chloride (PVC), polyurethane (polyurethanes, PU), polycarbonate (PC) , high hardness polycarbonate (high hardness PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), polyetherimide (PEI) ), a single plastic material such as acrylic, etc., may be a mixture of two or more plastic materials, and may be a composite plastic in which plastic and inorganic fibers such as glass fibers or carbon fibers are mixed. Therefore, it can be applied to all plastic products including sheets, films, injection moldings, sculptures and beads.

The silsesquioxane composite polymer represented by Formula 1 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the following formula (10); and a second step of adding an organic silane compound and stirring the reaction solution to acidity by adding an acidic catalyst to the reactor to introduce the [D]d(OR ² ) ₂ structure in Chemical Formula 10 after the first step step; and a third step of converting the reaction solution to basic by adding a basic catalyst to the reactor after the second step to carry out the condensation reaction.

[Formula 10]

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

The silsesquioxane composite polymer represented by Formula 2 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the above formula (10); And after the first step, in order to introduce [D]d(OR ³ ) ₂ and [D]d(OR ⁴ ) ₂ structures in Formula 10 as shown in Formula 2, an acidic catalyst is added to the reactor to acidify the reaction solution. After adjustment, a second step of adding an excess of an organosilane compound and stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; And through the third step reaction, it can be prepared by proceeding with a purification step in which the cage structure, which is a by-product produced alone, is removed by recrystallization.

The silsesquioxane composite polymer represented by Formula 3 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the above formula (10); and a second step of adding an organic silane compound and stirring after adjusting the reaction solution to acidity by adding an acid catalyst to the reactor to introduce the [D]d(OR ⁵ ) ₂ structure in Chemical Formula 10 after the first step step; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and a fourth step of adding an acidic catalyst to the reactor to introduce the [E]eX ₂ structure at the end of the composite polymer after the third step, converting the reaction solution into an acidic atmosphere, mixing an organosilane compound and stirring can be manufactured.

The silsesquioxane composite polymer represented by Formula 4 of the present invention is

A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and controlling the degree of condensation; and after the first step, an acidic catalyst was added to the reactor to introduce the [B]b structure and [D]d(OR ⁷ ) ₂ structure in Chemical Formula 10 to adjust the reaction solution to acidity, and then to prepare an organosilane compound a second step of adding and stirring; and a third step of converting the reaction solution to basic by adding a basic catalyst to the reactor after the second step to carry out the condensation reaction.

The silsesquioxane composite polymer represented by Formula 5 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the above formula (10); And after the first step, in order to introduce the [B]b structure and [D]d(OR ⁸ ) ₂ , [D]d(OR ⁹ ) ₂ structure in Chemical Formula 10, an acidic catalyst is added to the reactor to prepare the reaction solution. a second step of adding and stirring an excess of an organosilane compound after adjusting to acidity; and a third step of the condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and a fourth step of removing the single cage-forming structure through recrystallization and filtering after the third step.

The silsesquioxane composite polymer represented by Formula 6 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, then adding an organic silane compound and condensing to prepare the above formula (10); and after the first step, an acidic catalyst was added to the reactor to introduce the [B]b structure and [D]d(OR ¹⁰ ) ₂ structure in Chemical Formula 10 to adjust the reaction solution to acidity, and then, an organosilane compound a second step of adding and stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after the second step to convert the reaction solution to basic; and a fourth step of adding an acidic catalyst to the reactor to introduce the [E]eX ₂ structure at the end of the composite polymer after the third step, converting the reaction solution into an acidic atmosphere, mixing an organosilane compound and stirring can be manufactured.

Preferably, in the method for preparing Formulas 1 to 6, the pH of the reaction solution in the first step of the present invention is preferably 9 to 11.5, and the pH of the reaction solution in the second step is preferably 2 to 4, The pH of the reaction solution in the third step is preferably 8 to 11.5, and the pH of the reaction solution in the fourth step of introducing Ee is preferably 1.5 to 4. When it is within the above range, the yield of the prepared silsesquioxane composite polymer may be high, and mechanical properties of the prepared silsesquioxane composite polymer may be improved.

The silsesquioxane composite polymer represented by Formula 7 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and preparing two types of Chemical Formula 10 with a controlled degree of condensation; In order to introduce the [B]b structure and [D]d(OR ¹² ) ₂ structure to the formula 10 obtained in step 1, an acidic catalyst was added to the reactor to adjust the reaction solution to be acidic, and then an organosilane compound was added, a second step of stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after each of the two-step reactions to convert the reaction solution to basic; and step 4 of condensing and linking the two or more substances obtained through step 3 under basic conditions.

The silsesquioxane composite polymer represented by Formula 8 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and preparing two types of Chemical Formula 10 with a controlled degree of condensation; In order to introduce the [B]b structure and [D]d(OR ¹⁴ ) ₂ structure to Chemical Formula 10 obtained in step 1, an acidic catalyst was added to the reactor to adjust the reaction solution to be acidic, and then an organosilane compound was added, a second step of stirring; a third step of performing a condensation reaction by adding a basic catalyst to the reactor after each of the two-step reactions to convert the reaction solution to basic; a fourth step of condensing and connecting two or more substances obtained through the third step under basic conditions; a fifth step of adding an organic silane compound and stirring after adjusting the reaction solution to acidity by adding an acid catalyst to the reactor for introducing [D]d(OR ¹³ ) ₂ after step 4; and a sixth step of performing a condensation reaction by adding a basic catalyst to the reactor after the five-step reaction to convert the reaction solution to basic.

The silsesquioxane composite polymer represented by Formula 9 of the present invention is

A first step of mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and preparing two types of Chemical Formula 10 with a controlled degree of condensation; a second step of adding an organic silane compound and stirring after adjusting the reaction solution to acidity by adding an acid catalyst to the reactor to introduce the [B]b structure to Chemical Formula 10 obtained in step 1; A third step of performing a condensation reaction by adding a basic catalyst to the reactor after each of the two-step reactions to convert the reaction solution to basic; a fourth step of condensing and linking two or more compounds obtained through the third step under basic conditions; After the fourth step [D]d(OR ⁵ ) ₂ A fifth step of adding an organic silane compound and stirring after adjusting the reaction solution to be acidic by adding an acidic catalyst to the reactor for introducing; a sixth step of performing a condensation reaction by adding a basic catalyst to the reactor after the five-step reaction to convert the reaction solution to basic; After the sixth step, an acidic catalyst is introduced into the reactor to introduce the [E]eX ₂ structure at the end of the composite polymer, the reaction solution is converted into an acidic atmosphere, and a seventh step of mixing and stirring an organosilane compound. can be manufactured.

Preferably, in the method for preparing the polymer of Chemical Formulas 7 to 9, the pH of the reaction solution in the first step is preferably 9 to 11.5, and the pH of the reaction solution in the second step is preferably 2 to 4, The pH of the reaction solution in step 3 is preferably 8 to 11.5, the pH of the reaction solution in step 4 is preferably 9 to 11.5, and the pH of the reaction solution in step 5 is preferably 2 to 4, It is preferable that the pH of the reaction solution of the sixth step is 8 to 11.5, and the pH of the reaction solution of the seventh step of introducing Ee is preferably 1.5 to 4. When it is within the above range, the yield of the prepared silsesquioxane composite polymer may be high, and mechanical properties of the prepared silsesquioxane composite polymer may be improved.

In addition, if necessary, in order to further introduce the [B]b structure and [D]d(OR) ₂ structure to each composite polymer, an acidic catalyst is added to the reactor to adjust the reaction solution to acidity, then an organosilane compound is added, stirring; and a [B]b repeating unit may be further included in the composite polymer through the step of adding a basic catalyst to the reactor after the step to convert the reaction solution to basic and performing a condensation reaction.

In addition, if necessary, in order to introduce the [E]eX ₂ structure at the end of each composite polymer, an acidic catalyst is put into the reactor to convert the reaction solution into an acidic atmosphere, and an organosilane compound is mixed and stirred. It may further include a repeating unit of [E]e at the end.

In the method for producing the silsesquioxane composite polymer, a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and this is neutralized and acidified with an acidic catalyst to induce re-hydrolysis, and again two or more basic catalysts are used. Acidity and basicity can be continuously controlled in one reactor by carrying out the basic condensation using a mixed catalyst of

In this case, the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal-based basic catalyst and an amine-based basic catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Preferably, the amine-based basic catalyst is tetramethylammonium hydroxide (TMAH), and the metal-based basic catalyst is potassium hydroxide (KOH) or sodium bicarbonate (NaHCO ₃ ). The content of each component in the mixed catalyst may be arbitrarily adjusted in a ratio of preferably 10 to 90: 10 to 90 parts by weight of the amine-based basic catalyst and the metal-based basic catalyst. If it is within the above range, it is possible to minimize the reactivity of the functional group with the catalyst during hydrolysis, and this has the advantage that defects of organic functional groups such as Si-OH or Si-alkoxy are significantly reduced, so that the degree of condensation can be freely controlled. In addition, the acid catalyst may be used without limitation as long as it is an acidic material commonly used in the art, for example, a general acidic material such as HCl, H ₂ SO ₄ , HNO ₃ , CH ₃ COOH may be used, In addition, organic acidic substances such as latic acid, tartaric acid, maleic acid, and citric acid can be applied.

In the method for producing the silsesquioxane composite polymer of the present invention, the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Alcohols such as cellosolve, ketones such as lactate, acetone, and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- In addition to polar solvents such as methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acro Various solvents such as nitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, and benzyl alcohol can be used.

In addition, as the organosilane compound, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , which is a silsesquioxane composite polymer of the present invention, of Formulas 1 to 9, Organosilanes comprising 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 may be used and , preferably by increasing the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property of an organosilane compound containing a phenyl group or an amino group, or by increasing the curing density of the composite polymer to increase the mechanical strength and hardness of the cured layer An organic silane compound containing an epoxy group or (meth)acryl group having the effect of improving the silane may be used.

Specific examples of the organosilane compound include (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3 -glycidoxypropyl) dimethylethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrime oxysilane, dimethyltetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, Among these, it can also be used individually by 1 type or in combination of 2 or more types. It is more preferable to use a mixture of two or more for the physical properties of the final composition.

In the present invention, n of the [(SiO _3/2 R) _4+2n O] structure introduced into the repeating unit [D]d of the above formulas may be substituted with an integer of 1 to 20, preferably 3 to 10, , more preferably, the average n value is 4 to 5, for example, when n is 4, when expressing a substituted structure, it is as follows:

[Formula 11]

In the above formula, R is as defined above.

In the present invention, n of the [(SiO _3/2 R) _4+2n R] structure introduced into the repeating unit [B]b or [E]e of the above formulas may be substituted with an integer of 1 to 20, preferably It is 3 to 10, and more preferably, the average n value is 4 to 5. For example, when n is 4, a substituted structure is expressed as shown in Formula 12:

[Formula 12]

In the above formula, R is as defined above.

As a specific example, the silsesquioxane polymer according to the present invention may be a polymer shown in Tables 1 to 18 below. In Tables 1 to 9, ECHE means (Epoxycyclohexyl)ethyl, GlyP means Glycidoxypropyl, and POMMA means (methacryloyloxy)propyl, and when two or more are described, it means mixed use. n is each independently 1 to 8;

The silsesquioxane composite polymer of Formula 1 may be a polymer shown in Table 1 or 2 below.

No R1 R2 R16 R19 Y of R 1-1 OH, methoxy H, methyl ECHE ECHE ECHE 1-2 OH, methoxy H, methyl phenyl phenyl phenyl 1-3 OH, methoxy H, methyl methyl methyl methyl 1-4 OH, methoxy H, methyl GlyP GlyP GlyP 1-5 OH, methoxy H, methyl POMMA POMMA POMMA 1-6 OH, methoxy H, methyl ECHE phenyl phenyl 1-7 OH, methoxy H, methyl ECHE methyl methyl 1-8 OH, methoxy H, methyl ECHE GlyP GlyP 1-9 OH, methoxy H, methyl ECHE POMMA POMMA 1-10 OH, methoxy H, methyl phenyl ECHE ECHE 1-11 OH, methoxy H, methyl phenyl methyl methyl 1-12 OH, methoxy H, methyl phenyl GlyP GlyP 1-13 OH, methoxy H, methyl phenyl POMMA POMMA 1-14 OH, methoxy H, methyl methyl ECHE ECHE 1-15 OH, methoxy H, methyl methyl phenyl phenyl 1-16 OH, methoxy H, methyl methyl GlyP GlyP 1-17 OH, methoxy H, methyl methyl POMMA POMMA 1-18 OH, methoxy H, methyl GlyP ECHE ECHE 1-19 OH, methoxy H, methyl GlyP phenyl phenyl 1-20 OH, methoxy H, methyl GlyP methyl methyl 1-21 OH, methoxy H, methyl GlyP POMMA POMMA 1-22 OH, methoxy H, methyl POMMA ECHE ECHE 1-23 OH, methoxy H, methyl POMMA phenyl phenyl 1-24 OH, methoxy H, methyl POMMA methyl methyl 1-25 OH, methoxy H, methyl POMMA GlyP GlyP

No R1 R2 R16 R19 R of Y n 2-1 OH, methoxy H, methyl ECHE alkyl thiol ECHE 1 to 8 2-2 OH, CF ₃ H, ethyl phenyl phenyl phenyl 1 to 8 2-3 OH, methoxy H, acetyltyl alkyl thiol methyl methyl 1 to 8 2-4 CF ₃ ,methoxy vinyl, methyl GlyP dodecyl GlyP 1 to 8 2-5 OH, methoxy H, methyl POMMA alkyl thiol POMMA 1 to 8 2-6 OH, C ₈ F ₁₃ H, F ECHE phenyl phenyl 1 to 8 2-7 OH, CF ₃ CF ₃ ,methyl ECHE octyl methyl 1 to 8 2-8 OH, C ₈ F ₁₃ H, methyl F alkyl thiol GlyP 1 to 8 2-9 OH, methoxy H, CF ₃ ECHE POMMA POMMA 1 to 8 2-10 OH, methoxy H, methyl phenyl alkyl thiol ECHE 1 to 8 2-11 OH, C ₈ F ₁₃ aryl, methyl alkyl thiol methyl hexyl 1 to 8 2-12 OH, alkyl thiol H, methacrylic phenyl GlyP GlyP 1 to 8 2-13 OH, methoxy H, methyl alkyl thiol POMMA POMMA 1 to 8 2-14 OH, acrylic H, octyl methyl ECHE aminopropyl 1 to 8 2-15 vinyl, methoxy H, methyl methyl alkyl thiol phenyl 1 to 8 2-16 alkylamine H, methyl methyl GlyP GlyP 1 to 8 2-17 OH, ethyl, methyl Alkyl thiol, methyl methyl POMMA POMMA 1 to 8 2-18 acetoxy, methoxy H, methyl GlyP ECHE aminopropyl 1 to 8 2-19 propoxy, methoxy H, CF ₃ GlyP phenyl phenyl 1 to 8 2-20 OH, methoxy H, methyl aminopropyl methyl octyl 1 to 8 2-21 C ₈ F ₁₃ ,methoxy C ₈ F ₁₃ ,methyl GlyP POMMA POMMA 1 to 8 2-22 OH, aryl H, profile POMMA profile ECHE 1 to 8 2-23 OH, methoxy F, methyl POMMA phenyl phenyl 1 to 8 2-24 CF ₃ , Methacrylic H, methyl POMMA methyl methyl 1 to 8 2-25 OH, methoxy H, ethyl aminopropyl GlyP GlyP 1 to 8

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

No R3 R4 R16 R19 Y of R 3-1 H, methyl H, methyl ECHE ECHE ECHE 3-2 H, methyl H, methyl phenyl phenyl phenyl 3-3 H, methyl H, methyl methyl methyl methyl 3-4 H, methyl H, methyl GlyP GlyP GlyP 3-5 H, methyl H, methyl POMMA POMMA POMMA 3-6 H, methyl H, methyl ECHE phenyl phenyl 3-7 H, methyl H, methyl ECHE methyl methyl 3-8 H, methyl H, methyl ECHE GlyP GlyP 3-9 H, methyl H, methyl ECHE POMMA POMMA 3-10 H, methyl H, methyl phenyl ECHE ECHE 3-11 H, methyl H, methyl phenyl methyl methyl 3-12 H, methyl H, methyl phenyl GlyP GlyP 3-13 H, methyl H, methyl phenyl POMMA POMMA 3-14 H, methyl H, methyl methyl ECHE ECHE 3-15 H, methyl H, methyl methyl phenyl phenyl 3-16 H, methyl H, methyl methyl GlyP GlyP 3-17 H, methyl H, methyl methyl POMMA POMMA 3-18 H, methyl H, methyl GlyP ECHE ECHE 3-19 H, methyl H, methyl GlyP phenyl phenyl 3-20 H, methyl H, methyl GlyP methyl methyl 3-21 H, methyl H, methyl GlyP POMMA POMMA 3-22 H, methyl H, methyl POMMA ECHE ECHE 3-23 H, methyl H, methyl POMMA phenyl phenyl 3-24 H, methyl H, methyl POMMA methyl methyl 3-25 H, methyl H, methyl POMMA GlyP GlyP

No R3 R4 R16 R19 Y of R 4-1 OH, methoxy H, methyl ECHE alkyl thiol ECHE 4-2 OH, CF ₃ H, ethyl phenyl phenyl phenyl 4-3 OH, methoxy H, acetyltyl alkyl thiol methyl methyl 4-4 CF ₃ ,methoxy vinyl, methyl POMMA dodecyl GlyP 4-5 OH, acrylic H, methyl POMMA alkyl thiol octyl 4-6 vinyl, methoxy H, F ECHE phenyl POMMA 4-7 alkylamine CF ₃ ,methyl ECHE octyl methyl 4-8 OH, ethyl, methyl H, methyl F aminopropyl GlyP 4-9 acetoxy, methoxy H, CF ₃ aminopropyl POMMA hexyl 4-10 propoxy, methoxy H, methyl phenyl alkyl thiol ECHE 4-11 OH, C ₈ F ₁₃ aryl, methyl alkyl thiol methyl hexyl 4-12 OH, methoxy H, methacrylic phenyl GlyP GlyP 4-13 CF ₃ ,methoxy H, methyl octyl POMMA POMMA 4-14 OH, acrylic H, octyl methyl ECHE aminopropyl 4-15 vinyl, methoxy H, methyl octyl alkyl thiol phenyl 4-16 alkylamine H, methyl octyl GlyP GlyP 4-17 OH, methoxy Alkyl thiol, methyl methyl POMMA POMMA 4-18 acetoxy, methoxy H, methyl GlyP ECHE aminopropyl 4-19 propoxy, methoxy H, CF ₃ GlyP aminopropyl phenyl 4-20 OH, methoxy H, methyl aminopropyl methyl octyl 4-21 propoxy, methoxy C ₈ F ₁₃ ,methyl GlyP POMMA POMMA 4-22 OH, methoxy H, profile POMMA profile ECHE 4-23 C ₈ F ₁₃ ,methoxy F, methyl POMMA phenyl phenyl 4-24 OH, aryl H, methyl GlyP methyl GlyP 4-25 OH, methoxy H, ethyl aminopropyl GlyP GlyP

As a specific example, the silsesquioxane composite polymer of Formula 3 may be a polymer shown in Tables 5 or 6 below.

No R5 R16 R19 R20 Y of R X of R 5-1 H, methyl ECHE ECHE ECHE ECHE ECHE 5-2 H, methyl phenyl phenyl phenyl phenyl phenyl 5-3 H, methyl methyl methyl methyl methyl methyl 5-4 H, methyl GlyP EGCDX GlyP EGCDX GlyP 5-5 H, methyl POMMA POMMA POMMA POMMA POMMA 5-6 H, methyl ECHE ECHE phenyl ECHE phenyl 5-7 H, methyl ECHE ECHE methyl ECHE methyl 5-8 H, methyl ECHE ECHE GlyP ECHE GlyP 5-9 H, methyl ECHE ECHE POMMA ECHE POMMA 5-10 H, methyl ECHE phenyl ECHE phenyl ECHE 5-11 H, methyl ECHE methyl ECHE methyl ECHE 5-12 H, methyl ECHE GlyP ECHE GlyP ECHE 5-13 H, methyl ECHE POMMA ECHE POMMA ECHE 5-14 H, methyl phenyl phenyl ECHE phenyl ECHE 5-15 H, methyl phenyl phenyl methyl phenyl methyl 5-16 H, methyl phenyl phenyl EGDCX phenyl EGDCX 5-17 H, methyl phenyl phenyl POMMA phenyl POMMA 5-18 H, methyl phenyl ECHE phenyl ECHE phenyl 5-19 H, methyl phenyl methyl phenyl methyl phenyl 5-20 H, methyl phenyl GlyP phenyl GlyP phenyl 5-21 H, methyl phenyl POMMA phenyl POMMA phenyl 5-22 H, methyl methyl methyl ECHE methyl ECHE 5-23 H, methyl methyl methyl phenyl methyl phenyl 5-25 H, methyl methyl methyl GlyP methyl GlyP 5-25 H, methyl methyl methyl POMMA methyl POMMA 5-26 H, methyl methyl ECHE methyl ECHE methyl 5-27 H, methyl methyl phenyl methyl phenyl methyl 5-28 H, methyl methyl GlyP methyl GlyP methyl 5-29 H, methyl methyl POMMA methyl POMMA methyl 5-30 H, methyl GlyP GlyP ECHE GlyP ECHE 5-31 H, methyl GlyP GlyP phenyl GlyP phenyl 5-32 H, methyl GlyP GlyP methyl GlyP methyl 5-33 H, methyl GlyP GlyP POMMA GlyP POMMA 5-34 H, methyl GlyP ECHE GlyP ECHE GlyP 5-35 H, methyl GlyP phenyl GlyP phenyl GlyP 5-36 H, methyl GlyP methyl GlyP methyl GlyP 5-37 H, methyl GlyP POMMA GlyP POMMA GlyP 5-35 H, methyl POMMA POMMA ECHE POMMA ECHE 5-39 H, methyl POMMA POMMA phenyl POMMA phenyl 5-40 H, methyl POMMA POMMA methyl POMMA methyl 5-41 H, methyl POMMA POMMA GlyP POMMA GlyP 5-42 H, methyl POMMA ECHE POMMA ECHE POMMA 5-43 H, methyl POMMA phenyl POMMA phenyl POMMA 5-44 H, methyl POMMA methyl POMMA methyl POMMA 5-45 H, methyl POMMA GlyP POMMA GlyP POMMA

No R5 R16 R19 R20 Y of R X of R 6-1 H, methyl ECHE ECHE ECHE ECHE ECHE 6-2 H, ethyl phenyl phenyl phenyl phenyl phenyl 6-3 H, acetyltyl alkyl thiol methyl methyl methyl methyl 6-4 vinyl, methyl POMMA dodecyl GlyP EGCDX GlyP 6-5 H, methyl POMMA alkyl thiol POMMA POMMA POMMA 6-6 H, F ECHE phenyl phenyl ECHE phenyl 6-7 CF ₃ ,methyl ECHE octyl methyl ECHE methyl 6-8 H, methyl F aminopropyl GlyP ECHE GlyP 6-9 H, CF ₃ aminopropyl POMMA POMMA ECHE POMMA 6-10 H, methyl phenyl alkyl thiol ECHE phenyl ECHE 6-11 aryl, methyl alkyl thiol methyl ECHE methyl ECHE 6-12 H, methacrylic phenyl GlyP ECHE GlyP ECHE 6-13 H, methyl octyl POMMA ECHE POMMA ECHE 6-14 H, octyl methyl ECHE ECHE phenyl ECHE 6-15 H, methyl octyl alkyl thiol methyl phenyl methyl 6-16 H, methyl octyl GlyP EGDCX phenyl EGDCX 6-17 Alkyl thiol, methyl methyl POMMA POMMA phenyl POMMA 6-18 H, methyl GlyP GlyP phenyl ECHE phenyl 6-19 H, CF ₃ POMMA POMMA phenyl methyl phenyl 6-20 H, methyl ECHE aminopropyl phenyl GlyP phenyl 6-21 C ₈ F ₁₃ ,methyl alkyl thiol phenyl phenyl POMMA phenyl 6-22 H, profile GlyP GlyP ECHE methyl ECHE 6-23 F, methyl POMMA POMMA phenyl methyl phenyl 6-24 H, methyl ECHE aminopropyl GlyP methyl GlyP 6-25 H, ethyl aminopropyl phenyl POMMA methyl POMMA 6-26 H, acetyltyl methyl octyl methyl ECHE methyl 6-27 vinyl, methyl POMMA POMMA methyl phenyl methyl 6-28 H, methyl methyl methyl methyl GlyP methyl 6-29 H, F dodecyl GlyP methyl POMMA methyl 6-30 CF ₃ ,methyl alkyl thiol octyl ECHE GlyP ECHE 6-31 H, methyl phenyl POMMA phenyl GlyP phenyl 6-32 H, octyl octyl methyl methyl GlyP methyl 6-33 H, methyl aminopropyl GlyP POMMA GlyP POMMA 6-34 H, methyl POMMA hexyl GlyP ECHE GlyP 6-35 H, acetyltyl alkyl thiol ECHE GlyP phenyl GlyP 6-36 vinyl, methyl methyl hexyl GlyP methyl GlyP 6-37 H, methyl GlyP GlyP GlyP POMMA GlyP 6-38 H, F POMMA POMMA ECHE POMMA ECHE 6-39 CF ₃ ,methyl ECHE aminopropyl phenyl POMMA phenyl 6-40 H, methyl alkyl thiol phenyl methyl POMMA methyl 6-41 vinyl, methyl GlyP GlyP GlyP POMMA GlyP 6-42 H, methyl POMMA POMMA POMMA ECHE POMMA 6-43 H, F ECHE aminopropyl POMMA phenyl POMMA 6-44 CF ₃ ,methyl aminopropyl phenyl POMMA methyl POMMA 6-45 H, methyl POMMA GlyP POMMA GlyP POMMA

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

No R6 R7 R16 R17 R18 R19 X of R Y of R 7-1 OH, methoxy H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE 7-2 OH, methoxy H, methyl phenyl phenyl H, methyl phenyl phenyl phenyl 7-3 OH, methoxy H, methyl methyl methyl H, methyl methyl methyl methyl 7-4 OH, methoxy H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP 7-5 OH, methoxy H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA 7-6 OH, methoxy H, methyl ECHE ECHE H, methyl phenyl ECHE phenyl 7-7 OH, methoxy H, methyl ECHE ECHE H, methyl methyl ECHE methyl 7-8 OH, methoxy H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP 7-9 OH, methoxy H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA 7-10 OH, methoxy H, methyl phenyl phenyl H, methyl ECHE phenyl ECHE 7-11 OH, methoxy H, methyl phenyl phenyl H, methyl methyl phenyl methyl 7-12 OH, methoxy H, methyl phenyl phenyl H, methyl GlyP phenyl GlyP 7-13 OH, methoxy H, methyl phenyl phenyl H, methyl POMMA phenyl POMMA 7-14 OH, methoxy H, methyl methyl methyl H, methyl ECHE methyl ECHE 7-15 OH, methoxy H, methyl methyl methyl H, methyl phenyl methyl phenyl 7-16 OH, methoxy H, methyl methyl methyl H, methyl GlyP methyl GlyP 7-17 OH, methoxy H, methyl methyl methyl H, methyl POMMA methyl POMMA 7-18 OH, methoxy H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE 7-19 OH, methoxy H, methyl GlyP GlyP H, methyl phenyl GlyP phenyl 7-20 OH, methoxy H, methyl GlyP GlyP H, methyl methyl GlyP methyl 7-21 OH, methoxy H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA 7-22 OH, methoxy H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE 7-23 OH, methoxy H, methyl POMMA POMMA H, methyl phenyl POMMA phenyl 7-24 OH, methoxy H, methyl POMMA POMMA H, methyl methyl POMMA methyl 7-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP

No R6 R7 R16 R17 R18 R19 X of R Y of R 8-1 OH, methoxy H, methyl ECHE alkyl thiol H, methyl ECHE alkyl thiol ECHE 8-2 OH, CF ₃ H, ethyl ECHE phenyl H, octyl phenyl phenyl phenyl 8-3 OH, methoxy H, acetyltyl ECHE methyl H, methyl methyl methyl methyl 8-4 CF ₃ ,methoxy vinyl, methyl phenyl GlyP H, methyl GlyP GlyP GlyP 8-5 OH, methoxy H, methyl phenyl POMMA Alkyl thiol, methyl POMMA POMMA POMMA 8-6 OH, C ₈ F ₁₃ H, F phenyl ECHE H, methyl phenyl ECHE phenyl 8-7 OH, CF ₃ CF ₃ ,methyl ECHE ECHE H, CF ₃ methyl ECHE methyl 8-8 OH, C ₈ F ₁₃ H, methyl hexyl ECHE H, ethyl GlyP ECHE GlyP 8-9 OH, methoxy H, CF ₃ GlyP ECHE H, acetyltyl POMMA ECHE POMMA 8-10 OH, methoxy H, methyl POMMA phenyl vinyl, methyl ECHE phenyl ECHE 8-11 OH, C ₈ F ₁₃ aryl, methyl aminopropyl phenyl H, methyl hexyl phenyl hexyl 8-12 OH, alkyl thiol H, methacrylic phenyl phenyl H, F GlyP phenyl GlyP 8-13 OH, methoxy H, methyl GlyP ECHE vinyl, methyl POMMA phenyl POMMA 8-14 OH, acrylic H, octyl POMMA hexyl H, methyl aminopropyl methyl aminopropyl 8-15 vinyl, methoxy H, methyl aminopropyl GlyP H, F phenyl methyl phenyl 8-16 alkylamine H, methyl phenyl POMMA CF ₃ ,methyl GlyP methyl GlyP 8-17 OH, ethyl, methyl Alkyl thiol, methyl octyl aminopropyl H, methyl POMMA methyl POMMA 8-18 acetoxy, methoxy H, methyl POMMA phenyl H, CF ₃ aminopropyl GlyP aminopropyl 8-19 propoxy, methoxy H, CF ₃ ECHE GlyP H, methyl phenyl GlyP phenyl 8-20 OH, methoxy H, methyl phenyl POMMA H, methyl octyl GlyP octyl 8-21 C ₈ F ₁₃ ,methoxy C ₈ F ₁₃ ,methyl methyl aminopropyl H, methyl POMMA GlyP POMMA 8-22 OH, aryl H, profile GlyP phenyl Alkyl thiol, methyl ECHE POMMA ECHE 8-23 OH, methoxy F, methyl POMMA octyl H, methyl phenyl POMMA phenyl 8-24 CF ₃ , Methacrylic H, methyl POMMA POMMA H, CF ₃ methyl POMMA methyl 8-25 OH, methoxy H, ethyl POMMA ECHE H, methyl GlyP POMMA GlyP

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

No R8 R9 R16 R17 R18 R19 X of R Y of R 9-1 H, methyl H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE 9-2 H, methyl H, methyl phenyl phenyl H, methyl phenyl phenyl phenyl 9-3 H, methyl H, methyl methyl methyl H, methyl methyl methyl methyl 9-4 H, methyl H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP 9-5 H, methyl H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA 9-6 H, methyl H, methyl ECHE ECHE H, methyl phenyl ECHE phenyl 9-7 H, methyl H, methyl ECHE ECHE H, methyl methyl ECHE methyl 9-8 H, methyl H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP 9-9 H, methyl H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA 9-10 H, methyl H, methyl phenyl phenyl H, methyl ECHE phenyl ECHE 9-11 H, methyl H, methyl phenyl phenyl H, methyl methyl phenyl methyl 9-12 H, methyl H, methyl phenyl phenyl H, methyl GlyP phenyl GlyP 9-13 H, methyl H, methyl phenyl phenyl H, methyl POMMA phenyl POMMA 9-14 H, methyl H, methyl methyl methyl H, methyl ECHE methyl ECHE 9-15 H, methyl H, methyl methyl methyl H, methyl phenyl methyl phenyl 9-16 H, methyl H, methyl methyl methyl H, methyl GlyP methyl GlyP 9-17 H, methyl H, methyl methyl methyl H, methyl POMMA methyl POMMA 9-18 H, methyl H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE 9-19 H, methyl H, methyl GlyP GlyP H, methyl phenyl GlyP phenyl 9-20 H, methyl H, methyl GlyP GlyP H, methyl methyl GlyP methyl 9-21 H, methyl H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA 9-22 H, methyl H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE 9-23 H, methyl H, methyl POMMA POMMA H, methyl phenyl POMMA phenyl 9-24 H, methyl H, methyl POMMA POMMA H, methyl methyl POMMA methyl 9-25 H, methyl H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP

No R8 R9 R16 R17 R18 R19 B of R D of R 10-1 H, methyl CF ₃ ,methyl ECHE alkyl thiol H, methyl ECHE alkyl thiol ECHE 10-2 H, ethyl H, methyl ECHE phenyl Alkyl thiol, methyl hexyl phenyl hexyl 10-3 H, acetyltyl H, CF ₃ ECHE methyl H, methyl GlyP methyl GlyP 10-4 vinyl, methyl H, methyl phenyl GlyP H, CF ₃ POMMA GlyP POMMA 10-5 H, methyl H, methyl phenyl POMMA H, ethyl aminopropyl POMMA aminopropyl 10-6 H, F H, octyl phenyl ECHE H, F phenyl ECHE phenyl 10-7 CF ₃ ,methyl H, methyl ECHE ECHE vinyl, methyl GlyP ECHE GlyP 10-8 H, methyl H, methyl hexyl ECHE H, methyl POMMA ECHE POMMA 10-9 H, CF ₃ Alkyl thiol, methyl GlyP ECHE H, F aminopropyl ECHE aminopropyl 10-10 H, methyl H, methyl POMMA phenyl CF ₃ ,methyl phenyl phenyl phenyl 10-11 aryl, methyl H, methyl aminopropyl phenyl H, methyl octyl phenyl octyl 10-12 H, methacrylic H, methyl phenyl phenyl H, CF ₃ POMMA phenyl POMMA 10-13 H, methyl Alkyl thiol, methyl GlyP ECHE H, methyl ECHE ECHE ECHE 10-14 H, octyl H, methyl POMMA hexyl H, methyl phenyl hexyl phenyl 10-15 H, methyl H, F aminopropyl GlyP H, octyl methyl GlyP methyl 10-16 H, methyl CF ₃ ,methyl phenyl POMMA H, methyl GlyP POMMA GlyP 10-17 Alkyl thiol, methyl H, methyl octyl aminopropyl H, methyl POMMA aminopropyl POMMA 10-18 H, methyl H, CF ₃ POMMA phenyl Alkyl thiol, methyl aminopropyl phenyl aminopropyl 10-19 H, CF ₃ H, methyl ECHE GlyP H, methyl phenyl GlyP phenyl 10-20 H, methyl H, methyl phenyl POMMA H, methyl octyl POMMA octyl 10-21 C ₈ F ₁₃ ,methyl H, methyl methyl aminopropyl H, methyl POMMA aminopropyl POMMA 10-22 H, profile Alkyl thiol, methyl GlyP phenyl Alkyl thiol, methyl ECHE phenyl ECHE 10-23 F, methyl H, methyl POMMA octyl H, methyl phenyl octyl phenyl 10-24 H, methyl H, CF ₃ POMMA POMMA H, CF ₃ methyl POMMA methyl 10-25 H, ethyl H, methyl POMMA ECHE H, methyl GlyP ECHE GlyP

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

No R16 R17 R18 R19 R20 X of R Y of R E x R 11-1 ECHE ECHE H, methyl ECHE ECHE ECHE ECHE ECHE 11-2 phenyl phenyl H, methyl phenyl phenyl phenyl phenyl phenyl 11-3 methyl methyl H, methyl methyl methyl methyl methyl methyl 11-4 GlyP EGCDX H, methyl EGCDX GlyP EGCDX EGCDX GlyP 11-5 POMMA POMMA H, methyl POMMA POMMA POMMA POMMA POMMA 11-6 ECHE ECHE H, methyl ECHE phenyl ECHE ECHE phenyl 11-7 ECHE ECHE H, methyl ECHE methyl ECHE ECHE methyl 11-8 ECHE ECHE H, methyl ECHE GlyP ECHE ECHE GlyP 11-9 ECHE ECHE H, methyl ECHE POMMA ECHE ECHE POMMA 11-10 ECHE phenyl H, methyl phenyl ECHE phenyl phenyl ECHE 11-11 ECHE methyl H, methyl methyl ECHE methyl methyl ECHE 11-12 ECHE GlyP H, methyl GlyP ECHE GlyP GlyP ECHE 11-13 ECHE POMMA H, methyl POMMA ECHE POMMA POMMA ECHE 11-14 phenyl phenyl H, methyl phenyl ECHE phenyl phenyl ECHE 11-15 phenyl phenyl H, methyl phenyl methyl phenyl phenyl methyl 11-16 phenyl phenyl H, methyl phenyl EGDCX phenyl phenyl EGDCX 11-17 phenyl phenyl H, methyl phenyl POMMA phenyl phenyl POMMA 11-18 phenyl ECHE H, methyl ECHE phenyl ECHE ECHE phenyl 11-19 phenyl methyl H, methyl methyl phenyl methyl methyl phenyl 11-20 phenyl GlyP H, methyl GlyP phenyl GlyP GlyP phenyl 11-21 phenyl POMMA H, methyl POMMA phenyl POMMA POMMA phenyl 11-22 methyl methyl H, methyl methyl ECHE methyl methyl ECHE 11-23 methyl methyl H, methyl methyl phenyl methyl methyl phenyl 11-24 methyl methyl H, methyl methyl GlyP methyl methyl GlyP 11-25 methyl methyl H, methyl methyl POMMA methyl methyl POMMA 11-26 methyl ECHE H, methyl ECHE methyl ECHE ECHE methyl 11-27 methyl phenyl H, methyl phenyl methyl phenyl phenyl methyl 11-28 methyl GlyP H, methyl GlyP methyl GlyP GlyP methyl 11-29 methyl POMMA H, methyl POMMA methyl POMMA POMMA methyl 11-30 GlyP GlyP H, methyl GlyP ECHE GlyP GlyP ECHE 11-31 GlyP GlyP H, methyl GlyP phenyl GlyP GlyP phenyl 11-32 GlyP GlyP H, methyl GlyP methyl GlyP GlyP methyl 11-33 GlyP GlyP H, methyl GlyP POMMA GlyP GlyP POMMA 11-34 GlyP ECHE H, methyl ECHE GlyP ECHE ECHE GlyP 11-35 GlyP phenyl H, methyl phenyl GlyP phenyl phenyl GlyP 11-36 GlyP methyl H, methyl methyl GlyP methyl methyl GlyP 11-37 GlyP POMMA H, methyl POMMA GlyP POMMA POMMA GlyP 11-38 POMMA POMMA H, methyl POMMA ECHE POMMA POMMA ECHE 11-39 POMMA POMMA H, methyl POMMA phenyl POMMA POMMA phenyl 11-40 POMMA POMMA H, methyl POMMA methyl POMMA POMMA methyl 11-41 POMMA POMMA H, methyl POMMA GlyP POMMA POMMA GlyP 11-42 POMMA ECHE H, methyl ECHE POMMA ECHE ECHE POMMA 11-43 POMMA phenyl H, methyl phenyl POMMA phenyl phenyl POMMA 11-44 POMMA methyl H, methyl methyl POMMA methyl methyl POMMA 11-45 POMMA GlyP H, methyl GlyP POMMA GlyP GlyP POMMA

No R16 R17 R18 R19 R20 X of R Y of R E x R 12-1 ECHE POMMA H, methyl ECHE POMMA POMMA ECHE POMMA 12-2 phenyl POMMA H, ethyl phenyl POMMA POMMA phenyl POMMA 12-3 POMMA ECHE H, acetyltyl methyl ECHE ECHE methyl ECHE 12-4 methyl ECHE vinyl, methyl EGCDX ECHE ECHE EGCDX ECHE 12-5 POMMA F H, methyl POMMA F F POMMA F 12-6 profile aminopropyl CF ₃ ,methyl ECHE aminopropyl aminopropyl ECHE aminopropyl 12-7 phenyl phenyl H, methyl ECHE phenyl phenyl ECHE phenyl 12-8 methyl alkyl thiol H, acetyltyl ECHE alkyl thiol alkyl thiol ECHE alkyl thiol 12-9 GlyP phenyl vinyl, methyl ECHE phenyl phenyl ECHE phenyl 12-10 ECHE octyl H, methyl phenyl octyl octyl phenyl octyl 12-11 alkyl thiol methyl H, methyl methyl methyl methyl methyl methyl 12-12 phenyl octyl vinyl, methyl GlyP octyl octyl GlyP octyl 12-13 octyl octyl H, methyl POMMA octyl octyl POMMA octyl 12-14 methyl methyl H, F phenyl methyl methyl phenyl methyl 12-15 octyl GlyP CF ₃ ,methyl phenyl ECHE GlyP phenyl ECHE 12-16 octyl GlyP vinyl, methyl phenyl phenyl GlyP phenyl phenyl 12-17 methyl aminopropyl H, methyl phenyl POMMA aminopropyl phenyl POMMA 12-18 GlyP GlyP H, F ECHE methyl GlyP ECHE methyl 12-19 GlyP POMMA CF ₃ ,methyl methyl POMMA POMMA methyl POMMA 12-20 aminopropyl methyl H, methyl GlyP profile methyl GlyP profile 12-21 GlyP POMMA Alkyl thiol, methyl POMMA phenyl POMMA POMMA phenyl 12-22 POMMA profile H, acetyltyl methyl methyl profile methyl methyl 12-23 POMMA methyl vinyl, methyl methyl GlyP methyl methyl GlyP 12-24 GlyP GlyP vinyl, methyl methyl ECHE GlyP methyl ECHE 12-25 aminopropyl GlyP H, methyl methyl GlyP GlyP methyl GlyP 12-26 methyl aminopropyl H, F ECHE aminopropyl aminopropyl ECHE aminopropyl 12-27 methyl GlyP CF ₃ ,methyl phenyl GlyP GlyP phenyl GlyP 12-28 methyl octyl H, methyl GlyP octyl octyl GlyP octyl 12-29 methyl methyl H, acetyltyl POMMA methyl methyl POMMA methyl 12-30 aminopropyl GlyP vinyl, methyl GlyP GlyP GlyP GlyP GlyP 12-31 GlyP GlyP H, methyl GlyP GlyP GlyP GlyP GlyP 12-32 POMMA aminopropyl H, methyl GlyP aminopropyl aminopropyl GlyP aminopropyl 12-33 methyl GlyP vinyl, methyl GlyP GlyP GlyP GlyP GlyP 12-34 POMMA POMMA H, methyl ECHE POMMA POMMA ECHE POMMA 12-35 profile POMMA H, F phenyl POMMA POMMA phenyl POMMA 12-36 methyl GlyP CF ₃ ,methyl methyl GlyP GlyP methyl GlyP 12-37 GlyP aminopropyl vinyl, methyl POMMA aminopropyl aminopropyl POMMA aminopropyl 12-38 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl 12-39 aminopropyl methyl H, F POMMA methyl methyl POMMA methyl 12-40 aminopropyl methyl CF ₃ ,methyl POMMA methyl methyl POMMA methyl 12-41 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl 12-42 POMMA GlyP Alkyl thiol, methyl ECHE GlyP GlyP ECHE GlyP 12-43 POMMA aminopropyl H, acetyltyl phenyl aminopropyl aminopropyl phenyl aminopropyl 12-44 POMMA GlyP vinyl, methyl methyl GlyP GlyP methyl GlyP 12-45 POMMA POMMA H, methyl GlyP POMMA POMMA GlyP POMMA

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

No R11 R12 R16 R17 R18 R19 X of R Y of R 13-1 OH, methoxy H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE 13-2 OH, methoxy H, methyl phenyl phenyl H, methyl phenyl phenyl phenyl 13-3 OH, methoxy H, methyl methyl methyl H, methyl methyl methyl methyl 13-4 OH, methoxy H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP 13-5 OH, methoxy H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA 13-6 OH, methoxy H, methyl ECHE ECHE H, methyl phenyl ECHE phenyl 13-7 OH, methoxy H, methyl ECHE ECHE H, methyl methyl ECHE methyl 13-8 OH, methoxy H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP 13-9 OH, methoxy H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA 13-10 OH, methoxy H, methyl phenyl phenyl H, methyl ECHE phenyl ECHE 13-11 OH, methoxy H, methyl phenyl phenyl H, methyl methyl phenyl methyl 13-12 OH, methoxy H, methyl phenyl phenyl H, methyl GlyP phenyl GlyP 13-13 OH, methoxy H, methyl phenyl phenyl H, methyl POMMA phenyl POMMA 13-14 OH, methoxy H, methyl methyl methyl H, methyl ECHE methyl ECHE 13-15 OH, methoxy H, methyl methyl methyl H, methyl phenyl methyl phenyl 13-16 OH, methoxy H, methyl methyl methyl H, methyl GlyP methyl GlyP 13-17 OH, methoxy H, methyl methyl methyl H, methyl POMMA methyl POMMA 13-18 OH, methoxy H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE 13-19 OH, methoxy H, methyl GlyP GlyP H, methyl phenyl GlyP phenyl 13-20 OH, methoxy H, methyl GlyP GlyP H, methyl methyl GlyP methyl 13-21 OH, methoxy H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA 13-22 OH, methoxy H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE 13-23 OH, methoxy H, methyl POMMA POMMA H, methyl phenyl POMMA phenyl 13-24 OH, methoxy H, methyl POMMA POMMA H, methyl methyl POMMA methyl 13-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP

No R11 R12 R16 R17 R18 R19 X of R Y of R 14-1 OH, methoxy H, methyl ECHE alkyl thiol H, methyl ECHE alkyl thiol ECHE 14-2 OH, CF ₃ H, ethyl ECHE phenyl H, ethyl phenyl phenyl phenyl 14-3 OH, methoxy H, acetyltyl ECHE methyl H, acetyltyl methyl methyl methyl 14-4 CF ₃ ,methoxy vinyl, methyl phenyl GlyP vinyl, methyl GlyP GlyP GlyP 14-5 OH, methoxy H, methyl phenyl POMMA H, methyl POMMA POMMA POMMA 14-6 OH, C ₈ F ₁₃ H, F phenyl ECHE H, F phenyl ECHE phenyl 14-7 OH, CF ₃ CF ₃ ,methyl ECHE ECHE CF ₃ ,methyl methyl ECHE methyl 14-8 OH, C ₈ F ₁₃ H, methyl hexyl ECHE H, methyl GlyP ECHE GlyP 14-9 OH, methoxy H, CF ₃ GlyP ECHE H, CF ₃ POMMA ECHE POMMA 14-10 OH, methoxy H, methyl POMMA phenyl H, methyl ECHE phenyl ECHE 14-11 OH, C ₈ F ₁₃ aryl, methyl aminopropyl phenyl aryl, methyl hexyl phenyl hexyl 14-12 OH, alkyl thiol H, methacrylic phenyl phenyl H, methacrylic GlyP phenyl GlyP 14-13 OH, methoxy H, methyl GlyP ECHE H, methyl POMMA ECHE POMMA 14-14 OH, acrylic H, octyl POMMA hexyl H, octyl aminopropyl hexyl aminopropyl 14-15 vinyl, methoxy H, methyl aminopropyl GlyP H, methyl phenyl GlyP phenyl 14-16 alkylamine H, methyl phenyl POMMA H, methyl GlyP POMMA GlyP 14-17 OH, ethyl, methyl Alkyl thiol, methyl octyl aminopropyl Alkyl thiol, methyl POMMA aminopropyl POMMA 14-18 acetoxy, methoxy H, methyl POMMA phenyl H, methyl aminopropyl phenyl aminopropyl 14-19 propoxy, methoxy H, CF ₃ ECHE GlyP H, CF ₃ phenyl GlyP phenyl 14-20 OH, methoxy H, methyl phenyl POMMA H, methyl octyl POMMA octyl 14-21 C ₈ F ₁₃ ,methoxy C ₈ F ₁₃ ,methyl methyl aminopropyl C ₈ F ₁₃ ,methyl POMMA aminopropyl POMMA 14-22 OH, aryl H, profile GlyP phenyl H, profile ECHE phenyl ECHE 14-23 OH, methoxy F, methyl POMMA octyl F, methyl phenyl octyl phenyl 14-24 CF ₃ , Methacrylic H, methyl POMMA POMMA H, methyl methyl POMMA methyl 14-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP

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

No R13 R14 R16 R17 R18 R19 X of R Y of R 15-1 H, methyl H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE 15-2 H, methyl H, methyl phenyl phenyl H, methyl phenyl phenyl phenyl 15-3 H, methyl H, methyl methyl methyl H, methyl methyl methyl methyl 15-4 H, methyl H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP 15-5 H, methyl H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA 15-6 H, methyl H, methyl ECHE ECHE H, methyl phenyl ECHE phenyl 15-7 H, methyl H, methyl ECHE ECHE H, methyl methyl ECHE methyl 15-8 H, methyl H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP 15-9 H, methyl H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA 15-10 H, methyl H, methyl phenyl phenyl H, methyl ECHE phenyl ECHE 15-11 H, methyl H, methyl phenyl phenyl H, methyl methyl phenyl methyl 15-12 H, methyl H, methyl phenyl phenyl H, methyl GlyP phenyl GlyP 15-13 H, methyl H, methyl phenyl phenyl H, methyl POMMA phenyl POMMA 15-14 H, methyl H, methyl methyl methyl H, methyl ECHE methyl ECHE 15-15 H, methyl H, methyl methyl methyl H, methyl phenyl methyl phenyl 15-16 H, methyl H, methyl methyl methyl H, methyl GlyP methyl GlyP 15-17 H, methyl H, methyl methyl methyl H, methyl POMMA methyl POMMA 15-18 H, methyl H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE 15-19 H, methyl H, methyl GlyP GlyP H, methyl phenyl GlyP phenyl 15-20 H, methyl H, methyl GlyP GlyP H, methyl methyl GlyP methyl 15-21 H, methyl H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA 15-22 H, methyl H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE 15-23 H, methyl H, methyl POMMA POMMA H, methyl phenyl POMMA phenyl 15-24 H, methyl H, methyl POMMA POMMA H, methyl methyl POMMA methyl 15-25 H, methyl H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP

No R13 R14 R16 R17 R18 R19 X of R Y of R 16-1 H, methyl CF ₃ ,methyl ECHE alkyl thiol H, methyl ECHE alkyl thiol ECHE 16-2 H, ethyl H, methyl ECHE phenyl Alkyl thiol, methyl hexyl phenyl hexyl 16-3 H, acetyltyl H, CF ₃ ECHE methyl H, methyl GlyP methyl GlyP 16-4 vinyl, methyl H, methyl phenyl GlyP H, CF ₃ POMMA GlyP POMMA 16-5 H, methyl H, methyl phenyl POMMA H, ethyl aminopropyl POMMA aminopropyl 16-6 H, F H, octyl phenyl ECHE H, F phenyl ECHE phenyl 16-7 CF ₃ ,methyl H, methyl ECHE ECHE vinyl, methyl GlyP ECHE GlyP 16-8 H, methyl H, methyl hexyl ECHE H, methyl POMMA ECHE POMMA 16-9 H, CF ₃ Alkyl thiol, methyl GlyP ECHE H, F aminopropyl ECHE aminopropyl 16-10 H, methyl H, methyl POMMA phenyl CF ₃ ,methyl phenyl phenyl phenyl 16-11 aryl, methyl H, methyl aminopropyl phenyl H, methyl octyl phenyl octyl 16-12 H, methacrylic H, methyl phenyl phenyl H, CF ₃ POMMA phenyl POMMA 16-13 H, methyl Alkyl thiol, methyl GlyP ECHE H, methyl ECHE ECHE ECHE 16-14 H, octyl H, methyl POMMA hexyl H, methyl phenyl hexyl phenyl 16-15 H, methyl H, F aminopropyl GlyP H, octyl methyl GlyP methyl 16-16 H, methyl CF ₃ ,methyl phenyl POMMA H, methyl GlyP POMMA GlyP 16-17 Alkyl thiol, methyl H, methyl octyl aminopropyl H, methyl POMMA aminopropyl POMMA 16-18 H, methyl H, CF ₃ POMMA phenyl Alkyl thiol, methyl aminopropyl phenyl aminopropyl 16-19 H, CF ₃ H, methyl ECHE GlyP H, methyl phenyl GlyP phenyl 16-20 H, methyl H, methyl phenyl POMMA H, methyl octyl POMMA octyl 16-21 C ₈ F ₁₃ ,methyl H, methyl methyl aminopropyl H, methyl POMMA aminopropyl POMMA 16-22 H, profile Alkyl thiol, methyl GlyP phenyl Alkyl thiol, methyl ECHE phenyl ECHE 16-23 F, methyl H, methyl POMMA octyl H, methyl phenyl octyl phenyl 16-24 H, methyl H, CF ₃ POMMA POMMA H, CF ₃ methyl POMMA methyl 16-25 H, ethyl H, methyl POMMA ECHE H, methyl GlyP ECHE GlyP

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

No R16 R17 R18 R19 R20 X of R Y of R end of E 17-1 ECHE ECHE H, methyl ECHE ECHE ECHE ECHE ECHE 17-2 phenyl phenyl H, methyl phenyl phenyl phenyl phenyl phenyl 17-3 methyl methyl H, methyl methyl methyl methyl methyl methyl 17-4 GlyP EGCDX H, methyl EGCDX GlyP EGCDX EGCDX GlyP 17-5 POMMA POMMA H, methyl POMMA POMMA POMMA POMMA POMMA 17-6 ECHE ECHE H, methyl ECHE phenyl ECHE ECHE phenyl 17-7 ECHE ECHE H, methyl ECHE methyl ECHE ECHE methyl 17-8 ECHE ECHE H, methyl ECHE GlyP ECHE ECHE GlyP 17-9 ECHE ECHE H, methyl ECHE POMMA ECHE ECHE POMMA 17-10 ECHE phenyl H, methyl phenyl ECHE phenyl phenyl ECHE 17-11 ECHE methyl H, methyl methyl ECHE methyl methyl ECHE 17-12 ECHE GlyP H, methyl GlyP ECHE GlyP GlyP ECHE 17-13 ECHE POMMA H, methyl POMMA ECHE POMMA POMMA ECHE 17-14 phenyl phenyl H, methyl phenyl ECHE phenyl phenyl ECHE 17-15 phenyl phenyl H, methyl phenyl methyl phenyl phenyl methyl 17-16 phenyl phenyl H, methyl phenyl EGDCX phenyl phenyl EGDCX 17-17 phenyl phenyl H, methyl phenyl POMMA phenyl phenyl POMMA 17-18 phenyl ECHE H, methyl ECHE phenyl ECHE ECHE phenyl 17-19 phenyl methyl H, methyl methyl phenyl methyl methyl phenyl 17-20 phenyl GlyP H, methyl GlyP phenyl GlyP GlyP phenyl 17-21 phenyl POMMA H, methyl POMMA phenyl POMMA POMMA phenyl 17-22 methyl methyl H, methyl methyl ECHE methyl methyl ECHE 17-23 methyl methyl H, methyl methyl phenyl methyl methyl phenyl 17-24 methyl methyl H, methyl methyl GlyP methyl methyl GlyP 17-25 methyl methyl H, methyl methyl POMMA methyl methyl POMMA 17-26 methyl ECHE H, methyl ECHE methyl ECHE ECHE methyl 17-27 methyl phenyl H, methyl phenyl methyl phenyl phenyl methyl 17-28 methyl GlyP H, methyl GlyP methyl GlyP GlyP methyl 17-29 methyl POMMA H, methyl POMMA methyl POMMA POMMA methyl 17-30 GlyP GlyP H, methyl GlyP ECHE GlyP GlyP ECHE 17-31 GlyP GlyP H, methyl GlyP phenyl GlyP GlyP phenyl 17-32 GlyP GlyP H, methyl GlyP methyl GlyP GlyP methyl 17-33 GlyP GlyP H, methyl GlyP POMMA GlyP GlyP POMMA 17-34 GlyP ECHE H, methyl ECHE GlyP ECHE ECHE GlyP 17-35 GlyP phenyl H, methyl phenyl GlyP phenyl phenyl GlyP 17-36 GlyP methyl H, methyl methyl GlyP methyl methyl GlyP 17-37 GlyP POMMA H, methyl POMMA GlyP POMMA POMMA GlyP 17-38 POMMA POMMA H, methyl POMMA ECHE POMMA POMMA ECHE 17-39 POMMA POMMA H, methyl POMMA phenyl POMMA POMMA phenyl 17-40 POMMA POMMA H, methyl POMMA methyl POMMA POMMA methyl 17-41 POMMA POMMA H, methyl POMMA GlyP POMMA POMMA GlyP 17-42 POMMA ECHE H, methyl ECHE POMMA ECHE ECHE POMMA 17-43 POMMA phenyl H, methyl phenyl POMMA phenyl phenyl POMMA 17-44 POMMA methyl H, methyl methyl POMMA methyl methyl POMMA 17-45 POMMA GlyP H, methyl GlyP POMMA GlyP GlyP POMMA

No R16 R17 R18 R19 R20 X of R Y of R E's
terminal R 18-1 ECHE POMMA H, methyl ECHE POMMA POMMA ECHE POMMA 18-2 phenyl POMMA H, ethyl phenyl POMMA POMMA phenyl POMMA 18-3 POMMA ECHE H, acetyltyl methyl ECHE ECHE methyl ECHE 18-4 methyl ECHE vinyl, methyl EGCDX ECHE ECHE EGCDX ECHE 18-5 POMMA F H, methyl POMMA F F POMMA F 18-6 profile aminopropyl CF ₃ ,methyl ECHE aminopropyl aminopropyl ECHE aminopropyl 18-7 phenyl phenyl H, methyl ECHE phenyl phenyl ECHE phenyl 18-8 methyl alkyl thiol H, acetyltyl ECHE alkyl thiol alkyl thiol ECHE alkyl thiol 18-9 GlyP phenyl vinyl, methyl ECHE phenyl phenyl ECHE phenyl 18-10 ECHE octyl H, methyl phenyl octyl octyl phenyl octyl 18-11 alkyl thiol methyl H, methyl methyl methyl methyl methyl methyl 18-12 phenyl octyl vinyl, methyl GlyP octyl octyl GlyP octyl 18-13 octyl octyl H, methyl POMMA octyl octyl POMMA octyl 18-14 methyl methyl H, F phenyl methyl methyl phenyl methyl 18-15 octyl GlyP CF ₃ ,methyl phenyl ECHE GlyP phenyl ECHE 18-16 octyl GlyP vinyl, methyl phenyl phenyl GlyP phenyl phenyl 18-17 methyl aminopropyl H, methyl phenyl POMMA aminopropyl phenyl POMMA 18-18 GlyP GlyP H, F ECHE methyl GlyP ECHE methyl 18-19 GlyP POMMA CF ₃ ,methyl methyl POMMA POMMA methyl POMMA 18-20 aminopropyl methyl H, methyl GlyP profile methyl GlyP profile 18-21 GlyP POMMA Alkyl thiol, methyl POMMA phenyl POMMA POMMA phenyl 18-22 POMMA profile H, acetyltyl methyl methyl profile methyl methyl 18-23 POMMA methyl vinyl, methyl methyl GlyP methyl methyl GlyP 18-24 GlyP GlyP vinyl, methyl methyl ECHE GlyP methyl ECHE 18-25 aminopropyl GlyP H, methyl methyl GlyP GlyP methyl GlyP 18-26 methyl aminopropyl H, F ECHE aminopropyl aminopropyl ECHE aminopropyl 18-27 methyl GlyP CF ₃ ,methyl phenyl GlyP GlyP phenyl GlyP 18-28 methyl octyl H, methyl GlyP octyl octyl GlyP octyl 18-29 methyl methyl H, acetyltyl POMMA methyl methyl POMMA methyl 18-30 aminopropyl GlyP vinyl, methyl GlyP GlyP GlyP GlyP GlyP 18-31 GlyP GlyP H, methyl GlyP GlyP GlyP GlyP GlyP 18-32 POMMA aminopropyl H, methyl GlyP aminopropyl aminopropyl GlyP aminopropyl 18-33 methyl GlyP vinyl, methyl GlyP GlyP GlyP GlyP GlyP 18-34 POMMA POMMA H, methyl ECHE POMMA POMMA ECHE POMMA 18-35 profile POMMA H, F phenyl POMMA POMMA phenyl POMMA 18-36 methyl GlyP CF ₃ ,methyl methyl GlyP GlyP methyl GlyP 18-37 GlyP aminopropyl vinyl, methyl POMMA aminopropyl aminopropyl POMMA aminopropyl 18-38 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl 18-39 aminopropyl methyl H, F POMMA methyl methyl POMMA methyl 18-40 aminopropyl methyl CF ₃ ,methyl POMMA methyl methyl POMMA methyl 18-41 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl 18-42 POMMA GlyP Alkyl thiol, methyl ECHE GlyP GlyP ECHE GlyP 18-43 POMMA aminopropyl H, acetyltyl phenyl aminopropyl aminopropyl phenyl aminopropyl 18-44 POMMA GlyP vinyl, methyl methyl GlyP GlyP methyl GlyP 18-45 POMMA POMMA H, methyl GlyP POMMA POMMA GlyP POMMA

The degree of condensation of the silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to obtain wide applicability by securing excellent storage stability. That is, the content of the alkoxy group bonded to Si at the ends and the center can be controlled from 50% to 0.01% of the total polymer bonding group.

In addition, the weight average molecular weight of the silsesquioxane composite polymer in the present invention may be 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 silsesquioxane can be improved at the same time.

In the present invention, the plastic coating composition comprising the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, preferably represented by any one of Formulas 3 to 9 It is preferable to use a silsesquioxane composite polymer. In this case, physical properties of the transparent substrate including surface hardness can be further improved by including the repeating unit [B]b or [E]e.

In the present invention, when the silsesquioxane composite polymer is in the liquid phase, the plastic coating composition can be coated alone as a solvent-free type, and in the solid phase, the plastic coating composition may include an organic solvent. In addition, the coating composition may further include an initiator or a curing agent.

Preferably, the coating composition comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, an organic solvent commonly used in the art that is compatible with the composite polymer, and an initiator, , optionally by further including additives such as curing agents, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, and plasticizing effect.

In the coating composition of the present invention, the silsesquioxane composite polymer is preferably included in an amount of at least 5 parts by weight or more, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the coating composition. It is preferably included in a negative amount. When within the above range, the mechanical properties of the cured film of the coating composition may be further improved.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and cellosolve; ketones such as lactate, acetone, and methyl (isobutyl) ethyl ketone; glycols such as ethylene glycol; Furan-based solvents such as tetrahydrofuran, polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Various solvents such as dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrynitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, and benzyl alcohol may be used, but are not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the complex polymer, the initiator, and optionally added additives.

In addition, in the coating composition of the present invention, the initiator or curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.

As a specific example, when an organic type capable of post-curing, such as an unsaturated hydrocarbon, a thiol type, an epoxy type, an amine type, an isocyanate type, etc. is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change by heat or light can be achieved within the polymer itself, but preferably, the curing process can be achieved by diluting it in the organic solvent as described above.

In addition, in the present invention, various initiators can be used for curing and post-reaction of the composite polymer, and the initiator is preferably included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the total weight of the composition, and when included in an amount within the above range, After curing, transmittance and coating stability can be satisfied at the same time.

In addition, when an unsaturated hydrocarbon is introduced into the organic functional group, a radical initiator may be used, and the radical initiator includes trichloro acetophenone, diethoxy acetophenone, 1-phenyl-2-hydro Roxy-2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl)-2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide), camphor quinone, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl- Photoradical initiators such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, and 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t- Butylparoxy maleic acid, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, N-butyl-4, Thermal radical initiators, such as 4'-di(t-butylperoxy)valerate, and various mixtures thereof, etc. can be used.

In addition, when an epoxy etc. are contained in the said organic functional group, as a photoinitiator (cation), sulfonium types, such as triphenylsulfonium, diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium, or bis (dode iodonium such as silphenyl) iodonium, diazonium such as phenyldiazonium, ammonium such as 1-benzyl-2-cyanopyrininium and 1-(naphthylmethyl)-2-cyanopridinium, (4- Methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate iodonium, bis(4-t-butylphenyl)hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafluoroborate, tri-p-toylsulfonium hexafluorophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- A combination of Fe cations such as cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe and [BQ ₄ ] ^-onium salts such as BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- may be used. (Wherein, Q is a phenyl group substituted with at least two or more fluorine or trifluoromethyl groups).

In addition, as a cationic initiator acting by heat, a cationic or protonic acid catalyst such as triflate, boron trifluoride ether complex, boron trifluoride, etc., various onium salts such as ammonium salt, phosphonium salt and sulfonium salt, and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide, etc. can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above do.

In addition, depending on the type of the organic functional group, amine curing agents ethylenediamine, triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane, dipropylenetriamine, 3-(2-aminoethyl)amino-propyl amine, N,N'-bis(3-aminopropyl)-ethylenediamine, 4,9-dioxadothecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, Hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis(4-animocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, etc. can be used. .

In addition, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetra Acid anhydride curing agents such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2,4-diethyl glutaric anhydride can also be widely used.

The curing agent is preferably included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the composition.

In addition, as a curing accelerator for accelerating the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, and 2-methylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, imidazole compounds such as 1-methylimidazole, 1, 5-diazabicyclo[4.3.0]nonene-5,1,8-diazabicyclo[5.4.0]undecene-7, triphenylphosphine, diphenyl(p-triyl)phosphine, tris(alkylphenyl) ) Phosphine, tris (alkoxyphenyl) phosphine, ethyl triphenyl phosphonium phosphate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate, tetrabutyl phosphonium hydrogen difluoride, tetrabutyl phosphonium dihydrogen tri Fluorine or the like may also be used.

In the present invention, additives such as UV absorbers, antioxidants, defoamers, leveling agents, water repellents, flame retardants, and adhesion improvers are additionally included for the purpose of improving hardness, strength, durability, moldability, etc. through the curing process or post-reaction. can These additives are not particularly limited in their use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, physical properties such as flexibility, light transmittance, heat resistance, hardness, and strength. Preferably, the additives are each independently included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.

Additives usable in the present invention include polyether-modified polydimethylsiloxane (for example, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, manufactured by BYK). BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxyfunctional poly-dimethyl-siloxane (Polyether modified hydroxyfunctional poly-dimethyl-siloxane, for example, manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylpolysiloxane (eg, BYK-077, BYK-085, etc.), polyether modified methylalkylpolysiloxane (eg, BYK- 320, BYK-325, etc.), polyester polymethylalkylsiloxane (Polyester modified poly-methyl-alkyl-siloxane, e.g., BYK-315, etc.), Aralkyl modified methylalkyl polysiloxane, e.g. For example, BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane-based (Polyester modified hydroxy functional polydimethylsiloxane, for example, BYK-370, etc.), polyester acrylic polydimethylsiloxane-based (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy polydimethylsiloxane (Polyeher-polyester modified hydroxy functional polydimethylsiloxane, such as BYK-375, etc.), polyether poly Dimethylsiloxane (Polyether modified dimethylpolysiloxane, for example, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337, etc.), Non-ionic acrylic copolymer, for example , BYK-380, etc.), ionic polyacrylic copolymer (eg, BYK-381, etc.), polyacrylate (eg, BYK-353, BYK-356, BYK-354, BYK) -355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352, etc.), polymethacrylate-based (Polymethacrylate, such as BYK-390, etc.), polyether acrylic polydimethyl Siloxane-based (Polyether modified acryl functional polydimethylsiloxane, for example, BYK-UV 3500, BYK-UV3530, etc.), polyether siloxane-based (Polyether modified siloxane, for example, BYK-347, etc.), alcohol alkoxylates , for example, BYK-DYNWET 800, etc.), acrylate-based (Acrylate, for example, BYK-392, etc.), hydroxy silicone polyacrylate (OH-functional), such as BYK -Silclean 3700, etc.) and the like.

In the present invention, the method of coating the plastic coating composition on the plastic surface is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, dipping method, Of course, those skilled in the art can arbitrarily select and apply from known methods such as impregnation method and gravure coating, and even in the curing method, photocuring or thermal curing can be appropriately selected and applied according to the functional group of the composite polymer. . Preferably, in the case of thermosetting, the curing temperature is 80 to 120 °C.

In the present invention, the coating thickness of the coating composition is arbitrarily adjustable, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, even more preferably 1 to 100 um. When it is within the above range, it is possible to stably secure a surface hardness of 7H or more, and exhibit excellent physical properties in terms of substrate surface properties. In particular, when the coating layer is laminated to a thickness of 10 μm or more, the surface hardness can stably represent 9H.

In addition, the present invention is a silsesquioxane composite polymer coated plastic, characterized in that it comprises a cured product coated with a plastic coating composition containing a silsesquioxane composite polymer represented by any one of Formulas 1 to 9 on the surface of the cured product To provide a product including the silsesquioxane composite polymer coated plastic, the silsesquioxane composite polymer coated plastic may be manufactured by the plastic coating method.

The silsesquioxane composite polymer coating plastic according to the present invention has excellent adhesion between the silsesquioxane composite polymer coating layer and the plastic, and the formed silsesquioxane composite polymer coating layer has very high surface hardness, excellent transparency, and scratch resistance. It has water-repellent properties, antifouling properties, anti-fingerprint properties, thermal stability and gloss properties, and excellent adhesion to plastic substrates. , wire coverings, optical lenses, soundproof walls, plastic signs, plastic sculptures, furniture, lighting, sunroofs, helmets, etc. can be usefully applied to various products.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples. In the examples of the present invention, ECHETMS is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy)propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltritetramethoxysilane, ECHETMDS is Di(epoxymethoxycyclohexyloxane) tetramethoxysilane, ECHETMDS is Di(epoxymethoxycyclohexyethyl) Di(glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS stands for Di(methacryloyloxy)propy, PTMDS stands for Di(phenyl) tetramethoxy disiloxane, and MTMDS stands for Di(Methyl) tetramethoxy disiloxane.

[Example 1] Preparation of coating composition comprising copolymers 1 and 9

As for the synthesis step, continuous hydrolysis and condensation were carried out step by step.

[Example 1-a] Preparation of catalyst

For basicity control, catalyst 1a was prepared by mixing 10 wt% potassium hydroxide (KOH) aqueous solution with 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution.

[Example 1-b] Synthesis of linear silsesquioxane structure

5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, and 1 part by weight of the catalyst prepared in Example 1-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and after stirring at room temperature for 1 hour, 2 20 parts by weight of -(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and then 15 parts by weight of tetrahydrolurane was added dropwise, followed by further stirring for 5 hours. After removing the catalyst and impurities by collecting the mixed solution during stirring, washing twice, and filtering, the SI-OH functional group generated at the terminal group was confirmed through IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that silsesquioxane having a linear structure such as the structure of Chemical Formula 4 had a molecular weight equivalent to 8,000 styrene.

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

To the mixed solution of Example 1-b, 5 parts by weight of 0.36 wt% HCl aqueous solution was added dropwise very slowly, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 °C for 30 minutes. Then, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a precursor of the D structure in which the alkoxy is open is formed separately from the linear polymer. After taking a small sample and analyzing it with H-NMR and IR to check the residual ratio of methoxy, when the residual ratio is 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution is slowly added dropwise to adjust the pH to acid. gave. Then, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that a cage-type polymer was produced in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR. As a result, the analysis peaks of the structure introduced using a phenyl group appeared as two sharp peaks, and the AD polymer as in Formula 1 was 50% It could be confirmed that the above was manufactured. In addition, the molecular weight in terms of styrene was measured to be 11,000, and the n value was 4-6. ²⁹ Si-NMR (CDCl ₃ ) δ

[Example 1-d] Preparation of photocurable resin composition

30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30 wt % 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 part by weight of BYK-UV 3500 were added to 100 parts by weight of the coating composition, respectively, and stirred for 10 minutes to prepare a photocurable coating composition.

[Example 1-e] Preparation of thermosetting resin composition

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

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

Only Example 1-c was composed of a coating composition without a separate composition.

In addition, by applying the monomers described in Table 19 below, a silsesquioxane composite polymer was prepared and a coating composition was prepared. At this time, the manufacturing method was equally applied to the methods used in Examples 1-b, 1-c, 1-d, 1-e and 1-f.

practice
Way 1-b method
Applicable monomer 1-c method
Applicable monomer Molecular Weight
(Mw) precursor introduction of cage One ECHETMS PTMDS PTMS 11,000 1-1 PTMS PTMDS PTMS 8,000 1-2 MTMS MTMDS MTMS 48,000 1-3 GPTMS GPTMDS GPTMS 25,000 1-4 MAPTMS MAPTMDS MAPTMS 21,000 1-5 ECHETMS ECHETMDS ECHETMS 3,000 1-6 ECHETMS MTMDS MTMS 9,000 1-7 ECHETMS GPTMDS GPTMS 11,000 1-8 ECHETMS MAPTMDS MAPTMS 18,000 1-9 PTMS ECHETMDS ECHETMS 36,000 1-10 PTMS MTMDS MTMS 120,000 1-11 PTMS GPTMDS GPTMS 11,000 1-12 PTMS MAPTMDS MAPTMS 110,000 1-13 MTMS ECHETMDS ECHETMS 18,000 1-14 MTMS PTMDS PTMS 5,000 1-15 MTMS GPTMDS GPTMS 80,000 1-16 MTMS MAPTMDS MAPTMS 35,000 1-17 GPTMS ECHETMDS ECHETMS 7,000 1-18 GPTMS PTMDS PTMS 120,000 1-19 GPTMS MTMDS MTMS 100,000 1-20 GPTMS MAPTMDS MAPTMS 4,000 1-21 MAPTMS ECHETMDS ECHETMS 35,000 1-22 MAPTMS PTMDS PTMS 2,800 1-23 MAPTMS MTMDS MTMS 8,000 1-24 MAPTMS GPTMDS GPTMS 180,000

Example 2 : Silsesquioxane Synthesis of D-A-D Structured Composite Polymers

The following example was used to prepare a composite polymer having a DAD structure, and a coating composition was prepared by a method equivalent to the method described in Example 1 above. For the preparation of the catalyst and the linear structure, the methods of Examples 1-a and 1-b were used in the same manner, and then, the preparation was carried out in the following manner in order to generate a continuous DAD structure.

[Example 2-a] Creation of an excess of continuous cage structure

To the mixed solution of Example 1-b, 5 parts by weight of 0.36 wt% HCl aqueous solution was added dropwise very slowly, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 °C for 30 minutes. After that, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at a time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state to adjust the pH of the mixed solution. At this time, a precursor of the D structure in which the alkoxy is open is formed separately from the linear polymer. After taking a small sample and analyzing it with H-NMR and IR to check the residual ratio of methoxy, when the residual ratio is 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution is slowly added dropwise to adjust the pH to acid. gave. Then, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that a cage-type polymer was produced in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR. As a result, the analysis peaks of the structure introduced using a phenyl group appeared as two sharp shapes, indicating that an AD polymer as in Formula 1 was prepared without separately remaining by-products. could check In addition, the molecular weight in terms of styrene was measured to be 14,000, and the n value was 4-6. In addition, unlike the AD structure in Si-NMR analysis, the peak near -68ppm that was seen at the end of the A structure disappeared, confirming that the end of the A structure was all converted to 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)

In addition, silsesquioxane composite polymers and coating compositions were prepared by applying the monomers described in Table 20 below. At this time, the manufacturing method was equally applied to the method used in Example 2.

practice
Way 1-b method
Applicable monomer 2-a method
Applicable monomer Molecular Weight
(Mw) precursor introduction of cage 2 ECHETMS PTMDS PTMS 14,000 2-1 PTMS PTMDS PTMS 9,000 2-2 MTMS MTMDS MTMS 52,000 2-3 GPTMS GPTMDS GPTMS 30,000 2-4 MAPTMS MAPTMDS MAPTMS 24,000 2-5 ECHETMS ECHETMDS ECHETMS 6,000 2-6 ECHETMS MTMDS MTMS 12,000 2-7 ECHETMS GPTMDS GPTMS 13,000 2-8 ECHETMS MAPTMDS MAPTMS 21,000 2-9 PTMS ECHETMDS ECHETMS 38,000 2-10 PTMS MTMDS MTMS 150,000 2-11 PTMS GPTMDS GPTMS 18,000 2-12 PTMS MAPTMDS MAPTMS 123,000 2-13 MTMS ECHETMDS ECHETMS 23,000 2-14 MTMS PTMDS PTMS 9,000 2-15 MTMS GPTMDS GPTMS 91,000 2-16 MTMS MAPTMDS MAPTMS 41,000 2-17 GPTMS ECHETMDS ECHETMS 12,000 2-18 GPTMS PTMDS PTMS 131,000 2-19 GPTMS MTMDS MTMS 110,000 2-20 GPTMS MAPTMDS MAPTMS 6,000 2-21 MAPTMS ECHETMDS ECHETMS 38,000 2-22 MAPTMS PTMDS PTMS 5,000 2-23 MAPTMS MTMDS MTMS 12,000 2-24 MAPTMS GPTMDS GPTMS 192,000

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

The following example was used to prepare a composite polymer having an EAD structure, and a coating composition was prepared by a method equivalent to the method described in Example 1 above. The catalyst and the linear structure were prepared in the same manner as in Example 1, and then the EAD structure was prepared by the following method.

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

To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride was added dropwise without separate purification, and 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted to have acidity, and the pH was adjusted to 30 at a temperature of 4°C. stirred for minutes. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, the parts that have not yet been hydrolyzed in the molecular structure are easily converted into hydrolysates in the acidic aqueous solution layer separated from the solvent, and are condensed with the generated separate reactants in the organic solvent layer to introduce E into the terminal unit. After stirring for 5 hours, the stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

[Example 3-b] Incorporation of cage into end E structure

After the organic layer obtained in Example 3-a was prepared without further purification, the ends were converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in which the reaction is in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state to adjust the pH of the mixed solution. At this time, a cage-type polymer is introduced at the end of the E structure, and the reaction proceeds continuously in the reactor to form a polymer as shown in Chemical Formula 3. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

After obtaining the mixture in which the reaction was completed in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed under reduced pressure. Thereafter, by precipitation twice in methanol, unreacted monomers were removed, and 30 parts by weight was dissolved in a solvent in which tetrahydrofuran and aqueous solution were mixed at a weight ratio of 9.5:0.5 and stored at a temperature of -20 °C for 2 days. This is to promote recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Formula 3 was obtained along with various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, and the n value was 4-6. In particular, the result of Formula 3 is as follows.

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

In addition, by applying the monomers described in Table 21 below, a silsesquioxane composite polymer and coating composition were prepared. At this time, the manufacturing method was equally applied to the method used in Example 3.

practice
Way 1-b method
Applicable monomer 1-c method
Applicable monomer 3-a
Way
Applicable monomer 3-b
Way
Applicable monomer Mw precursor introduction of cage 3 ECHETMS PTMDS PTMS MTMDS MAPTMS 17,000 3-1 ECHETMS ECHETMDS ECHETMS ECHETMDS ECHETMS 12,000 3-2 PTMS PTMDS PTMS PTMDS PTMS 18,000 3-3 MTMS MTMDS MTMS MTMDS MTMS 59,000 3-4 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 41,000 3-5 MAPTMS MAPTMDS MAPTMS MAPTMDS MAPTMS 31,000 3-6 ECHETMS ECHETMDS ECHETMS PTMDS PTMS 16,000 3-7 ECHETMS ECHETMDS ECHETMS MTMDS MTMS 12,000 3-8 ECHETMS ECHETMDS ECHETMS GPTMDS GPTMS 16,000 3-9 ECHETMS ECHETMDS ECHETMS MAPTMDS MAPTMS 92,000 3-10 ECHETMS PTMDS PTMS ECHETMDS ECHETMS 25,000 3-11 ECHETMS MTMDS MTMS ECHETMDS ECHETMS 38,000 3-12 ECHETMS GPTMDS GPTMS ECHETMDS ECHETMS 56,000 3-13 ECHETMS MAPTMDS MAPTMS ECHETMDS ECHETMS 97,000 3-14 PTMS PTMDS PTMS ECHETMDS ECHETMS 24,000 3-15 PTMS PTMDS PTMS MTMDS MTMS 31,000 3-16 PTMS PTMDS PTMS ECHETMDS ECHETMS 21,000 3-17 PTMS PTMDS PTMS MAPTMDS MAPTMS 64,000 3-18 PTMS ECHETMDS ECHETMS PTMDS PTMS 120,000 3-19 PTMS MTMDS MTMS PTMDS PTMS 210,000 3-20 PTMS GPTMDS GPTMS PTMDS PTMS 23,000 3-21 PTMS MAPTMDS MAPTMS PTMDS PTMS 160,000 3-22 MTMS MTMDS MTMS ECHETMDS ECHETMS 63,000 3-23 MTMS MTMDS MTMS PTMDS PTMS 52,000 3-24 MTMS MTMDS MTMS GPTMDS GPTMS 73,000 3-25 MTMS MTMDS MTMS MAPTMDS MAPTMS 98,000 3-26 MTMS ECHETMDS ECHETMS MTMDS MTMS 41,000 3-27 MTMS PTMDS PTMS MTMDS MTMS 15,000 3-28 MTMS GPTMDS GPTMS MTMDS MTMS 110,000 3-29 MTMS MAPTMDS MAPTMS MTMDS MTMS 45,000 3-30 GPTMS GPTMDS GPTMS ECHETMDS ECHETMS 35,000 3-31 GPTMS GPTMDS GPTMS PTMDS PTMS 33,000 3-32 GPTMS GPTMDS GPTMS MTMDS MTMS 48,000 3-33 GPTMS GPTMDS GPTMS MAPTMDS MAPTMS 29,000 3-34 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 19,000 3-35 GPTMS PTMDS PTMS GPTMDS GPTMS 156,000 3-36 GPTMS MTMDS MTMS GPTMDS GPTMS 116,000 3-37 GPTMS MAPTMDS MAPTMS GPTMDS GPTMS 12,000 3-38 MAPTMS MAPTMDS MAPTMS ECHETMDS ECHETMS 31,000 3-39 MAPTMS MAPTMDS MAPTMS PTMDS PTMS 28,000 3-40 MAPTMS MAPTMDS MAPTMS MTMDS MTMS 35,000 3-41 MAPTMS MAPTMDS MAPTMS GPTMDS GPTMS 31,000 3-42 MAPTMS ECHETMDS ECHETMS MAPTMDS MAPTMS 57,000 3-43 MAPTMS PTMDS PTMS MAPTMDS MAPTMS 9,000 3-44 MAPTMS MTMDS MTMS MAPTMDS MAPTMS 19,000 3-45 MAPTMS GPTMDS GPTMS MAPTMDS MAPTMS 213,000

Example 4 : Synthesis of A-B-D structure complex silsesquioxane polymer

In the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method equivalent to the method described in Example 1.

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

For basicity control, catalyst 1a was prepared by mixing 10 wt% potassium hydroxide (KOH) aqueous solution with 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution.

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

5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, and 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and after stirring at room temperature for 1 hour, 2 10 parts by weight of -(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydrolurane was added dropwise again, followed by stirring for an additional 2 hours. After removing the catalyst and impurities and filtering the mixed solution while stirring, washing twice to remove linear silsesquioxane in which the residual alkoxy group remains at 0.1 mmol/g or less through ¹ H-NMR analysis obtained, which is then used to introduce the cage as a continuous reaction. The morphology analysis of the linear structure confirmed that the overall structure was a linear structure through XRD analysis. As a result of measuring the molecular weight, it was confirmed that silsesquioxane having a linear structure had a molecular weight equivalent to 6,000 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 shift reaction for generation of intra-chain cage structure (introduction of B, D structures)

5 parts by weight of 0.36 wt% HCl aqueous solution was very slowly added dropwise to the mixed solution of Example 4-b in which the reaction was in progress, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4° C. for 30 minutes. Then, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise at a time, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution to a basic state. At this time, it was confirmed that a cage-type structure was created separately from the linear structure and introduced into the polymer chain, the temperature was changed to room temperature, and the tetrahydrofuran in the mixed solution was removed in a vacuum, and the entire reactant was converted into an aqueous mixture. made to be After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR and ¹ H-NMR. As a result, the amount of alkoxy group in structure B was changed to 0.025 mmol/g, so that the repeating units of B and D were about It was confirmed that it was introduced in a ratio of 5:5. In addition, the molecular weight in terms of styrene was measured to be 10,000. In addition, even though the cage-type structure was introduced, the molecular weight distribution of the single cage-type material was not found in the GPC form of the polymer, so it was confirmed that the cage structure was well introduced into the polymer chain through a continuous reaction.

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 in structure B (introduction of structures B, D)

After the organic layer obtained in Example 4-c was prepared without further purification, the ends were converted into a cage structure using a trifunctional monomer. After dissolving 100 parts by weight of the material obtained in Example 4-c in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Then, 10 parts by weight of 0.36 wt% HCl was added to the prepared mixed solution, and after stirring for 10 minutes, 3 parts by weight of Methyltrimethoxysilane was added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a cage-shaped polymer is introduced into the X portion of the B structure, and the reaction proceeds continuously in the reactor to form a polymer as shown in Chemical Formula 4. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

In Example 4-d, 200 parts by weight of methylene chloride was put into the mixture in which the reaction was completed, fractional washing was performed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, by precipitation twice in methanol, unreacted monomers were removed, and 30 parts by weight was dissolved in a solvent in which tetrahydrofuran and aqueous solution were mixed at a weight ratio of 9.5:0.5 and stored at a temperature of -20 °C for 2 days. This is to promote recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Formula 4 was obtained without various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight was 12,000 in terms of styrene, and the n value of X was 4-6, and the n value of Y was 4-6. In particular, the result of Chemical Formula 4 is as follows.

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

In addition, silsesquioxane composite polymers and coating compositions were prepared by applying the monomers described in Table 22 below. At this time, the manufacturing method was equally applied to the method used in Example 4.

practice
Way 4-b method
Applicable monomer 4-c method
Applicable monomer 4-d method
Applicable monomer Molecular Weight
(Mw) 4 ECHETMS PTMDS MTMS 12,000 4-1 PTMS PTMDS PTMS 15,000 4-2 MTMS MTMDS MTMS 16,000 4-3 GPTMS GPTMDS GPTMS 56,000 4-4 MAPTMS MAPTMDS MAPTMS 9,500 4-5 ECHETMS ECHETMDS ECHETMS 7,500 4-6 ECHETMS MTMDS MTMS 16,000 4-7 ECHETMS GPTMDS GPTMS 23,000 4-8 ECHETMS MAPTMDS MAPTMS 9,500 4-9 PTMS ECHETMDS ECHETMS 72,000 4-10 PTMS MTMDS MTMS 68,000 4-11 PTMS GPTMDS GPTMS 11,000 4-12 PTMS MAPTMDS MAPTMS 110,000 4-13 MTMS ECHETMDS ECHETMS 23,000 4-14 MTMS PTMDS PTMS 9,500 4-15 MTMS GPTMDS GPTMS 64,000 4-16 MTMS MAPTMDS MAPTMS 12,000 4-17 GPTMS ECHETMDS ECHETMS 8,000 4-18 GPTMS PTMDS PTMS 451,000 4-19 GPTMS MTMDS MTMS 320,000 4-20 GPTMS MAPTMDS MAPTMS 15,000 4-21 MAPTMS ECHETMDS ECHETMS 45,000 4-22 MAPTMS PTMDS PTMS 351,000 4-23 MAPTMS MTMDS MTMS 14,000 4-24 MAPTMS GPTMDS GPTMS 160,000

Example 5 : Synthesis of D-A-B-D structure complex silsesquioxane polymer

The following method was used to prepare a composite polymer having a DABD structure, and a coating composition was prepared in the same manner as in Example 1.

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

5 parts by weight of 0.36 wt% HCl aqueous solution was very slowly added dropwise to the mixed solution of Example 4-b in which the reaction was in progress, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4° C. for 30 minutes. After that, the amount of Diphenyltetramethoxydisiloxane was prepared in an amount of 25 parts by weight, which is 5 times that of Example 4-b, and added dropwise at once, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was again added to the pH of the mixed solution in a basic state was regulated After completion of the reaction, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After mixing and stirring for 4 hours, a portion was taken and analyzed through ²⁹ Si-NMR and ¹ H-NMR. As a result, the amount of alkoxy group present in structure B was changed to 0.012 mmol/g, and the repeating units of B and D were about It was confirmed that it was introduced in a 1:9 ratio. In addition, the molecular weight in terms of styrene was measured to be 24,000. In addition, even though the cage-type structure was introduced, the molecular weight distribution of the single cage-type material was not found in the GPC form of the polymer, so it was confirmed that the cage structure was well introduced into the polymer chain through a continuous reaction.

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 in structure B (introduction of structures B, D)

After the organic layer obtained in Example 5-a was prepared without further purification, the ends were converted into a cage structure using a trifunctional monomer. After dissolving 100 parts by weight of the material obtained in Example 5-a in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Then, 10 parts by weight of 0.36 wt% HCl was added to the prepared mixed solution, and after stirring for 10 minutes, 3 parts by weight of Methyltrimethoxysilane was added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a cage-type polymer is introduced into the X portion of the B structure, and the reaction proceeds continuously in the reactor to form a polymer as shown in Chemical Formula 5. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

In Example 5-b, 200 parts by weight of methylene chloride was put into the mixture in which the reaction was completed, fractional washing was performed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, it was precipitated twice in methanol to remove unreacted monomers, and dissolved in 30 parts by weight in a solvent in which tetrahydrofuran and aqueous solution were mixed in a 9.5:0.5 weight ratio, and stored at a temperature of -20 °C for 2 days. This is to promote recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight was 16,000 in terms of styrene, and the n value of X was 4-6, and the n value of Y was 4-6. In particular, the result of Chemical Formula 5 is as follows.

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

In addition, silsesquioxane composite polymers and coating compositions were prepared by applying the monomers described in Table 23 below. At this time, the manufacturing method was equally applied to the method used in Example 5.

practice
Way 4-b method
Applicable monomer 4-a method
Applicable monomer 5-b method
Applicable monomer Molecular Weight
(Mw) 2 ECHETMS PTMDS MTMS 16,000 5-1 PTMS PTMDS PTMS 19,000 5-2 MTMS MTMDS MTMS 20,000 5-3 GPTMS GPTMDS GPTMS 63,000 5-4 MAPTMS MAPTMDS MAPTMS 12,000 5-5 ECHETMS ECHETMDS ECHETMS 14,500 5-6 ECHETMS MTMDS MTMS 19,000 5-7 ECHETMS GPTMDS GPTMS 25,000 5-8 ECHETMS MAPTMDS MAPTMS 11,500 5-9 PTMS ECHETMDS ECHETMS 78,000 5-10 PTMS MTMDS MTMS 79,000 5-11 PTMS GPTMDS GPTMS 15,000 5-12 PTMS MAPTMDS MAPTMS 124,000 5-13 MTMS ECHETMDS ECHETMS 30,000 5-14 MTMS PTMDS PTMS 12,000 5-15 MTMS GPTMDS GPTMS 64,000 5-16 MTMS MAPTMDS MAPTMS 13,000 5-17 GPTMS ECHETMDS ECHETMS 12,000 5-18 GPTMS PTMDS PTMS 631,000 5-19 GPTMS MTMDS MTMS 421,000 5-20 GPTMS MAPTMDS MAPTMS 18,000 5-21 MAPTMS ECHETMDS ECHETMS 65,000 2-22 MAPTMS PTMDS PTMS 425,000 5-23 MAPTMS MTMDS MTMS 25,000 5-24 MAPTMS GPTMDS GPTMS 213,000

Example 6 : Synthesis of silsesquioxane E-A-B-D structure composite polymer

The following method was used to prepare a composite polymer having an EABD structure, and a coating composition was prepared in the same manner as in Example 1.

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

20 parts by weight of methylene chloride was added dropwise to the mixture obtained in Example 4-c without separate purification, and 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have acidity, and the temperature was 4° C. for 30 minutes. stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, the parts that have not yet been hydrolyzed in the molecular structure are easily converted into hydrolysates in the acidic aqueous solution layer separated from the solvent, and are condensed with the generated separate reactants in the organic solvent layer to introduce E into the terminal unit. After stirring for 5 hours, the stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

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

The organic layer obtained in Example 6-a was prepared without further purification, and the ends were converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in which the reaction is in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state to adjust the pH of the mixed solution. At this time, a cage-type polymer is introduced at the end of the E structure, and the reaction proceeds continuously in the reactor to form the polymer shown in Chemical Formula 6. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

After obtaining the mixture in which the reaction was completed in Example 6-b, it was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed under reduced pressure. Then, it was precipitated twice in methanol to remove unreacted monomers, and dissolved in 30 parts by weight in a solvent in which tetrahydrofuran and aqueous solution were mixed in a 9.5:0.5 weight ratio, and stored at a temperature of -20 °C for 2 days. This is to facilitate recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Formula 6 was obtained along with various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. In this case, the molecular weight was 21,000 in terms of styrene, and the n value of X was 4-6, and the n value of Y was 4-6. In particular, the result of Chemical Formula 6 is as follows.

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

In addition, a silsesquioxane composite polymer was prepared by applying the monomers described in Table 24 below. At this time, the manufacturing method was equally applied to the method used in Example 6.

practice
Way 4-b method
Applicable monomer 4-c method
Applicable monomer 6-a
Way
Applicable monomer 6-b
Way
Applicable monomer Mw 6 ECHETMS PTMDS MTMDS MAPTMS 21,000 6-1 ECHETMS ECHETMDS ECHETMDS ECHETMS 18,000 6-2 PTMS PTMDS PTMDS PTMS 19,000 6-3 MTMS MTMDS MTMDS MTMS 31,000 6-4 GPTMS ECHETMDS GPTMDS GPTMS 63,000 6-5 MAPTMS MAPTMDS MAPTMDS MAPTMS 125,000 6-6 ECHETMS ECHETMDS PTMDS PTMS 18,000 6-7 ECHETMS ECHETMDS MTMDS MTMS 14,000 6-8 ECHETMS ECHETMDS GPTMDS GPTMS 20,000 6-9 ECHETMS ECHETMDS MAPTMDS MAPTMS 91,000 6-10 ECHETMS PTMDS ECHETMDS ECHETMS 18,000 6-11 ECHETMS MTMDS ECHETMDS ECHETMS 121,000 6-12 ECHETMS GPTMDS ECHETMDS ECHETMS 80,000 6-13 ECHETMS MAPTMDS ECHETMDS ECHETMS 112,000 6-14 PTMS PTMDS ECHETMDS ECHETMS 35,000 6-15 PTMS PTMDS MTMDS MTMS 91,000 6-16 PTMS PTMDS ECHETMDS ECHETMS 45,000 6-17 PTMS PTMDS MAPTMDS MAPTMS 75,000 6-18 PTMS ECHETMDS PTMDS PTMS 140,000 6-19 PTMS MTMDS PTMDS PTMS 220,000 6-20 PTMS GPTMDS PTMDS PTMS 51,000 6-21 PTMS MAPTMDS PTMDS PTMS 73,000 6-22 MTMS MTMDS ECHETMDS ECHETMS 69,000 6-23 MTMS MTMDS PTMDS PTMS 51,000 6-24 MTMS MTMDS GPTMDS GPTMS 91,000 6-25 MTMS MTMDS MAPTMDS MAPTMS 128,000 6-26 MTMS ECHETMDS MTMDS MTMS 68,000 6-27 MTMS PTMDS MTMDS MTMS 45,000 6-28 MTMS GPTMDS MTMDS MTMS 265,000 6-29 MTMS MAPTMDS MTMDS MTMS 105,000 6-30 GPTMS GPTMDS ECHETMDS ECHETMS 101,000 6-31 GPTMS GPTMDS PTMDS PTMS 95,000 6-32 GPTMS GPTMDS MTMDS MTMS 73,000 6-33 GPTMS GPTMDS MAPTMDS MAPTMS 51,000 6-34 GPTMS ECHETMDS GPTMDS GPTMS 31,000 6-35 GPTMS PTMDS GPTMDS GPTMS 315,000 6-36 GPTMS MTMDS GPTMDS GPTMS 125,000 6-37 GPTMS MAPTMDS GPTMDS GPTMS 45,000 6-38 MAPTMS MAPTMDS ECHETMDS ECHETMS 94,000 6-39 MAPTMS MAPTMDS PTMDS PTMS 35,000 6-40 MAPTMS MAPTMDS MTMDS MTMS 80,000 6-41 MAPTMS MAPTMDS GPTMDS GPTMS 83,000 6-42 MAPTMS ECHETMDS MAPTMDS MAPTMS 74,000 6-43 MAPTMS PTMDS MAPTMDS MAPTMS 10,000 6-44 MAPTMS MTMDS MAPTMDS MAPTMS 65,000 6-45 MAPTMS GPTMDS MAPTMDS MAPTMS 418,000

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

As for the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows, and a coating composition was prepared in a method equivalent to that of Example 1.

[Example 7-a] Preparation of catalyst

For basicity control, catalyst 1a was prepared by mixing 10 wt% potassium hydroxide (KOH) aqueous solution with 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution.

[Example 7-b] Linear silsesquioxane synthesis (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 Example 7-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and after stirring at room temperature for 1 hour, 2 20 parts by weight of -(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and then 15 parts by weight of tetrahydrourean was added dropwise, followed by further stirring for 5 hours. After removing the catalyst and impurities by collecting the mixed solution during stirring, washing twice, and filtering, the SI-OH functional group generated at the terminal group was confirmed through IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that silsesquioxane having a linear structure had a molecular weight equivalent to 6,000 styrene.

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

5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, and 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and after stirring at room temperature for 1 hour, 2 10 parts by weight of -(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydrolurane was added dropwise again, followed by stirring for an additional 2 hours. After removing the catalyst and impurities and filtering the mixed solution while stirring, washing twice to remove linear silsesquioxane in which the residual alkoxy group remains at 0.1 mmol/g or less through ¹ H-NMR analysis obtained, which is then used to introduce the cage as a continuous reaction. The morphological analysis of the linear structure confirmed that the overall structure was a linear structure through XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.

[Example 7-d] Synthesis of linear silsesquioxane 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 prepared Example 7-a catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, and after stirring at room temperature for 1 hour, Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, respectively, and then 10 parts by weight of tetrahydroleulan was added dropwise, followed by further stirring for 24 hours. After removing the catalyst and impurities by collecting the mixed solution during stirring, washing twice, and filtering, the SI-OH functional group generated at the terminal group was confirmed through IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that silsesquioxane having a linear structure had a molecular weight equivalent to 15,000 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 7-e] Creation of continuous cage structure (introduction of D structure)

5 parts by weight of 0.36 wt% HCl aqueous solution was added dropwise very slowly to the mixed solution of Example 7-d, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 °C for 30 minutes. Then, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at once to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a precursor of the D structure in which the alkoxy is open is formed separately from the linear polymer. After taking a small sample and analyzing it with H-NMR and IR to check the residual ratio of methoxy, when the residual ratio is 10%, 10 parts by weight of 0.36 wt% HCl aqueous solution is slowly added dropwise to adjust the pH to acid. gave. Then, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that a cage-type polymer was produced in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR. As a result, the analysis peaks of the structure introduced using a phenyl group appeared as two sharp shapes, and it was confirmed that a polymer such as Formula 7 was prepared without separately remaining by-products. could In addition, 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 in structure B (Completion of structure A-B-A-D)

The organic layer of the resultant obtained in Example 7-e was prepared without further purification, and the ends were converted into a cage structure using a trifunctional monomer. After dissolving 100 parts by weight of the material obtained in Example 7-e in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Then, 10 parts by weight of 0.36 wt% HCl was added to the prepared mixed solution, and after stirring for 10 minutes, 3 parts by weight of Methyltrimethoxysilane was added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a cage-type polymer is introduced into the X portion of the B structure, and the reaction proceeds continuously in the reactor to form a polymer as shown in Chemical Formula 7. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

In Example 7-f, 200 parts by weight of methylene chloride was added to the reaction mixture, followed by fractional washing with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, by precipitation twice in methanol, unreacted monomers were removed, and 30 parts by weight was dissolved in a solvent in which tetrahydrofuran and aqueous solution were mixed at a weight ratio of 9.5:0.5 and stored at a temperature of -20 °C for 2 days. This is to facilitate recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products through vacuum reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight was a value of 24,000 in terms of styrene, the n value of X was 4-6, and the n value of Y was 4-6.

In addition, a silsesquioxane composite polymer was prepared by applying the monomers described in Table 25 below. At this time, the manufacturing method was equally applied to the method used in Example 7.

practice
Way 7-b,c method
Applicable monomer 7-e method
Applicable monomer 7-f method
Applicable monomer Molecular Weight
(Mw) 7 ECHETMS PTMDS MTMS 24,000 7-1 PTMS PTMDS PTMS 11,000 7-2 MTMS MTMDS MTMS 13,000 7-3 GPTMS GPTMDS GPTMS 23,000 7-4 MAPTMS MAPTMDS MAPTMS 14,500 7-5 ECHETMS ECHETMDS ECHETMS 12,500 7-6 ECHETMS MTMDS MTMS 53,000 7-7 ECHETMS GPTMDS GPTMS 11,000 7-8 ECHETMS MAPTMDS MAPTMS 9,000 7-9 PTMS ECHETMDS ECHETMS 48,000 7-10 PTMS MTMDS MTMS 90,000 7-11 PTMS GPTMDS GPTMS 32,000 7-12 PTMS MAPTMDS MAPTMS 150,000 7-13 MTMS ECHETMDS ECHETMS 17,000 7-14 MTMS PTMDS PTMS 38,500 7-15 MTMS GPTMDS GPTMS 15,000 7-16 MTMS MAPTMDS MAPTMS 17,000 7-17 GPTMS ECHETMDS ECHETMS 6,000 7-18 GPTMS PTMDS PTMS 18,000 7-19 GPTMS MTMDS MTMS 457,000 7-20 GPTMS MAPTMDS MAPTMS 16,000 7-21 MAPTMS ECHETMDS ECHETMS 97,000 7-22 MAPTMS PTMDS PTMS 951,000 7-23 MAPTMS MTMDS MTMS 15,000 7-24 MAPTMS GPTMDS GPTMS 12,000

Example 8 : Synthesis of D-A-B-A-D structure complex silsesquioxane polymer

The following example was used to prepare a composite polymer having a DABD structure, and a coating composition was prepared in the same manner as in Example 1.

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

15 parts by weight of 0.36 wt% HCl aqueous solution was very slowly added dropwise to the mixed solution of Example 7-d in which the reaction was in progress, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4° C. for 30 minutes. Then, the amount of diphenyltetramethoxydisiloxane was prepared in an amount of 25 parts by weight, which is 5 times that of Example 7-e, and added dropwise at a time, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again by adding 20 parts by weight of the catalyst to a basic state. was regulated After completion of the reaction, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, so that the entire reactant was converted into an aqueous mixture. After 4 hours of mixing and stirring, a portion was taken and analyzed through ²⁹ Si-NMR and ¹ H-NMR. As a result, the amount of alkoxy group present in structure B was changed to 0.006 mmol/g, and the repeating units of B and D were about It was confirmed that it was introduced in a ratio of 5:5. In addition, the molecular weight in terms of styrene was measured to be 32,000. In addition, even though the cage-type structure was introduced, the molecular weight distribution of the single cage-type material was not found in the GPC form of the polymer, so it was confirmed that the cage structure was well introduced into the polymer chain through a continuous reaction.

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] Introduction of X in structure B

After the organic layer obtained in Example 8-a was prepared without further purification, the ends were converted into a cage structure using a trifunctional monomer. After dissolving 100 parts by weight of the material obtained in Example 8-a in 50 parts by weight of tetrahydrofuran, 5 parts by weight of distilled water was added to prepare a mixed solution. Then, 10 parts by weight of 0.36 wt% HCl was added to the prepared mixed solution, and after stirring for 10 minutes, 3 parts by weight of Methyltrimethoxysilane was added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution to a basic state. At this time, a cage-type polymer is introduced into the X portion of the B structure, and the reaction proceeds continuously in the reactor to form a polymer as shown in Chemical Formula 8. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

In Example 8-b, 200 parts by weight of methylene chloride was added to the reaction mixture, followed by fractional washing with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, by precipitation twice in methanol, unreacted monomers were removed, and 30 parts by weight was dissolved in a solvent in which tetrahydrofuran and aqueous solution were mixed at a weight ratio of 9.5:0.5 and stored at a temperature of -20 °C for 2 days. This is to facilitate recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Formula 1 was obtained without various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight was 36,000 in terms of styrene, the n value of X was 4-6, and the n value of Y was 4-6. In particular, the result of Chemical Formula 8 is as follows.

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

In addition, silsesquioxane composite polymers and coating compositions were prepared by applying the monomers described in Table 26 below. At this time, the manufacturing method was equally applied to the method used in Example 8.

practice
Way 7-b,c method
Applicable monomer 8-a method
Applicable monomer 8-b method
Applicable monomer Molecular Weight
(Mw) 8 ECHETMS PTMDS MTMS 36,000 8-1 PTMS PTMDS PTMS 14,000 8-2 MTMS MTMDS MTMS 18,000 8-3 GPTMS GPTMDS GPTMS 27,000 8-4 MAPTMS MAPTMDS MAPTMS 19,500 8-5 ECHETMS ECHETMDS ECHETMS 19,500 8-6 ECHETMS MTMDS MTMS 58,000 8-7 ECHETMS GPTMDS GPTMS 19,000 8-8 ECHETMS MAPTMDS MAPTMS 12,000 8-9 PTMS ECHETMDS ECHETMS 53,000 8-10 PTMS MTMDS MTMS 113,000 8-11 PTMS GPTMDS GPTMS 42,000 8-12 PTMS MAPTMDS MAPTMS 173,000 8-13 MTMS ECHETMDS ECHETMS 19,000 8-14 MTMS PTMDS PTMS 45,000 8-15 MTMS GPTMDS GPTMS 32,000 8-16 MTMS MAPTMDS MAPTMS 34,000 8-17 GPTMS ECHETMDS ECHETMS 12,000 8-18 GPTMS PTMDS PTMS 24,000 8-19 GPTMS MTMDS MTMS 486,000 8-20 GPTMS MAPTMDS MAPTMS 32,000 8-21 MAPTMS ECHETMDS ECHETMS 181,000 8-22 MAPTMS PTMDS PTMS 981,000 8-23 MAPTMS MTMDS MTMS 21,000 8-24 MAPTMS GPTMDS GPTMS 20,000

Example 9 : Synthesis of silsesquioxane E-A-B-A-D structure composite polymer

The following example was used to prepare a composite polymer having an EABAD structure, and a coating composition was prepared in the same manner as in Example 1.

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

20 parts by weight of methylene chloride was added dropwise to the mixture obtained in Example 7-g without separate purification, and 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted to have acidity, and the pH was adjusted to have acidity, and at a temperature of 4° C. for 30 minutes. stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise at a time. At this time, the parts that have not yet been hydrolyzed in the molecular structure are easily converted into hydrolysates in the acidic aqueous solution layer separated from the solvent, and are condensed with the generated separate reactants in the organic solvent layer to introduce E into the terminal unit. After stirring for 5 hours, the stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

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

The organic layer of the resultant obtained in Example 9-a was prepared without further purification, and the ends were 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 which the reaction is in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to give basic state to adjust the pH of the mixed solution. At this time, a cage-type polymer is introduced at the end of the E structure, and the reaction proceeds continuously in the reactor to form a polymer shown in Chemical Formula 9. However, since it was obtained together with other by-products, separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in a vacuum to prepare a tablet.

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

After obtaining the mixture in which the reaction was completed in Example 9-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed under reduced pressure. Thereafter, by precipitation twice in methanol, unreacted monomers were removed, and 30 parts by weight was dissolved in a solvent in which tetrahydrofuran and aqueous solution were mixed at a weight ratio of 9.5:0.5 and stored at a temperature of -20 °C for 2 days. This is to promote recrystallization of the material that cannot be introduced into the polymer and is closed in a cage structure, so that purification can be performed easily.

After filtering the solid materials obtained after the recrystallization process, it was confirmed that the polymer of Formula 9 was obtained along with various by-products through vacuum pressure reduction. In addition, when comparing the GPC result with the NMR result, it can be confirmed that a complex polymer can be obtained without problems, considering that a sharp cage form is derived as a result without a small molecule obtained alone in each stage of polymer growth. there was. At this time, the molecular weight could obtain a value of 28,000 in terms of styrene, the n value of X was 4-6, and the n value of Y was 4-6.

In addition, a silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. At this time, the manufacturing method was equally applied to the method used in Example 9.

practice
Way 7-b,c method
Applicable monomer 7-e method
Applicable monomer 9-a
Way
Applicable monomer 9-b
Way
Applicable monomer Mw 9 ECHETMS PTMDS MTMDS MAPTMS 28,000 9-1 ECHETMS ECHETMDS ECHETMDS ECHETMS 24,000 9-2 PTMS PTMDS PTMDS PTMS 21,000 9-3 MTMS MTMDS MTMDS MTMS 36,000 9-4 GPTMS ECHETMDS GPTMDS GPTMS 62,000 9-5 MAPTMS MAPTMDS MAPTMDS MAPTMS 153,000 9-6 ECHETMS ECHETMDS PTMDS PTMS 24,000 9-7 ECHETMS ECHETMDS MTMDS MTMS 19,000 9-8 ECHETMS ECHETMDS GPTMDS GPTMS 26,000 9-9 ECHETMS ECHETMDS MAPTMDS MAPTMS 99,000 9-10 ECHETMS PTMDS ECHETMDS ECHETMS 21,000 9-11 ECHETMS MTMDS ECHETMDS ECHETMS 142,000 9-12 ECHETMS GPTMDS ECHETMDS ECHETMS 70,000 9-13 ECHETMS MAPTMDS ECHETMDS ECHETMS 72,000 9-14 PTMS PTMDS ECHETMDS ECHETMS 15,000 9-15 PTMS PTMDS MTMDS MTMS 51,000 9-16 PTMS PTMDS ECHETMDS ECHETMS 85,000 9-17 PTMS PTMDS MAPTMDS MAPTMS 95,000 9-18 PTMS ECHETMDS PTMDS PTMS 160,000 9-19 PTMS MTMDS PTMDS PTMS 240,000 9-20 PTMS GPTMDS PTMDS PTMS 56,000 9-21 PTMS MAPTMDS PTMDS PTMS 71,000 9-22 MTMS MTMDS ECHETMDS ECHETMS 81,000 9-23 MTMS MTMDS PTMDS PTMS 63,000 9-24 MTMS MTMDS GPTMDS GPTMS 121,000 9-25 MTMS MTMDS MAPTMDS MAPTMS 153,000 9-26 MTMS ECHETMDS MTMDS MTMS 82,000 9-27 MTMS PTMDS MTMDS MTMS 63,000 9-28 MTMS GPTMDS MTMDS MTMS 310,000 9-29 MTMS MAPTMDS MTMDS MTMS 125,000 9-30 GPTMS GPTMDS ECHETMDS ECHETMS 97,000 9-31 GPTMS GPTMDS PTMDS PTMS 45,000 9-32 GPTMS GPTMDS MTMDS MTMS 61,000 9-33 GPTMS GPTMDS MAPTMDS MAPTMS 52,000 9-34 GPTMS ECHETMDS GPTMDS GPTMS 37,000 9-35 GPTMS PTMDS GPTMDS GPTMS 365,000 9-36 GPTMS MTMDS GPTMDS GPTMS 85,000 9-37 GPTMS MAPTMDS GPTMDS GPTMS 75,000 9-38 MAPTMS MAPTMDS ECHETMDS ECHETMS 144,000 9-39 MAPTMS MAPTMDS PTMDS PTMS 85,000 9-40 MAPTMS MAPTMDS MTMDS MTMS 60,000 9-41 MAPTMS MAPTMDS GPTMDS GPTMS 53,000 9-42 MAPTMS ECHETMDS MAPTMDS MAPTMS 12,000 9-43 MAPTMS PTMDS MAPTMDS MAPTMS 10,000 9-44 MAPTMS MTMDS MAPTMDS MAPTMS 32,000 9-45 MAPTMS GPTMDS MAPTMDS MAPTMS 231,000

[Experiment]

PC (i-components, Glastic 0.5T), PET (SKC, V5400), PMMA (EVONIK, Plexiglas OF058), PVC (Shindong-A Synthetic Co., Ltd., transparent PVC film 1 mm), PU (SONG-STOMER P-7100) The coating composition prepared in Examples 1 to 9 was coated on a film prepared by

- Surface hardness measurement : In general, the pencil hardness method (JIS 5600-5-4) is generally evaluated with a 750 g load. Under a harsher condition, a 1 kgf load, the pencil is moved horizontally at a speed of 0.5 mm per second at a 45 degree angle to the coated surface 10 mm It moved and scraped the coating film and evaluated it as a scratch mark. If scratch marks of 3 mm or more are not confirmed 2 or more times out of 5 experiments, select and evaluate a pencil of higher hardness. was evaluated and shown in Tables 28 and 29 below. As a result of the evaluation, glass-level 9H hardness was confirmed regardless of the substrate type at a coating thickness of 10 μm or more.

Example (coating thickness 10 um) PET PC PMMA before coating after coating before coating after coating before coating after coating Photocurable coating composition of Example 1 2B 9H 6B or less 9H 2H 9H Thermosetting coating composition of Example 2 9H 9H 9H Photocurable coating composition of Example 3 9H 9H 9H Thermosetting coating composition of Example 4 9H 9H 9H Photocurable coating composition of Example 5 9H 9H 9H Thermosetting coating composition of Example 6 9H 9H 9H Polymer self-coating composition of Example 6 9H 9H 9H Thermosetting coating composition of Example 7 9H 9H 9H Photocurable coating composition of Example 8 9H 9H 9H Thermosetting coating composition of Example 9 9H 9H 9H

Example (coating thickness 10 um) PVC PU before coating after coating before coating after coating Photocurable coating composition of Example 1 4B 9H 6B 9H Thermosetting coating composition of Example 2 9H 9H Photocurable coating composition of Example 3 9H 9H Thermosetting coating composition of Example 4 9H 9H Photocurable coating composition of Example 5 9H 9H Thermosetting coating composition of Example 6 9H 9H Polymer self-coating composition of Example 6 9H 9H Thermosetting coating composition of Example 7 9H 9H Photocurable coating composition of Example 8 9H 9H Thermosetting coating composition of Example 9 9H 9H

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

Warpage evaluation criteria are within ±0.1 mm: ◎, within ±0.2 mm: ○, -0.3 mm or less or 0.3 mm or more: X. The evaluation result was excellent in all the base materials.

Example (coating thickness 10 um)
YI (ASTMD1925) PET PC PMMA before coating after coating before coating after coating before coating after coating Photocurable coating composition of Example 1-1 X ◎ ○ ◎ X ○ Thermosetting coating composition of Example 2-2 ◎ ◎ ○ Photocurable coating composition of Example 3-3 ◎ ◎ ◎ Thermosetting coating composition of Example 4-4 ◎ ◎ ◎ Photocurable coating composition of Example 5-5 ◎ ◎ ◎ Thermosetting coating composition of Example 6 ◎ ◎ ◎ Polymer self-coating composition of Example 6 ◎ ◎ ◎ Thermosetting coating composition of Examples 7-7 ◎ ◎ ◎ Photocurable coating composition of Examples 8-8 ◎ ◎ ◎ Thermosetting coating composition of Examples 9-9 ◎ ◎ ◎

Example (coating thickness 10 um)
YI (ASTMD1925) PVC PU before coating after coating before coating after coating Photocurable coating composition of Example 1-1 ○ ◎ X ○ Thermosetting coating composition of Example 2-2 ◎ ○ Photocurable coating composition of Example 3-3 ◎ ◎ Thermosetting coating composition of Example 4-4 ◎ ◎ Photocurable coating composition of Example 5-5 ◎ ◎ Thermosetting coating composition of Example 6 ◎ ◎ Polymer self-coating composition of Example 6 ◎ ◎ Thermosetting coating composition of Examples 7-7 ◎ ◎ Photocurable coating composition of Examples 8-8 ◎ ◎ Thermosetting coating composition of Examples 9-9 ◎ ◎

- Scratch test measurement (JIS K5600-5-9): The method for evaluating abrasion by steel wool is to wind the steel wool of #0000 around the tip of a sledgehammer weighing about 1 kg, rub the reciprocating specimen 15 times, and measure the haze. , In this evaluation, the test piece, which is a harsher condition, was rubbed 400 times, and haze was measured and visual evaluation was performed with a microscope. As a result, it was judged as a failure when the haze increase increased by 0.05% or more. It was confirmed that the coating with a coating thickness of 5 μm or more had excellent resistance to scratches on the surface.

- Adhesion evaluation (JIS K5600-5-6): Scratch the coating film at intervals of 1-5 mm with a cutter blade and attach cellophane tape on it. Adhesiveness was judged by the number falling out of 100, and the results for the photocurable coating composition of Example 6 are shown in Tables 32 and 33 below. The notation is "(Number that does not fall/100)" as the number that does not fall out of 100. It was confirmed that the adhesiveness was very good. Although not described in Tables 32 and 33, it was confirmed that the coating compositions of other examples of the present invention had excellent adhesion as a result of evaluation.

Evaluation items PET PC PMMA before coating after coating before coating after coating before coating after coating coating thickness - 10㎛ - 10㎛ - 10㎛ adhesion - pass
(100/100) - pass
(100/100) - pass
(100/100) Transmittance (%) UV-vis-500nm 92.4 93.8 91.4 91.6 91.9 91.6 Scratch test
(Steel wool, 1 kg _f load,
400 times) Fail pass Fail pass Fail pass Haze (%)
(◎: 0.00 to 0.10
○: 0.11 to 0.20,
X: 0.21 or more) ○ ◎ ○ ◎ ○ ◎

Evaluation items PVC PU before coating after coating before coating after coating coating thickness - 10㎛ - 10㎛ adhesion - pass
(100/100) - pass
(100/100) Transmittance (%) UV-vis-500nm 85.21 87.21 80.4 83.6 Scratch test
(Steel wool, 1 kg _f load,
400 times) Fail pass Fail pass Haze (%)
(◎: 0.00 to 0.10
○: 0.11 to 0.20,
X: 0.21 or more) ○ ◎ ○ ◎

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

Claims (14)

A plastic coating method comprising coating and curing a plastic coating composition comprising a silsesquioxane composite polymer represented by any one of the following formulas 1 to 9 on a plastic surface:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 1 to 9,
A is

and B is

and D is

and E is

is,
Y is each independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
each X is independently R ²² or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acrylic group, thiol group, isocyanate group, nitrile group, nitro group, phenyl group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₁ ~ C ₄₀ Alkoxy group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ Heterocycloalkyl group, C ₆ ~ C ₄₀ Aryl group, C ₃ ~ C ₄₀ Heteroaryl group, C ₃ ~ C ₄₀ aralkyl group, C ₃ ~ C ₄₀ aryloxy group, or C ₃ ~ C ₄₀ aryl thiol group,
a and d are each independently an integer from 1 to 100,000,
b is each independently an integer from 1 to 500,
e is each independently 1 or 2,
n is each independently an integer from 1 to 20; According to claim 1,
The plastic is polyethylene (polyethylene, PE), polypropylene (polypropylene, PP), polystyrene (PS), polyethylene terephthalate (polyethylene terephthalate, PET, PET), polyamides (polyamides, PA, nylon), polyester ( polyester, PES), polyvinyl chloride (PVC), polyurethane (polyurethanes, PU), polycarbonate (PC), high-hardness polycarbonate (high-hardness PC), polyvinylidene chloride (polyvinylidene chloride, PVDC) ), polytetrafluoroethylene (PTFE), polyetheretherketone (polyetheretherketone, PEEK), and polyetherimide (polyetherimide, PEI), characterized in that at least one selected from the group consisting of plastic coating method. According to claim 1,
The coating thickness is a plastic coating method, characterized in that 0.01 to 500 um. A plastic coating composition comprising a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 1 to 9,
A is

and B is

and D is

and E is

is,
Y is each independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
each X is independently R ²² or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acrylic group, thiol group, isocyanate group, nitrile group, nitro group, phenyl group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₁ ~ C ₄₀ Alkoxy group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ Heterocycloalkyl group, C ₆ ~ C ₄₀ Aryl group, C ₃ ~ C ₄₀ Heteroaryl group, C ₃ ~ C ₄₀ aralkyl group, C ₃ ~ C ₄₀ aryloxy group, or C ₃ ~ C ₄₀ aryl thiol group,
a and d are each independently an integer from 1 to 100,000,
b is each independently an integer from 1 to 500,
e is each independently 1 or 2,
n is each independently an integer from 1 to 20; 5. The method of claim 4,
a is 3 to 1000, b is 1 to 500, d is 1 to 500 plastic coating composition. 5. The method of claim 4,
A plastic coating composition, characterized in that the average of n values is 4 to 5. 5. The method of claim 4,
The plastic coating composition, characterized in that the weight average molecular weight of the silsesquioxane composite polymer is 1,000 to 1,000,000. 5. The method of claim 4,
The coating composition is a plastic coating composition, characterized in that the solvent-free type. 5. The method of claim 4,
The coating composition is
the silsesquioxane composite polymer;
initiator; and
organic solvents;
A plastic coating composition comprising a. 5. The method of claim 4,
The plastic coating composition, characterized in that the coating composition further comprises a pigment. A silsesquioxane composite polymer coated plastic comprising a cured product coated with a plastic coating composition containing a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 on the surface thereof:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 1 to 9,
A is

and B is

and D is

and E is

is,
Y is each independently O, NR ²¹ or [(SiO _3/2 R) _4+2n O], at least one is [(SiO _3/2 R) _4+2n O],
each X is independently R ²² or [(SiO _3/2 R) _4+2n R], at least one is [(SiO _3/2 R) _4+2n R],
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth)acryl group; thiol group; isocyanate group; nitrile group; nitro group; phenyl group; Deuterium, halogen, amine group, epoxy group, (meth)acrylic group, thiol group, isocyanate group, nitrile group, nitro group, phenyl group or unsubstituted C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₁ ~ C ₄₀ Alkoxy group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ Heterocycloalkyl group, C ₆ ~ C ₄₀ Aryl group, C ₃ ~ C ₄₀ Heteroaryl group, C ₃ ~ C ₄₀ aralkyl group, C ₃ ~ C ₄₀ aryloxy group, or C ₃ ~ C ₄₀ aryl thiol group,
a and d are each independently an integer from 1 to 100,000,
b is each independently an integer from 1 to 500,
e is each independently 1 or 2,
n is each independently an integer from 1 to 20; 12. The method of claim 11,
The silsesquioxane composite polymer coated plastic is a silsesquioxane composite polymer coated plastic, characterized in that it is formed by the plastic coating method of claim 1. An article comprising the silsesquioxane composite polymer coated plastic according to claim 11 . 14. The method of claim 13,
The above articles are optical films, protective films, plastics for electronic products, glasses, building exterior materials, building interior materials, plastic piping, electric wire coverings, optical lenses, soundproof walls, plastic signs, plastic sculptures, furniture, lighting, sunroofs, or An article characterized in that it is a helmet.