WO2015130146A1 - Transparent substrate having reinforced surfaces and method for manufacturing same - Google Patents

Transparent substrate having reinforced surfaces and method for manufacturing same Download PDF

Info

Publication number
WO2015130146A1
WO2015130146A1 PCT/KR2015/001971 KR2015001971W WO2015130146A1 WO 2015130146 A1 WO2015130146 A1 WO 2015130146A1 KR 2015001971 W KR2015001971 W KR 2015001971W WO 2015130146 A1 WO2015130146 A1 WO 2015130146A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
pomma
glyp
phenyl
eche
Prior art date
Application number
PCT/KR2015/001971
Other languages
French (fr)
Korean (ko)
Inventor
최승석
유재원
남동진
정희정
최지식
Original Assignee
주식회사 동진쎄미켐
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 동진쎄미켐 filed Critical 주식회사 동진쎄미켐
Priority to CN201580011148.8A priority Critical patent/CN106062053B/en
Priority claimed from KR1020150028601A external-priority patent/KR102367120B1/en
Publication of WO2015130146A1 publication Critical patent/WO2015130146A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to a surface-reinforced transparent substrate and a method for manufacturing the same.
  • the surface treatment is performed by using a silsesquioxane composite polymer including a linear silsesquioxane chain having a specific structure and a cage-type silsesquioxane in one polymer.
  • the present invention relates to a surface-reinforced transparent substrate and a method of manufacturing the same, which significantly improve the surface hardness and at the same time improve fingerprint resistance, scratch resistance, contamination resistance, heat resistance, permeability and haze characteristics.
  • Transparent substrates are used for various purposes. In particular, it is applied as a window cover substrate or protective film to various fields including electronic products such as smartphones, tablet PCs, notebook PCs, AIO (All-In-One) PCs, LCD monitors, TVs, billboards, touch panels, or Transparent substrates are used to protect internal articles.
  • electronic products such as smartphones, tablet PCs, notebook PCs, AIO (All-In-One) PCs, LCD monitors, TVs, billboards, touch panels, or Transparent substrates are used to protect internal articles.
  • transparent substrate glass is typical, but brittle (fragility) is strong, and transparent substrates made of plastic are widely used.
  • Transparent substrates made of plastic include PC (polycarbonate) and PET. Although PE or PMMA is used, in general, a transparent substrate made of a plastic material has a problem of low surface hardness, low durability, low fingerprint resistance, scratch resistance, stain resistance, heat resistance, permeability, and haze characteristics.
  • Korean Patent Application No. 2009-7009932 discloses a polycarbonate laminate having an improved surface hardness by coating acrylic resin on polycarbonate, but the improved surface hardness is still insufficient at 4H or less with a pencil hardness. .
  • ProtectM Co., Ltd. forms a transparent substrate by forming various layers such as a hard coating layer, a self-restored layer, an impact diffusion layer, a self-cleaning layer, an anti-fingerprint layer, and an external shock absorber layer as a protective film of a mobile phone.
  • various layers such as a hard coating layer, a self-restored layer, an impact diffusion layer, a self-cleaning layer, an anti-fingerprint layer, and an external shock absorber layer as a protective film of a mobile phone.
  • the present invention significantly improves the surface hardness of the transparent substrate even with a single layer formed on the transparent substrate, and at the same time, the fingerprint, scratch resistance, contamination resistance, heat resistance, permeability and haze characteristics are improved.
  • An object of the present invention is to provide an improved surface hardened transparent substrate and a method of manufacturing the same.
  • the present invention provides a method for strengthening the surface of a transparent substrate, characterized in that the coating composition comprising a silsesquioxane composite polymer of a specific structure on the transparent substrate and coating and curing.
  • Another object of the present invention is to provide an electronic product including the surface-reinforced transparent substrate.
  • the present invention provides a surface-reinforced transparent substrate, characterized in that the cured product of the silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 9 is laminated on a transparent substrate:
  • Each Y is 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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
  • a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
  • b are each independently an integer of 1 to 500
  • e are each independently 1 or 2, preferably 1,
  • n is independently an integer of 1-20, Preferably it is 3-10.
  • the present invention provides a method for strengthening the surface of a transparent substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the formulas (1) to (9) above on the transparent substrate.
  • the present invention provides an electronic product comprising the surface-reinforced transparent substrate.
  • the present invention provides a protective plate comprising the surface-reinforced transparent substrate.
  • the surface-reinforced transparent substrate according to the present invention significantly improves the surface hardness of the transparent substrate by including the cured product of the silsesquioxane composite polymer having a specific structure as a coating layer, and at the same time, the fingerprint resistance, scratch resistance, contamination resistance, heat resistance, permeability and The haze characteristics are improved, which makes it very useful for window cover substrates, protective films or protective plates of electronic products.
  • the surface-reinforced transparent substrate of the present invention is characterized in that the cured product of the silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is laminated on the transparent substrate:
  • Each Y is 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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
  • a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
  • b are each independently an integer of 1 to 500
  • e are each independently 1 or 2, preferably 1,
  • n is independently an integer of 1-20, Preferably it is 3-10.
  • the surface-reinforced transparent substrate of the present invention comprises a silsesquioxane polymer having a specific structure having [A] a and [D] d repeating units, and optionally having [B] b or [E] e repeating unit, on the surface of the transparent substrate.
  • the present invention provides a transparent substrate that is suitable for window cover substrates and protective films of electronic products and used as a protective plate for protecting internal articles.
  • R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
  • a first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [D] d (OR 3 ) 2 and [D] d (OR 4 ) 2 structures into the chemical formula 10 after the first step, as shown in the chemical formula 2.
  • a second step of adding and stirring an excess of the organic silane compound after the adjustment A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And through a third step of the reaction, it can be prepared by proceeding to the purification step to remove the cage structure as a by-product generated by recrystallization.
  • a third step of condensation reaction by adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic.
  • the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, The pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4.
  • the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5
  • the pH of the reaction solution of the second step is preferably 2 to 4
  • the pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4.
  • the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
  • step 1 Mixing a basic catalyst and an organic solvent in a reactor, followed by adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled;
  • the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added.
  • a second step of stirring A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
  • the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4 in the method for preparing the polymer of Formula 7 to 9,
  • the pH of the reaction solution of the third stage is preferably 8 to 11.5, the pH of the reaction solution of the fourth stage is preferably 9 to 11.5, the pH of the reaction solution of the fifth stage is preferably 2 to 4, It is preferable that it is 8-11.5 of the reaction liquid of a 6th step, and it is preferable that pH of the reaction liquid of the 7th step which introduces Ee is 1.5-4.
  • the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
  • an acidic catalyst is added to the reactor to convert the reaction solution into an acidic atmosphere, and an organic silane compound is mixed and stirred.
  • the terminal may further include a repeating unit of [E] e.
  • a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
  • the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba.
  • the amine based catalyst may be tetramethylammonium hydroxide (TMAH)
  • the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ).
  • the content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted.
  • the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation.
  • the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
  • the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art.
  • organic solvent commonly used in the art.
  • solvents such as nit
  • the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , 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 can be used
  • the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the mechanical strength and hardness of the cured layer by increasing the curing density of the composite polymer
  • the organosilane compound containing the epoxy group or (meth) acryl group which has the effect of improving the can be used.
  • organosilane compound examples include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane,
  • 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, and More preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by Formula 11 below:
  • R is as defined above.
  • n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, preferably Below 3 to 10, more preferably, the average n value is 4 to 5, for example, when n is 4 to represent a structure substituted by the formula (12):
  • R is as defined above.
  • the silsesquioxane polymer according to the present invention may be a polymer shown in Tables 1 to 18 below.
  • ECHE Epoxycyclohexyl
  • GlyP means Glycidoxypropyl
  • POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use.
  • n is 1-8 each independently.
  • the silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
  • the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
  • the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
  • the silsesquioxane composite polymer of Formula 5 may be a polymer described in Tables 9 and 10.
  • the silsesquioxane composite polymer of Chemical Formula 6 may be a polymer described in Tables 11 and 12 below.
  • the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
  • the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
  • the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
  • the silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
  • the weight average molecular weight of the silsesquioxane composite polymer according to 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 the silsesquioxane can be improved simultaneously.
  • the method for laminating the cured product of the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 on a transparent substrate includes a coating composition comprising the silsesquioxane composite polymer represented by any one of Formulas 1 to 9. It may be formed by coating and curing the transparent substrate. It is also possible to use two or more composite polymers, and it is preferable to use the silsesquioxane composite polymer represented by any one of Formulas 3 to 9. In this case, the physical properties of the transparent substrate including the surface hardness can be further improved by including the repeating unit [B] b or [E] e.
  • the coating composition may be coated alone as a solvent-free type when the silsesquioxane composite polymer is a liquid, and may be configured to include an organic solvent in the case of a solid phase.
  • the coating composition may further include an initiator or a curing agent.
  • the coating composition is characterized in that it 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, the initiator It may optionally further include additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
  • additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
  • the silsesquioxane composite polymer may be included at least 5 parts by weight or more, based on 100 parts by weight of the coating composition, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight. It is preferably included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
  • organic solvent examples 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,
  • polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto.
  • the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.
  • an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group
  • various curing using heat or light is possible.
  • the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.
  • various initiators may be used, and the initiator may be included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, After curing, the transmittance and coating stability can be satisfied at the same time.
  • a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride.
  • sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations).
  • Iodonium such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopent
  • the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like 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.
  • triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutyl
  • phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
  • the curing agent is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the composition.
  • the present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction.
  • additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction.
  • Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength.
  • Each of the additives may be independently included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition.
  • Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aral
  • polyester hydroxy polydimethylsiloxane Polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc
  • a transparent substrate that can be used for the surface-reinforced transparent substrate of the present invention may be a plastic transparent substrate and glass, the transparent substrate is a substrate having a transmittance of at least 80% or more in a light source of 500 nm wavelength, the specific plastic transparent substrate Examples include Cyclic olefin copolymer (COC), Polyacrylate (PAc), Polycarbonate (PC), Polyethylene (PE), Polyetheretherketone (PEEK), Polyetherimide (PEI), Polyethylenenaphthalate (PEN), Polyethersulfone (PES), Polyethyleneterephtalate (PE), and PI (Polyimide), PO (Polyolefin), PMMA (Polymethylmethacrylate), PSF (Polysulfone), PVA (Polyvinylalcohol), PVCi (Polyvinylcinnamate), TAC (Triacetylcellulose), Polysilicon (Poly Silicone), Polyurethane (Polyurethane) and Epoxy Res
  • a method of coating the coating composition on a transparent substrate is known as spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, and the like.
  • the photocuring or thermosetting can be appropriately selected and applied according to the functional group of the composite polymer.
  • the curing temperature is 80 to 120 °C.
  • the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, even more preferably 1 to 100 um. Within the above range, not only can the surface hardness of 7H or more be stably secured, but also excellent physical properties of the substrate surface properties. In particular, when the coating layer is laminated to a thickness of 5 um or more can be applied as a substitute for glass because the surface hardness can be represented stably 9H.
  • the present invention also provides an electronic product including the surface-reinforced transparent substrate, preferably, the electronic product is a display device, and specific examples thereof include a smartphone, a tablet PC, a notebook PC, and an AIO (All-In-One). ) It may be a PC, an LCD monitor, a TV, a billboard or a touch panel, or a flexible smart device (wearable smart device) that requires flexibility of a substrate.
  • a display device preferably, the electronic product is a display device, and specific examples thereof include a smartphone, a tablet PC, a notebook PC, and an AIO (All-In-One).
  • It may be a PC, an LCD monitor, a TV, a billboard or a touch panel, or a flexible smart device (wearable smart device) that requires flexibility of a substrate.
  • the shape of the surface-reinforced transparent substrate included in the electronic product is not particularly limited and may be, for example, in the form of a window cover substrate or a protective film.
  • the electronic product according to the present invention significantly improves the surface hardness of the transparent substrate with only one single layer, and at the same time, has excellent anti-fingerprint, scratch resistance, contamination resistance, heat resistance, permeability and haze characteristics.
  • the present invention provides a protective plate comprising the surface-reinforced transparent substrate, the protective plate may be transparent to look inside or protect the electronics (display device) therein, for example, public buildings ( It may be a transparent protective plate that protects display devices in display installations of train stations, airports, bus terminals, etc.).
  • ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • GPTMS is Glycidoxypropytrimethoxysilane
  • MAPTMS is (methacryloyloxy) propyltrimethoxysilane
  • PTMS is Phenyltrimethoxysilane
  • MTMS is Methyltrimethoxysilane
  • ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane
  • MAPTMDS stands for Di (methacryloyloxy) propy
  • PTMDS stands for Di (phenyl) tetramethoxy disiloxane
  • MTMDS stands for Di
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Example 1-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours.
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
  • Example 1-b To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. 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 in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
  • Example 1-c 30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30 wt% to prepare a coating composition of 100 g. 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 of the coating composition, and stirred for 10 minutes to prepare a photocurable coating composition.
  • Example 1-c 50 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
  • Example 1-c alone constitute a coating composition without a separate composition.
  • Example 1 In order to manufacture a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method corresponding to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.
  • Example 1-b To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one 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. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer.
  • silsesquioxane composite polymer and the coating composition 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.
  • Example 1 In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method corresponding to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.
  • Example 1-c To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 ° C at a temperature of 4 ° C. Stirred for a minute. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
  • Example 3-a After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a 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. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • Example 3-b After the reaction mixture was obtained 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 by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was 17,000 in terms of styrene
  • the average value of n was 4.6
  • the results of formula (3) are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. In this case, the method used in Example 3 was equally applied.
  • a continuous hydrolysis and condensation were carried out step by step to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method corresponding to that described in Example 1.
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Example 4-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours.
  • the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
  • XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
  • Example 4-b To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, 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 in a basic state.
  • the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by 29 Si-NMR and 1 H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although 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, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 12,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula 4 results are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. In this case, the method used in Example 4 was equally applied.
  • Example 1 The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
  • Example 4-b To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted.
  • Example 5-a After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 16,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula (5) is as follows.
  • silsesquioxane composite polymer and the coating composition 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.
  • Example 1 The following method was used to prepare the composite polymer having the E-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
  • Example 4-c 20 parts by weight of methylene chloride was added dropwise to the mixture obtained in Example 4-c, 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
  • Example 6-a After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. 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. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • Example 6-b the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 21,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula (6) is as follows.
  • 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.
  • Synthesis step was carried out step by step, continuous hydrolysis and condensation step, the same method as in Example 1 to prepare a coating composition.
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Example 7-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours.
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
  • Example 7-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours.
  • the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
  • XRD analysis confirmed that the overall structure is a linear structure through the 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-a catalyst To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, 10 parts by weight of the prepared Example 7-a catalyst were added dropwise and stirred at room temperature for 1 hour, followed by Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours.
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.
  • Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. 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 in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was a styrene conversion value of 24,000
  • the average value of n of X was 4.6
  • the average value of n of Y was 4.6.
  • 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.
  • Example 1 In order to prepare a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared in the same manner as in Example 1.
  • Example 7-d 15 parts by weight of a 0.36 wt% HCl aqueous solution was added 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. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state.
  • the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (8). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 36,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula 8 results are as follows.
  • silsesquioxane composite polymer and the coating composition 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.
  • Example 1 In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
  • Example 7-g To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
  • Example 9-a After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time 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 give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • Example 9-b After the reaction mixture was obtained 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 by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in a styrene conversion value of 28,000, the average value of n of X was 4.6, the average value of n of Y was 4.6.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. In this case, the method used in Example 9 was equally applied.
  • the coating composition prepared in Examples 1 to 9 was coated on PC, PET and PMMA transparent substrates, and cured to measure surface properties.
  • the pencil hardness method (JIS 5600-5-4) is generally rated at 500 g load, which is 3 kg horizontally at a rate of 0.5 mm per second at a 45-degree angle to the coating surface under a more severe 1 kgf load.
  • the coating film was moved to evaluate the scratches. If no traces of scratches are found in five experiments, select a pencil with a higher hardness.If more than two scratches are found, select a pencil and the pencil hardness lower than the pencil hardness is evaluated as pencil hardness of the coating It is shown in Table 28 below.
  • the evaluation results confirmed the 9H hardness of the glass level regardless of the substrate type at a coating thickness of 10 um or more.
  • Flexural evaluation criteria are within ⁇ 0.1 mm before reliability evaluation and within ⁇ 0.3 mm after reliability evaluation.
  • the evaluation result was excellent in all the PET, PC, and PMMA base materials.
  • the surface-reinforced transparent substrate of the present invention not only shows very excellent surface hardness and optical properties, but also excellent in other physical properties.
  • the surface-reinforced transparent substrate according to the present invention significantly improves the surface hardness of the transparent substrate by including the cured product of the silsesquioxane composite polymer having a specific structure as a coating layer, and at the same time, the fingerprint resistance, scratch resistance, contamination resistance, heat resistance, permeability and The haze characteristics are improved, which makes it very useful for window cover substrates, protective films or protective plates of electronic products.

Abstract

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

Description

표면강화 투명기판 및 이의 제조방법Surface-Reinforced Transparent Substrate and Manufacturing Method Thereof
본 발명은 표면강화 투명기판 및 이의 제조방법에 관한 것으로, 하나의 고분자 내에 특정 구조의 선형 실세스퀴옥산 사슬 및 케이지형 실세스퀴옥산을 포함하는 실세스퀴옥산 복합 고분자를 이용하여 표면을 처리함으로써 표면경도가 현저히 개선되고, 동시에 내지문성, 내스크레치성, 내오염성, 내열성, 투과도 및 헤이즈 특성이 향상된 표면강화 투명기판 및 이의 제조방법에 관한 것이다.The present invention relates to a surface-reinforced transparent substrate and a method for manufacturing the same. The surface treatment is performed by using a silsesquioxane composite polymer including a linear silsesquioxane chain having a specific structure and a cage-type silsesquioxane in one polymer. The present invention relates to a surface-reinforced transparent substrate and a method of manufacturing the same, which significantly improve the surface hardness and at the same time improve fingerprint resistance, scratch resistance, contamination resistance, heat resistance, permeability and haze characteristics.
투명기판은 다양한 용도로 사용되고 있다. 특히 스마트폰, 테블릿 PC, 노트북 PC, AIO(All-In-One) PC, LCD 모니터, TV, 광고판, 터치패널 등 전자제품을 포함하여 다양한 분야에 윈도우 커버 기판 또는 보호필름으로 적용되며, 또는 내부 물품을 보호하는 보호판의 용도로 투명기판이 사용되고 있다.Transparent substrates are used for various purposes. In particular, it is applied as a window cover substrate or protective film to various fields including electronic products such as smartphones, tablet PCs, notebook PCs, AIO (All-In-One) PCs, LCD monitors, TVs, billboards, touch panels, or Transparent substrates are used to protect internal articles.
투명기판의 일예로는 유리가 대표적이나 취성(잘 깨지는 성질)이 강하여 플라스틱 재질의 투명기판들이 널리 사용되고 있다.As an example of a transparent substrate, glass is typical, but brittle (fragility) is strong, and transparent substrates made of plastic are widely used.
플라스틱 재질의 투명기판으로는 PC(폴리카보네이트), PET. PE 또는 PMMA가 사용되고 있으나, 일반적으로 플라스틱 재질의 투명기판은 표면경도가 낮고, 내구성이 떨어지며, 내지문성, 내스크레치성, 내오염성, 내열성, 투과도 및 헤이즈 특성이 낮은 문제점이 있다.Transparent substrates made of plastic include PC (polycarbonate) and PET. Although PE or PMMA is used, in general, a transparent substrate made of a plastic material has a problem of low surface hardness, low durability, low fingerprint resistance, scratch resistance, stain resistance, heat resistance, permeability, and haze characteristics.
이를 해결하기 위하여 대한민국특허출원 제2009-7009932호에서는 폴리카보네이트에 아크릴수지를 코팅하여 표면경도를 향상시킨 폴리카보네이트 적층체를 개시하고 있으나, 개선된 표면경도가 연필경도로 4H 이하로 여전히 부족한 실정이다.In order to solve this problem, Korean Patent Application No. 2009-7009932 discloses a polycarbonate laminate having an improved surface hardness by coating acrylic resin on polycarbonate, but the improved surface hardness is still insufficient at 4H or less with a pencil hardness. .
또한 스마트폰과 같은 터치기능이 접목된 경우 프로텍트엠(주)에서는 휴대폰의 보호필름으로 하드코팅층-자체복원층-충격확산층-셀프클리닝층-지문방지층-외부충격흡수층 등 다양한 층을 형성하여 투명기판의 표면특성을 향상시키고자 하였으나 공정이 너무 복잡하고, 생산성이 떨어지는 문제점이 있었다. In addition, when a touch function such as a smartphone is applied, ProtectM Co., Ltd. forms a transparent substrate by forming various layers such as a hard coating layer, a self-restored layer, an impact diffusion layer, a self-cleaning layer, an anti-fingerprint layer, and an external shock absorber layer as a protective film of a mobile phone. To improve the surface properties of the but the process is too complex, there was a problem that the productivity is low.
상기와 같은 문제점을 해결하기 위해, 본 발명은 투명기판위에 형성되는 하나의 단일층 만으로도 투명기판의 표면경도가 현저히 개선되고, 동시에 내지문성, 내스크레치성, 내오염성, 내열성, 투과도 및 헤이즈 특성이 향상된 표면강화 투명기판 및 이의 제조방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention significantly improves the surface hardness of the transparent substrate even with a single layer formed on the transparent substrate, and at the same time, the fingerprint, scratch resistance, contamination resistance, heat resistance, permeability and haze characteristics are improved. An object of the present invention is to provide an improved surface hardened transparent substrate and a method of manufacturing the same.
또한 본 발명은 투명기판 위에 특정구조의 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화시키는 것을 특징으로 하는 투명기판의 표면강화방법을 제공한다.In another aspect, the present invention provides a method for strengthening the surface of a transparent substrate, characterized in that the coating composition comprising a silsesquioxane composite polymer of a specific structure on the transparent substrate and coating and curing.
또한 본 발명은 상기 표면강화 투명기판을 포함하는 전자제품을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an electronic product including the surface-reinforced transparent substrate.
또한 본 발명은 상기 표면강화 투명기판을 포함하는 보호판을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a protective plate including the surface-reinforced transparent substrate.
상기 목적을 달성하기 위해 본 발명은 투명기판 위에 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자의 경화물이 적층된 것을 특징으로 하는 표면강화 투명기판을 제공한다:In order to achieve the above object, the present invention provides a surface-reinforced transparent substrate, characterized in that the cured product of the silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 9 is laminated on a transparent substrate:
[화학식 1][Formula 1]
Figure PCTKR2015001971-appb-I000001
Figure PCTKR2015001971-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2015001971-appb-I000002
Figure PCTKR2015001971-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2015001971-appb-I000003
Figure PCTKR2015001971-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2015001971-appb-I000004
Figure PCTKR2015001971-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2015001971-appb-I000005
Figure PCTKR2015001971-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2015001971-appb-I000006
Figure PCTKR2015001971-appb-I000006
[화학식 7][Formula 7]
Figure PCTKR2015001971-appb-I000007
Figure PCTKR2015001971-appb-I000007
[화학식 8][Formula 8]
Figure PCTKR2015001971-appb-I000008
Figure PCTKR2015001971-appb-I000008
[화학식 9][Formula 9]
Figure PCTKR2015001971-appb-I000009
Figure PCTKR2015001971-appb-I000009
상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,
A는
Figure PCTKR2015001971-appb-I000010
이고, B는
Figure PCTKR2015001971-appb-I000011
이고, D는
Figure PCTKR2015001971-appb-I000012
이고, E는
Figure PCTKR2015001971-appb-I000013
이며,A is
Figure PCTKR2015001971-appb-I000010
And B is
Figure PCTKR2015001971-appb-I000011
And D is
Figure PCTKR2015001971-appb-I000012
And E is
Figure PCTKR2015001971-appb-I000013
Is,
Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,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, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 바람직하기로는 중수소, 할로겐, 아민기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기, 사이클로헥실 에폭시기로 치환되거나 치환되지 않은 C1~C40의 알킬기, C2~C40의 알케닐기, 아민기, 에폭시기, 사이클로헥실 에폭시기, (메타)아크릴기, 사이올기, 페닐기 또는 이소시아네이트기를 포함하며,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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; 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; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C 1 to C 40 alkyl groups, C 2 to C 40 alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,
a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고, 바람직하기로는 a는 3 내지 1000이고, d는 1 내지 500이며, 더욱 바람직하기로는 a는 5 내지 300이고, d는 2 내지 100이며,a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
e는 각각 독립적으로 1 또는 2이며, 바람직하기로 1이며,e are each independently 1 or 2, preferably 1,
n은 각각 독립적으로 1 내지 20의 정수이며, 바람직하기로는 3 내지 10이다.n is independently an integer of 1-20, Preferably it is 3-10.
또한 본 발명은 투명기판 위에 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화시키는 것을 특징으로 하는 투명기판의 표면강화방법을 제공한다.In another aspect, the present invention provides a method for strengthening the surface of a transparent substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the formulas (1) to (9) above on the transparent substrate.
또한 본 발명은 상기 표면강화 투명기판을 포함하는 것을 특징으로 하는 전자제품을 제공한다.In another aspect, the present invention provides an electronic product comprising the surface-reinforced transparent substrate.
또한 본 발명은 상기 표면강화 투명기판을 포함하는 보호판을 제공한다.In another aspect, the present invention provides a protective plate comprising the surface-reinforced transparent substrate.
본 발명에 따른 표면강화 투명기판은 특정구조의 실세스퀴옥산 복합 고분자의 경화체를 코팅층으로 포함함으로써 투명기판의 표면경도를 현저히 개선하고, 동시에 내지문성, 내스크레치성, 내오염성, 내열성, 투과도 및 헤이즈 특성이 향상되어 전자제품의 윈도우 커버기판, 보호필름 또는 보호판에 매우 유용하게 사용할 수 있다.The surface-reinforced transparent substrate according to the present invention significantly improves the surface hardness of the transparent substrate by including the cured product of the silsesquioxane composite polymer having a specific structure as a coating layer, and at the same time, the fingerprint resistance, scratch resistance, contamination resistance, heat resistance, permeability and The haze characteristics are improved, which makes it very useful for window cover substrates, protective films or protective plates of electronic products.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 표면강화 투명기판은 투명기판 위에 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자의 경화물이 적층된 것을 특징으로 한다:The surface-reinforced transparent substrate of the present invention is characterized in that the cured product of the silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 is laminated on the transparent substrate:
[화학식 1][Formula 1]
Figure PCTKR2015001971-appb-I000014
Figure PCTKR2015001971-appb-I000014
[화학식 2][Formula 2]
Figure PCTKR2015001971-appb-I000015
Figure PCTKR2015001971-appb-I000015
[화학식 3][Formula 3]
Figure PCTKR2015001971-appb-I000016
Figure PCTKR2015001971-appb-I000016
[화학식 4][Formula 4]
Figure PCTKR2015001971-appb-I000017
Figure PCTKR2015001971-appb-I000017
[화학식 5][Formula 5]
Figure PCTKR2015001971-appb-I000018
Figure PCTKR2015001971-appb-I000018
[화학식 6][Formula 6]
Figure PCTKR2015001971-appb-I000019
Figure PCTKR2015001971-appb-I000019
[화학식 7][Formula 7]
Figure PCTKR2015001971-appb-I000020
Figure PCTKR2015001971-appb-I000020
[화학식 8][Formula 8]
Figure PCTKR2015001971-appb-I000021
Figure PCTKR2015001971-appb-I000021
[화학식 9][Formula 9]
Figure PCTKR2015001971-appb-I000022
Figure PCTKR2015001971-appb-I000022
상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,
A는
Figure PCTKR2015001971-appb-I000023
이고, B는
Figure PCTKR2015001971-appb-I000024
이고, D는
Figure PCTKR2015001971-appb-I000025
이고, E는
Figure PCTKR2015001971-appb-I000026
이며,A is
Figure PCTKR2015001971-appb-I000023
And B is
Figure PCTKR2015001971-appb-I000024
And D is
Figure PCTKR2015001971-appb-I000025
And E is
Figure PCTKR2015001971-appb-I000026
Is,
Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,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, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 바람직하기로는 중수소, 할로겐, 아민기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기, 사이클로헥실 에폭시기로 치환되거나 치환되지 않은 C1~C40의 알킬기, C2~C40의 알케닐기, 아민기, 에폭시기, 사이클로헥실 에폭시기, (메타)아크릴기, 사이올기, 페닐기 또는 이소시아네이트기를 포함하며,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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; 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; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C 1 to C 40 alkyl groups, C 2 to C 40 alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,
a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고, 바람직하기로는 a는 3 내지 1000이고, d는 1 내지 500이며, 더욱 바람직하기로는 a는 5 내지 300이고, d는 2 내지 100이며,a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
e는 각각 독립적으로 1 또는 2이며, 바람직하기로 1이며,e are each independently 1 or 2, preferably 1,
n은 각각 독립적으로 1 내지 20의 정수이며, 바람직하기로는 3 내지 10이다.n is independently an integer of 1-20, Preferably it is 3-10.
본 발명의 표면강화 투명기판은 [A]a와 [D]d 반복단위를 가지며, 선택적으로 [B]b 또는 [E]e 반복단위를 가지는 특정 구조의 실세스퀴옥산 고분자를 투명기판의 표면처리제로 사용함으로써 전자제품의 윈도우 커버 기판, 보호필름에 적합하며, 내부물품 보호용의 보호판으로 적용하기에 적합한 투명기판을 제공하는 것이다.The surface-reinforced transparent substrate of the present invention comprises a silsesquioxane polymer having a specific structure having [A] a and [D] d repeating units, and optionally having [B] b or [E] e repeating unit, on the surface of the transparent substrate. The present invention provides a transparent substrate that is suitable for window cover substrates and protective films of electronic products and used as a protective plate for protecting internal articles.
본 발명의 상기 화학식 1로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 1 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 하기 화학식 10를 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR2)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 10; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid after the first step, to introduce an [D] d (OR 2 ) 2 structure into the chemical formula 10, and then adding and stirring an organic silane compound. step; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.
[화학식 10][Formula 10]
Figure PCTKR2015001971-appb-I000027
Figure PCTKR2015001971-appb-I000027
상기 식에서 R1, R2, R16, D, a 및 d는 화학식 1 내지 9에서 정의한 바와 같다.Wherein R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
본 발명의 상기 화학식 2로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 2 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR3)2 및 [D]d(OR4)2 구조를 화학식 2와 같이 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 제3단계 반응을 거쳐, 단독으로 생성되는 부산물인 cage 구조를 재결정으로 제거하여주는 정제단계를 진행하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [D] d (OR 3 ) 2 and [D] d (OR 4 ) 2 structures into the chemical formula 10 after the first step, as shown in the chemical formula 2. A second step of adding and stirring an excess of the organic silane compound after the adjustment; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And through a third step of the reaction, it can be prepared by proceeding to the purification step to remove the cage structure as a by-product generated by recrystallization.
본 발명의 상기 화학식 3으로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 3 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR5)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid after the first step, to introduce an [D] d (OR 5 ) 2 structure into the chemical formula 10, and then adding and stirring an organic silane compound. step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX 2 structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.
본 발명의 상기 화학식 4로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 4 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도를 조절하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR7)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하여 제조될 수 있다.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 adjusting the degree of condensation; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR 7 ) 2 structure into the chemical formula 10 to adjust the reaction solution to acidic acid, and then the organic silane compound A second step of adding and stirring; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.
본 발명의 상기 화학식 5로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (5) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR8)2, [D]d(OR9)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 제3단계; 및 제3단계 이후 재결정과 필터과정을 통하여, 단독 cage 생성 구조를 제거하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [B] b structure and the [D] d (OR 8 ) 2 , [D] d (OR 9 ) 2 structure into the chemical formula 10 after the first step. A second step of adding and stirring an excess of the organic silane compound after adjusting to acidity; And a third step of condensation reaction by adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic. And a fourth step of removing the single cage generation structure through recrystallization and filtering after the third step.
본 발명의 상기 화학식 6으로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (6) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR10)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR 10 ) 2 structure into the chemical formula 10 to adjust the reaction solution to acidic, and then the organic silane compound A second step of adding and stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX 2 structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.
바람직하기로 상기 화학식 1 내지 6을 제조하는 방법에서 본 발명의 제1단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제2단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제3단계의 반응액의 pH는 8 내지 11.5인 것이 바람직하고, Ee을 도입하는 제4단계의 반응액의 pH는 1.5 내지 4인 것이 바람직하다. 상기 범위 내인 경우 제조되는 실세스퀴옥산 복합 고분자의 수율이 높을 뿐만 아니라 제조된 실세스퀴옥산 복합 고분자의 기계적 물성을 향상시킬 수 있다.Preferably the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, The pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
본 발명의 상기 화학식 7로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (7) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10를 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조 및 [D]d(OR12)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 3단계를 통해 얻어진 2가지 이상의 물질을 염기성 조건에서 축합하여 연결하는 4단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, followed by adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; In order to introduce the structure [B] b and the structure [D] d (OR 12 ) 2 to the formula (10) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; And four steps of condensing and connecting two or more materials obtained through the three steps under basic conditions.
본 발명의 상기 화학식 8로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (8) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조, [D]d(OR14)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 3단계를 통해 얻어진 2가지 이상의 물질을 염기성 조건에서 축합하여 연결하는 4단계; 상기 4단계 이후 [D]d(OR13)2를 도입하기 위한 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제5단계; 및 상기 5단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제6단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; In order to introduce the [B] b structure, the [D] d (OR 14 ) 2 structure into the formula (10) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
본 발명의 상기 화학식 9로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (9) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10를 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 3단계를 통해 얻어진 2가지 이상의 화합물을 염기성 조건에서 축합하여 연결하는 4단계; 상기 제4단계 이후 [D]d(OR5)2를 도입하기 위한 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제5단계; 상기 5단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제6단계; 상기 제6단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제7단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, followed by adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; A second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid in order to introduce the structure [B] b into the chemical formula 10 obtained in step 1, and then adding and stirring an organic silane compound; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two step reaction; Condensing and connecting two or more compounds obtained through the three steps in basic conditions; A fifth step of adding an acidic catalyst to a reactor for introducing [D] d (OR 5 ) 2 to adjust the reaction solution to acidic acid after the fourth step, and then adding and stirring an organic silane compound; A sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction; After the sixth step, to introduce the [E] eX 2 structure at the end of the composite polymer to the acidic catalyst in the reactor to convert the reaction solution into an acidic atmosphere and a mixture of the organosilane compound comprising a seventh step of stirring Can be prepared.
바람직하기로 상기 화학식 7 내지 9의 고분자를 제조하는 방법에서 제1단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제2단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제3단계의 반응액의 pH는 8 내지 11.5인 것이 바람직하고, 제4단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제5단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제6단계의 반응액의 8 내지 11.5인 것이 바람직하고, Ee를 도입하는 제7단계의 반응액의 pH는 1.5 내지 4인 것이 바람직하다. 상기 범위 내인 경우 제조되는 실세스퀴옥산 복합 고분자의 수율이 높을 뿐만 아니라 제조된 실세스퀴옥산 복합 고분자의 기계적 물성을 향상시킬 수 있다.Preferably, the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4 in the method for preparing the polymer of Formula 7 to 9, The pH of the reaction solution of the third stage is preferably 8 to 11.5, the pH of the reaction solution of the fourth stage is preferably 9 to 11.5, the pH of the reaction solution of the fifth stage is preferably 2 to 4, It is preferable that it is 8-11.5 of the reaction liquid of a 6th step, and it is preferable that pH of the reaction liquid of the 7th step which introduces Ee is 1.5-4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
또한 필요한 경우 각각의 복합 고분자에 [B]b 구조 및 [D]d(OR)2 구조를 더욱 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 단계; 및 상기 단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 단계를 통하여 복합 고분자 내에 [B]b 반복단위를 더욱 포함할 수 있다.If necessary, in order to further introduce the [B] b structure and the [D] d (OR) 2 structure to each of the composite polymers, an acidic catalyst was added to the reactor to adjust the reaction solution to acidic acid, and then an organic silane compound was added. Stirring; And [B] b repeating units in the composite polymer through the step of performing a condensation reaction by adding a basic catalyst to the reactor and converting the reaction solution to basic after the above step.
또한 필요한 경우 각각의 복합 고분자의 말단에 [E]eX2 구조를 도입하기 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제단계를 포함하여 복합 고분자의 말단에 [E]e의 반복단위를 더욱 포함할 수 있다.In addition, if necessary, in order to introduce an [E] eX 2 structure at the end of each of the composite polymers, an acidic catalyst is added to the reactor to convert the reaction solution into an acidic atmosphere, and an organic silane compound is mixed and stirred. The terminal may further include a repeating unit of [E] e.
상기 실세스퀴옥산 복합 고분자의 제조방법에서는 염기성 촉매로서 바람직하기로는 2종 이상의 염기성 촉매의 혼합촉매를 사용하고, 이를 산성 촉매로 중화 및 산성화하여 재 가수분해를 유도하며, 다시 2종 이상의 염기성 촉매의 혼합촉매를 이용하여 염기성으로 축합을 진행함으로써 하나의 반응기내에서 산도와 염기도를 연속적으로 조절할 수 있다.In the production method of the silsesquioxane composite polymer, a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
이때, 상기 염기성 촉매는 Li, Na, K, Ca 및 Ba 으로 이루어진 군에서 선택된 금속계 염기성 촉매 및 아민계 염기성 촉매에서 선택되는 2종 이상의 물질을 적절히 조합하여 제조될 수 있다. 바람직하게는 상기 아민계 염기성 촉매가 테트라메틸암모늄 하이드록시드(TMAH)이고, 금속계 염기성 촉매가 포타슘 하이드록시드(KOH) 또는 중탄산나트륨 (NaHCO3)일 수 있다. 상기 혼합촉매에서 각 성분의 함량은 바람직하기로는 아민계 염기성 촉매와 금속계 염기성 촉매의 비율이 10 내지 90: 10 내지 90 중량부의 비율에서 임의로 조절할 수 있다. 상기 범위 내인 경우 가수분해시 관능기와 촉매와의 반응성을 최소화시킬 수 있으며, 이로 인해 Si-OH 또는 Si-알콕시 등의 유기 관능기의 결함이 현저히 감소하여 축합도를 자유로이 조절할 수 있는 장점이 있다. 또한, 상기 산성 촉매로는 당분야에서 통상적으로 사용하는 산성 물질이라면 제한 없이 사용될 수 있으며, 예를 들어, HCl, H2SO4, HNO3, CH3COOH 등의 일반 산성물질을 사용할 수 있고, 또한 latic acid, tartaric acid, maleic acid, citric acid 등의 유기계 산성물질도 적용할 수 있다.In this case, the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Preferably, the amine based catalyst may be tetramethylammonium hydroxide (TMAH), and the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ). The content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted. Within the above range, the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation. In addition, the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
본 발명의 실세스퀴옥산 복합 고분자의 제조방법에서 상기 유기용매는 당분야에서 통상적으로 사용하는 유기용매라면 제한 없이 사용될 수 있으며, 예를 들어, 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 사용할 수 있다.In the method for preparing 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 cellosolves, ketones such as lactate, acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan systems such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Polar solvents such as methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane and acro Various solvents, such as nitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, benzyl alcohol, can be used.
또한, 상기 유기 실란계 화합물로는 본 발명의 실세스퀴옥산 복합 고분자인 화학식 1 내지 9의 R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22를 포함하는 유기 실란이 사용될 수 있으며, 바람직하기로 실세스퀴옥산 복합 고분자의 내화학성을 증가시켜 비팽윤성을 향상시키는 효과가 있는 페닐기 또는 아미노기를 포함하는 유기 실란 화합물, 또는 복합 고분자의 경화 밀도를 증가시켜 경화층의 기계적 강도 및 경도를 향상시키는 효과가 있는 에폭시기 또는 (메타)아크릴기를 포함하는 유기 실란 화합물을 사용할 수 있다.In addition, as the organosilane compound, the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , 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 can be used Preferably, the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the mechanical strength and hardness of the cured layer by increasing the curing density of the composite polymer The organosilane compound containing the epoxy group or (meth) acryl group which has the effect of improving the can be used.
상기 유기 실란계 화합물의 구체적인 예로는 (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3-(메타아크릴옥시)프로필트리메톡시실란, 3,4-에폭시부틸트리메톡시실란, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 아미노프로필트리에톡시실란, 비닐트리에톡시실란, 비닐트리-t-부톡시실란, 비닐트리이소부톡시실란, 비닐트리이소프로폭시실란, 비닐트리페녹시실란, 페닐트리에톡시실란, 페닐트리메톡시실란, 아미노프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란, 디메틸테트라메톡시실록산, 디페닐테트라메톡시실록산 등을 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 병용하여 사용할 수도 있다. 최종 제조되는 조성물의 물성을 위하여 2종 이상을 혼합하여 사용하는 것이 보다 바람직하다.Specific examples of the organosilane compound include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 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-aminopropyltrimeth Methoxysilane, dimethyl tetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, You may use individually by 1 type or in combination of 2 or more types. It is more preferable to mix and use 2 or more types for the physical property of the composition currently manufactured.
본 발명에서 상기 화학식들의 반복단위 [D]d에 도입된[(SiO3/2R)4+2nO] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 11과 같다: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, and More preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by Formula 11 below:
[화학식 11][Formula 11]
Figure PCTKR2015001971-appb-I000028
Figure PCTKR2015001971-appb-I000028
상기 식에서, R은 상기에서 정의한 바와 같다. Wherein R is as defined above.
본 발명에서, 상기 화학식들의 반복단위 [B]b 또는 [E]e에 도입된[(SiO3/2R)4+2nR] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 12와 같다: In the present invention, n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, preferably Below 3 to 10, more preferably, the average n value is 4 to 5, for example, when n is 4 to represent a structure substituted by the formula (12):
[화학식 12][Formula 12]
Figure PCTKR2015001971-appb-I000029
Figure PCTKR2015001971-appb-I000029
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
구체적인 예로 본 발명에 따른 실세스퀴옥산 고분자는 하기 표 1 내지 18에 고분자일 수 있다. 하기 표 1 내지 9에서 ECHE는 (Epoxycyclohexyl)ethyl, GlyP는 Glycidoxypropyl, POMMA는 (methacryloyloxy)propyl을 의미하며, 두 개 이상이 기재된 경우 혼합사용을 의미한다. n은 각각 독립적으로 1 내지 8이다.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, POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use. n is 1-8 each independently.
상기 화학식 1의 실세스퀴옥산 복합고분자는 하기 표 1 또는 2에 기재된 고분자일 수 있다.The silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
표 1
No R1 R2 R6 R9 Y의R
1-1 OH,메톡시 H,메틸 ECHE ECHE ECHE
1-2 OH,메톡시 H,메틸 페닐 페닐 페닐
1-3 OH,메톡시 H,메틸 메틸 메틸 메틸
1-4 OH,메톡시 H,메틸 GlyP GlyP GlyP
1-5 OH,메톡시 H,메틸 POMMA POMMA POMMA
1-6 OH,메톡시 H,메틸 ECHE 페닐 페닐
1-7 OH,메톡시 H,메틸 ECHE 메틸 메틸
1-8 OH,메톡시 H,메틸 ECHE GlyP GlyP
1-9 OH,메톡시 H,메틸 ECHE POMMA POMMA
1-10 OH,메톡시 H,메틸 페닐 ECHE ECHE
1-11 OH,메톡시 H,메틸 페닐 메틸 메틸
1-12 OH,메톡시 H,메틸 페닐 GlyP GlyP
1-13 OH,메톡시 H,메틸 페닐 POMMA POMMA
1-14 OH,메톡시 H,메틸 메틸 ECHE ECHE
1-15 OH,메톡시 H,메틸 메틸 페닐 페닐
1-16 OH,메톡시 H,메틸 메틸 GlyP GlyP
1-17 OH,메톡시 H,메틸 메틸 POMMA POMMA
1-18 OH,메톡시 H,메틸 GlyP ECHE ECHE
1-19 OH,메톡시 H,메틸 GlyP 페닐 페닐
1-20 OH,메톡시 H,메틸 GlyP 메틸 메틸
1-21 OH,메톡시 H,메틸 GlyP POMMA POMMA
1-22 OH,메톡시 H,메틸 POMMA ECHE ECHE
1-23 OH,메톡시 H,메틸 POMMA 페닐 페닐
1-24 OH,메톡시 H,메틸 POMMA 메틸 메틸
1-25 OH,메톡시 H,메틸 POMMA GlyP GlyP
Table 1
No R1 R2 R6 R9 Y, 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
표 2
No R1 R2 R6 R7 Y의R n
2-1 OH,메톡시 H,메틸 ECHE 알킬사이올 ECHE 1~8
2-2 OH, CF3 H,에틸 페닐 페닐 페닐 1~8
2-3 OH,메톡시 H,아세틸틸 알킬사이올 메틸 메틸 1~8
2-4 CF3,메톡시 비닐,메틸 GlyP 도데실 GlyP 1~8
2-5 OH,메톡시 H,메틸 POMMA 알킬사이올 POMMA 1~8
2-6 OH, C8F13 H, F ECHE 페닐 페닐 1~8
2-7 OH, CF3 CF3,메틸 ECHE 옥틸 메틸 1~8
2-8 OH, C8F13 H,메틸 F 알킬사이올 GlyP 1~8
2-9 OH,메톡시 H, CF3 ECHE POMMA POMMA 1~8
2-10 OH,메톡시 H,메틸 페닐 알킬사이올 ECHE 1~8
2-11 OH, C8F13 아릴,메틸 알킬사이올 메틸 헥실 1~8
2-12 OH,알킬사이올 H,메타크릴 페닐 GlyP GlyP 1~8
2-13 OH,메톡시 H,메틸 알킬사이올 POMMA POMMA 1~8
2-14 OH, 아크릴 H,옥틸 메틸 ECHE 아미노프로필 1~8
2-15 비닐 ,메톡시 H,메틸 메틸 알킬사이올 페닐 1~8
2-16 알킬아민 H,메틸 메틸 GlyP GlyP 1~8
2-17 OH,에틸,메틸 알킬사이올,메틸 메틸 POMMA POMMA 1~8
2-18 아세톡시,메톡시 H,메틸 GlyP ECHE 아미노프로필 1~8
2-19 프로폭시,메톡시 H, CF3 GlyP 페닐 페닐 1~8
2-20 OH, 메톡시 H,메틸 아미노프로필 메틸 옥틸 1~8
2-21 C8F13,메톡시 C8F13,메틸 GlyP POMMA POMMA 1~8
2-22 OH,아릴 H,프로필 POMMA 프로필 ECHE 1~8
2-23 OH,메톡시 F,메틸 POMMA 페닐 페닐 1~8
2-24 CF3,메타크릴 H,메틸 POMMA 메틸 메틸 1~8
2-25 OH,메톡시 H,에틸 아미노프로필 GlyP GlyP 1~8
TABLE 2
No R1 R2 R6 R7 Y, R n
2-1 OH, methoxy H, methyl ECHE Alkyl siol ECHE 1-8
2-2 OH, CF 3 H, ethyl Phenyl Phenyl Phenyl 1-8
2-3 OH, methoxy H, acetyltyl Alkyl siol methyl methyl 1-8
2-4 CF 3 , methoxy Vinyl, methyl GlyP Dodecyl GlyP 1-8
2-5 OH, methoxy H, methyl POMMA Alkyl siol POMMA 1-8
2-6 OH, C 8 F 13 H, F ECHE Phenyl Phenyl 1-8
2-7 OH, CF 3 CF 3 , methyl ECHE Octyl methyl 1-8
2-8 OH, C 8 F 13 H, methyl F Alkyl siol GlyP 1-8
2-9 OH, methoxy H, CF 3 ECHE POMMA POMMA 1-8
2-10 OH, methoxy H, methyl Phenyl Alkyl siol ECHE 1-8
2-11 OH, C 8 F 13 Aryl, methyl Alkyl siol methyl Hexyl 1-8
2-12 OH, alkyl siol H, methacryl Phenyl GlyP GlyP 1-8
2-13 OH, methoxy H, methyl Alkyl siol POMMA POMMA 1-8
2-14 OH, acrylic H, octyl methyl ECHE Aminopropyl 1-8
2-15 Vinyl, methoxy H, methyl methyl Alkyl siol Phenyl 1-8
2-16 Alkylamine H, methyl methyl GlyP GlyP 1-8
2-17 OH, ethyl, methyl Alkyl siol, methyl methyl POMMA POMMA 1-8
2-18 Acetoxy, methoxy H, methyl GlyP ECHE Aminopropyl 1-8
2-19 Propoxy, methoxy H, CF 3 GlyP Phenyl Phenyl 1-8
2-20 OH, methoxy H, methyl Aminopropyl methyl Octyl 1-8
2-21 C 8 F 13 , methoxy C 8 F 13 , methyl GlyP POMMA POMMA 1-8
2-22 OH, aryl H, profile POMMA profile ECHE 1-8
2-23 OH, methoxy F, methyl POMMA Phenyl Phenyl 1-8
2-24 CF 3 , methacryl H, methyl POMMA methyl methyl 1-8
2-25 OH, methoxy H, ethyl Aminopropyl GlyP GlyP 1-8
구체적인 예로 상기 화학식 2의 실세스퀴옥산 복합고분자는 하기 표 3 및 4에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
표 3
No R3 R4 R6 R7 Y의R
3-1 H,메틸 H,메틸 ECHE ECHE ECHE
3-2 H,메틸 H,메틸 페닐 페닐 페닐
3-3 H,메틸 H,메틸 메틸 메틸 메틸
3-4 H,메틸 H,메틸 GlyP GlyP GlyP
3-5 H,메틸 H,메틸 POMMA POMMA POMMA
3-6 H,메틸 H,메틸 ECHE 페닐 페닐
3-7 H,메틸 H,메틸 ECHE 메틸 메틸
3-8 H,메틸 H,메틸 ECHE GlyP GlyP
3-9 H,메틸 H,메틸 ECHE POMMA POMMA
3-10 H,메틸 H,메틸 페닐 ECHE ECHE
3-11 H,메틸 H,메틸 페닐 메틸 메틸
3-12 H,메틸 H,메틸 페닐 GlyP GlyP
3-13 H,메틸 H,메틸 페닐 POMMA POMMA
3-14 H,메틸 H,메틸 메틸 ECHE ECHE
3-15 H,메틸 H,메틸 메틸 페닐 페닐
3-16 H,메틸 H,메틸 메틸 GlyP GlyP
3-17 H,메틸 H,메틸 메틸 POMMA POMMA
3-18 H,메틸 H,메틸 GlyP ECHE ECHE
3-19 H,메틸 H,메틸 GlyP 페닐 페닐
3-20 H,메틸 H,메틸 GlyP 메틸 메틸
3-21 H,메틸 H,메틸 GlyP POMMA POMMA
3-22 H,메틸 H,메틸 POMMA ECHE ECHE
3-23 H,메틸 H,메틸 POMMA 페닐 페닐
3-24 H,메틸 H,메틸 POMMA 메틸 메틸
3-25 H,메틸 H,메틸 POMMA GlyP GlyP
TABLE 3
No R3 R4 R6 R7 Y, 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
표 4
No R3 R4 R6 R7 Y의R
4-1 OH,메톡시 H,메틸 ECHE 알킬사이올 ECHE
4-2 OH, CF3 H,에틸 페닐 페닐 페닐
4-3 OH,메톡시 H,아세틸틸 알킬사이올 메틸 메틸
4-4 CF3,메톡시 비닐,메틸 POMMA 도데실 GlyP
4-5 OH, 아크릴 H,메틸 POMMA 알킬사이올 옥틸
4-6 비닐 ,메톡시 H, F ECHE 페닐 POMMA
4-7 알킬아민 CF3,메틸 ECHE 옥틸 메틸
4-8 OH,에틸,메틸 H,메틸 F 아미노프로필 GlyP
4-9 아세톡시,메톡시 H, CF3 아미노프로필 POMMA 헥실
4-10 프로폭시,메톡시 H,메틸 페닐 알킬사이올 ECHE
4-11 OH, C8F13 아릴,메틸 알킬사이올 메틸 헥실
4-12 OH,메톡시 H,메타크릴 페닐 GlyP GlyP
4-13 CF3,메톡시 H,메틸 옥틸 POMMA POMMA
4-14 OH, 아크릴 H,옥틸 메틸 ECHE 아미노프로필
4-15 비닐 ,메톡시 H,메틸 옥틸 알킬사이올 페닐
4-16 알킬아민 H,메틸 옥틸 GlyP GlyP
4-17 OH,메톡시 알킬사이올,메틸 메틸 POMMA POMMA
4-18 아세톡시,메톡시 H,메틸 GlyP ECHE 아미노프로필
4-19 프로폭시,메톡시 H, CF3 GlyP 아미노프로필 페닐
4-20 OH, 메톡시 H,메틸 아미노프로필 메틸 옥틸
4-21 프로폭시,메톡시 C8F13,메틸 GlyP POMMA POMMA
4-22 OH, 메톡시 H,프로필 POMMA 프로필 ECHE
4-23 C8F13,메톡시 F,메틸 POMMA 페닐 페닐
4-24 OH,아릴 H,메틸 GlyP 메틸 GlyP
4-25 OH,메톡시 H,에틸 아미노프로필 GlyP GlyP
Table 4
No R3 R4 R6 R7 Y, R
4-1 OH, methoxy H, methyl ECHE Alkyl siol ECHE
4-2 OH, CF 3 H, ethyl Phenyl Phenyl Phenyl
4-3 OH, methoxy H, acetyltyl Alkyl siol methyl methyl
4-4 CF 3 , methoxy Vinyl, methyl POMMA Dodecyl GlyP
4-5 OH, acrylic H, methyl POMMA Alkyl siol 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 siol ECHE
4-11 OH, C 8 F 13 Aryl, methyl Alkyl siol methyl Hexyl
4-12 OH, methoxy H, methacryl 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 siol Phenyl
4-16 Alkylamine H, methyl Octyl GlyP GlyP
4-17 OH, methoxy Alkyl siol, 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
표 5
No R5 R6 R7 R8 R10 Y의 R X의 R
5-1 H,메틸 ECHE ECHE ECHE H,메틸 ECHE ECHE
5-2 H,메틸 페닐 페닐 페닐 H,메틸 페닐 페닐
5-3 H,메틸 메틸 메틸 메틸 H,메틸 메틸 메틸
5-4 H,메틸 GlyP EGCDX GlyP H,메틸 EGCDX GlyP
5-5 H,메틸 POMMA POMMA POMMA H,메틸 POMMA POMMA
5-6 H,메틸 ECHE ECHE 페닐 H,메틸 ECHE 페닐
5-7 H,메틸 ECHE ECHE 메틸 H,메틸 ECHE 메틸
5-8 H,메틸 ECHE ECHE GlyP H,메틸 ECHE GlyP
5-9 H,메틸 ECHE ECHE POMMA H,메틸 ECHE POMMA
5-10 H,메틸 ECHE 페닐 ECHE H,메틸 페닐 ECHE
5-11 H,메틸 ECHE 메틸 ECHE H,메틸 메틸 ECHE
5-12 H,메틸 ECHE GlyP ECHE H,메틸 GlyP ECHE
5-13 H,메틸 ECHE POMMA ECHE H,메틸 POMMA ECHE
5-14 H,메틸 페닐 페닐 ECHE H,메틸 페닐 ECHE
5-15 H,메틸 페닐 페닐 메틸 H,메틸 페닐 메틸
5-16 H,메틸 페닐 페닐 EGDCX H,메틸 페닐 EGDCX
5-17 H,메틸 페닐 페닐 POMMA H,메틸 페닐 POMMA
5-18 H,메틸 페닐 ECHE 페닐 H,메틸 ECHE 페닐
5-19 H,메틸 페닐 메틸 페닐 H,메틸 메틸 페닐
5-20 H,메틸 페닐 GlyP 페닐 H,메틸 GlyP 페닐
5-21 H,메틸 페닐 POMMA 페닐 H,메틸 POMMA 페닐
5-22 H,메틸 메틸 메틸 ECHE H,메틸 메틸 ECHE
5-23 H,메틸 메틸 메틸 페닐 H,메틸 메틸 페닐
5-25 H,메틸 메틸 메틸 GlyP H,메틸 메틸 GlyP
5-25 H,메틸 메틸 메틸 POMMA H,메틸 메틸 POMMA
5-26 H,메틸 메틸 ECHE 메틸 H,메틸 ECHE 메틸
5-27 H,메틸 메틸 페닐 메틸 H,메틸 페닐 메틸
5-28 H,메틸 메틸 GlyP 메틸 H,메틸 GlyP 메틸
5-29 H,메틸 메틸 POMMA 메틸 H,메틸 POMMA 메틸
5-30 H,메틸 GlyP GlyP ECHE H,메틸 GlyP ECHE
5-31 H,메틸 GlyP GlyP 페닐 H,메틸 GlyP 페닐
5-32 H,메틸 GlyP GlyP 메틸 H,메틸 GlyP 메틸
5-33 H,메틸 GlyP GlyP POMMA H,메틸 GlyP POMMA
5-34 H,메틸 GlyP ECHE GlyP H,메틸 ECHE GlyP
5-35 H,메틸 GlyP 페닐 GlyP H,메틸 페닐 GlyP
5-36 H,메틸 GlyP 메틸 GlyP H,메틸 메틸 GlyP
5-37 H,메틸 GlyP POMMA GlyP H,메틸 POMMA GlyP
5-35 H,메틸 POMMA POMMA ECHE H,메틸 POMMA ECHE
5-39 H,메틸 POMMA POMMA 페닐 H,메틸 POMMA 페닐
5-40 H,메틸 POMMA POMMA 메틸 H,메틸 POMMA 메틸
5-41 H,메틸 POMMA POMMA GlyP H,메틸 POMMA GlyP
5-42 H,메틸 POMMA ECHE POMMA H,메틸 ECHE POMMA
5-43 H,메틸 POMMA 페닐 POMMA H,메틸 페닐 POMMA
5-44 H,메틸 POMMA 메틸 POMMA H,메틸 메틸 POMMA
5-45 H,메틸 POMMA GlyP POMMA H,메틸 GlyP POMMA
Table 5
No R5 R6 R7 R8 R10 Y R X, R
5-1 H, methyl ECHE ECHE ECHE H, methyl ECHE ECHE
5-2 H, methyl Phenyl Phenyl Phenyl H, methyl Phenyl Phenyl
5-3 H, methyl methyl methyl methyl H, methyl methyl methyl
5-4 H, methyl GlyP EGCDX GlyP H, methyl EGCDX GlyP
5-5 H, methyl POMMA POMMA POMMA H, methyl POMMA POMMA
5-6 H, methyl ECHE ECHE Phenyl H, methyl ECHE Phenyl
5-7 H, methyl ECHE ECHE methyl H, methyl ECHE methyl
5-8 H, methyl ECHE ECHE GlyP H, methyl ECHE GlyP
5-9 H, methyl ECHE ECHE POMMA H, methyl ECHE POMMA
5-10 H, methyl ECHE Phenyl ECHE H, methyl Phenyl ECHE
5-11 H, methyl ECHE methyl ECHE H, methyl methyl ECHE
5-12 H, methyl ECHE GlyP ECHE H, methyl GlyP ECHE
5-13 H, methyl ECHE POMMA ECHE H, methyl POMMA ECHE
5-14 H, methyl Phenyl Phenyl ECHE H, methyl Phenyl ECHE
5-15 H, methyl Phenyl Phenyl methyl H, methyl Phenyl methyl
5-16 H, methyl Phenyl Phenyl EGDCX H, methyl Phenyl EGDCX
5-17 H, methyl Phenyl Phenyl POMMA H, methyl Phenyl POMMA
5-18 H, methyl Phenyl ECHE Phenyl H, methyl ECHE Phenyl
5-19 H, methyl Phenyl methyl Phenyl H, methyl methyl Phenyl
5-20 H, methyl Phenyl GlyP Phenyl H, methyl GlyP Phenyl
5-21 H, methyl Phenyl POMMA Phenyl H, methyl POMMA Phenyl
5-22 H, methyl methyl methyl ECHE H, methyl methyl ECHE
5-23 H, methyl methyl methyl Phenyl H, methyl methyl Phenyl
5-25 H, methyl methyl methyl GlyP H, methyl methyl GlyP
5-25 H, methyl methyl methyl POMMA H, methyl methyl POMMA
5-26 H, methyl methyl ECHE methyl H, methyl ECHE methyl
5-27 H, methyl methyl Phenyl methyl H, methyl Phenyl methyl
5-28 H, methyl methyl GlyP methyl H, methyl GlyP methyl
5-29 H, methyl methyl POMMA methyl H, methyl POMMA methyl
5-30 H, methyl GlyP GlyP ECHE H, methyl GlyP ECHE
5-31 H, methyl GlyP GlyP Phenyl H, methyl GlyP Phenyl
5-32 H, methyl GlyP GlyP methyl H, methyl GlyP methyl
5-33 H, methyl GlyP GlyP POMMA H, methyl GlyP POMMA
5-34 H, methyl GlyP ECHE GlyP H, methyl ECHE GlyP
5-35 H, methyl GlyP Phenyl GlyP H, methyl Phenyl GlyP
5-36 H, methyl GlyP methyl GlyP H, methyl methyl GlyP
5-37 H, methyl GlyP POMMA GlyP H, methyl POMMA GlyP
5-35 H, methyl POMMA POMMA ECHE H, methyl POMMA ECHE
5-39 H, methyl POMMA POMMA Phenyl H, methyl POMMA Phenyl
5-40 H, methyl POMMA POMMA methyl H, methyl POMMA methyl
5-41 H, methyl POMMA POMMA GlyP H, methyl POMMA GlyP
5-42 H, methyl POMMA ECHE POMMA H, methyl ECHE POMMA
5-43 H, methyl POMMA Phenyl POMMA H, methyl Phenyl POMMA
5-44 H, methyl POMMA methyl POMMA H, methyl methyl POMMA
5-45 H, methyl POMMA GlyP POMMA H, methyl GlyP POMMA
표 6
No R5 R6 R7 R8 R10 Y의 R X의 R
6-1 H,메틸 ECHE ECHE ECHE 알킬사이올,메틸 ECHE ECHE
6-2 H,에틸 페닐 페닐 페닐 H,메틸 페닐 페닐
6-3 H,아세틸틸 알킬사이올 메틸 메틸 H, CF3 메틸 메틸
6-4 비닐,메틸 POMMA 도데실 GlyP H,메틸 EGCDX GlyP
6-5 H,메틸 POMMA 알킬사이올 POMMA C8F13,메틸 POMMA POMMA
6-6 H, F ECHE 페닐 페닐 H,프로필 ECHE 페닐
6-7 CF3,메틸 ECHE 옥틸 메틸 F,메틸 ECHE 메틸
6-8 H,메틸 F 아미노프로필 GlyP H,메틸 ECHE GlyP
6-9 H, CF3 아미노프로필 POMMA POMMA H,에틸 ECHE POMMA
6-10 H,메틸 페닐 알킬사이올 ECHE H,아세틸틸 페닐 ECHE
6-11 아릴,메틸 알킬사이올 메틸 ECHE 비닐,메틸 메틸 ECHE
6-12 H,메타크릴 페닐 GlyP ECHE H,메틸 GlyP ECHE
6-13 H,메틸 옥틸 POMMA ECHE H, F POMMA ECHE
6-14 H,옥틸 메틸 ECHE ECHE CF3,메틸 페닐 ECHE
6-15 H,메틸 옥틸 알킬사이올 메틸 H,메틸 페닐 메틸
6-16 H,메틸 옥틸 GlyP EGDCX H,옥틸 페닐 EGDCX
6-17 알킬사이올,메틸 메틸 POMMA POMMA H,아세틸틸 페닐 POMMA
6-18 H,메틸 GlyP GlyP 페닐 비닐,메틸 ECHE 페닐
6-19 H, CF3 POMMA POMMA 페닐 H,메틸 메틸 페닐
6-20 H,메틸 ECHE 아미노프로필 페닐 H, F GlyP 페닐
6-21 C8F13,메틸 알킬사이올 페닐 페닐 CF3,메틸 POMMA 페닐
6-22 H,프로필 GlyP GlyP ECHE H,메틸 메틸 ECHE
6-23 F,메틸 POMMA POMMA 페닐 H, CF3 메틸 페닐
6-24 H,메틸 ECHE 아미노프로필 GlyP H,메틸 메틸 GlyP
6-25 H,에틸 아미노프로필 페닐 POMMA 아릴,메틸 메틸 POMMA
6-26 H,아세틸틸 메틸 옥틸 메틸 H,메타크릴 ECHE 메틸
6-27 비닐,메틸 POMMA POMMA 메틸 H,메틸 페닐 메틸
6-28 H,메틸 메틸 메틸 메틸 H,옥틸 GlyP 메틸
6-29 H, F 도데실 GlyP 메틸 H,메틸 POMMA 메틸
6-30 CF3,메틸 알킬사이올 옥틸 ECHE 비닐,메틸 GlyP ECHE
6-31 H,메틸 페닐 POMMA 페닐 H,메틸 GlyP 페닐
6-32 H,옥틸 옥틸 메틸 메틸 H, F GlyP 메틸
6-33 H,메틸 아미노프로필 GlyP POMMA CF3,메틸 GlyP POMMA
6-34 H,메틸 POMMA 헥실 GlyP H,메틸 ECHE GlyP
6-35 H,아세틸틸 알킬사이올 ECHE GlyP H,메틸 페닐 GlyP
6-36 비닐,메틸 메틸 헥실 GlyP H,메틸 메틸 GlyP
6-37 H,메틸 GlyP GlyP GlyP H,메틸 POMMA GlyP
6-38 H, F POMMA POMMA ECHE H,메틸 POMMA ECHE
6-39 CF3,메틸 ECHE 아미노프로필 페닐 H,메틸 POMMA 페닐
6-40 H,메틸 알킬사이올 페닐 메틸 H,메틸 POMMA 메틸
6-41 비닐,메틸 GlyP GlyP GlyP H,메틸 POMMA GlyP
6-42 H,메틸 POMMA POMMA POMMA H,메틸 ECHE POMMA
6-43 H, F ECHE 아미노프로필 POMMA H,메틸 페닐 POMMA
6-44 CF3,메틸 아미노프로필 페닐 POMMA H,메틸 메틸 POMMA
6-45 H,메틸 POMMA GlyP POMMA H,메틸 GlyP POMMA
Table 6
No R5 R6 R7 R8 R10 Y R X, R
6-1 H, methyl ECHE ECHE ECHE Alkyl siol, methyl ECHE ECHE
6-2 H, ethyl Phenyl Phenyl Phenyl H, methyl Phenyl Phenyl
6-3 H, acetyltyl Alkyl siol methyl methyl H, CF 3 methyl methyl
6-4 Vinyl, methyl POMMA Dodecyl GlyP H, methyl EGCDX GlyP
6-5 H, methyl POMMA Alkyl siol POMMA C 8 F 13 , methyl POMMA POMMA
6-6 H, F ECHE Phenyl Phenyl H, profile ECHE Phenyl
6-7 CF 3 , methyl ECHE Octyl methyl F, methyl ECHE methyl
6-8 H, methyl F Aminopropyl GlyP H, methyl ECHE GlyP
6-9 H, CF 3 Aminopropyl POMMA POMMA H, ethyl ECHE POMMA
6-10 H, methyl Phenyl Alkyl siol ECHE H, acetyltyl Phenyl ECHE
6-11 Aryl, methyl Alkyl siol methyl ECHE Vinyl, methyl methyl ECHE
6-12 H, methacryl Phenyl GlyP ECHE H, methyl GlyP ECHE
6-13 H, methyl Octyl POMMA ECHE H, F POMMA ECHE
6-14 H, octyl methyl ECHE ECHE CF 3 , methyl Phenyl ECHE
6-15 H, methyl Octyl Alkyl siol methyl H, methyl Phenyl methyl
6-16 H, methyl Octyl GlyP EGDCX H, octyl Phenyl EGDCX
6-17 Alkyl siol, methyl methyl POMMA POMMA H, acetyltyl Phenyl POMMA
6-18 H, methyl GlyP GlyP Phenyl Vinyl, methyl ECHE Phenyl
6-19 H, CF 3 POMMA POMMA Phenyl H, methyl methyl Phenyl
6-20 H, methyl ECHE Aminopropyl Phenyl H, F GlyP Phenyl
6-21 C 8 F 13 , methyl Alkyl siol Phenyl Phenyl CF 3 , methyl POMMA Phenyl
6-22 H, profile GlyP GlyP ECHE H, methyl methyl ECHE
6-23 F, methyl POMMA POMMA Phenyl H, CF 3 methyl Phenyl
6-24 H, methyl ECHE Aminopropyl GlyP H, methyl methyl GlyP
6-25 H, ethyl Aminopropyl Phenyl POMMA Aryl, methyl methyl POMMA
6-26 H, acetyltyl methyl Octyl methyl H, methacryl ECHE methyl
6-27 Vinyl, methyl POMMA POMMA methyl H, methyl Phenyl methyl
6-28 H, methyl methyl methyl methyl H, octyl GlyP methyl
6-29 H, F Dodecyl GlyP methyl H, methyl POMMA methyl
6-30 CF 3 , methyl Alkyl siol Octyl ECHE Vinyl, methyl GlyP ECHE
6-31 H, methyl Phenyl POMMA Phenyl H, methyl GlyP Phenyl
6-32 H, octyl Octyl methyl methyl H, F GlyP methyl
6-33 H, methyl Aminopropyl GlyP POMMA CF 3 , methyl GlyP POMMA
6-34 H, methyl POMMA Hexyl GlyP H, methyl ECHE GlyP
6-35 H, acetyltyl Alkyl siol ECHE GlyP H, methyl Phenyl GlyP
6-36 Vinyl, methyl methyl Hexyl GlyP H, methyl methyl GlyP
6-37 H, methyl GlyP GlyP GlyP H, methyl POMMA GlyP
6-38 H, F POMMA POMMA ECHE H, methyl POMMA ECHE
6-39 CF 3 , methyl ECHE Aminopropyl Phenyl H, methyl POMMA Phenyl
6-40 H, methyl Alkyl siol Phenyl methyl H, methyl POMMA methyl
6-41 Vinyl, methyl GlyP GlyP GlyP H, methyl POMMA GlyP
6-42 H, methyl POMMA POMMA POMMA H, methyl ECHE POMMA
6-43 H, F ECHE Aminopropyl POMMA H, methyl Phenyl POMMA
6-44 CF 3 , methyl Aminopropyl Phenyl POMMA H, methyl methyl POMMA
6-45 H, methyl POMMA GlyP POMMA H, methyl GlyP POMMA
구체적인 예로 상기 화학식 4의 실세스퀴옥산 복합고분자는 하기 표 7 및 8에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
표 7
No R1 R2 R6 R7 R8 R9 X의 R Y의 R
7-1 OH,메톡시 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
7-2 OH,메톡시 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
7-3 OH,메톡시 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
7-4 OH,메톡시 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
7-5 OH,메톡시 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
7-6 OH,메톡시 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
7-7 OH,메톡시 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
7-8 OH,메톡시 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
7-9 OH,메톡시 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
7-10 OH,메톡시 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
7-11 OH,메톡시 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
7-12 OH,메톡시 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
7-13 OH,메톡시 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
7-14 OH,메톡시 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
7-15 OH,메톡시 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
7-16 OH,메톡시 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
7-17 OH,메톡시 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
7-18 OH,메톡시 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
7-19 OH,메톡시 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
7-20 OH,메톡시 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
7-21 OH,메톡시 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
7-22 OH,메톡시 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
7-23 OH,메톡시 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
7-24 OH,메톡시 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
7-25 OH,메톡시 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
TABLE 7
No R1 R2 R6 R7 R8 R9 X, R Y 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
표 8
No R1 R2 R6 R7 R8 R9 X의 R Y의 R
8-1 OH,메톡시 H,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
8-2 OH, CF3 H,에틸 ECHE 페닐 H,옥틸 페닐 페닐 페닐
8-3 OH,메톡시 H,아세틸틸 ECHE 메틸 H,메틸 메틸 메틸 메틸
8-4 CF3,메톡시 비닐,메틸 페닐 GlyP H,메틸 GlyP GlyP GlyP
8-5 OH,메톡시 H,메틸 페닐 POMMA 알킬사이올,메틸 POMMA POMMA POMMA
8-6 OH, C8F13 H, F 페닐 ECHE H,메틸 페닐 ECHE 페닐
8-7 OH, CF3 CF3,메틸 ECHE ECHE H, CF3 메틸 ECHE 메틸
8-8 OH, C8F13 H,메틸 헥실 ECHE H,에틸 GlyP ECHE GlyP
8-9 OH,메톡시 H, CF3 GlyP ECHE H,아세틸틸 POMMA ECHE POMMA
8-10 OH,메톡시 H,메틸 POMMA 페닐 비닐,메틸 ECHE 페닐 ECHE
8-11 OH, C8F13 아릴,메틸 아미노프로필 페닐 H,메틸 헥실 페닐 헥실
8-12 OH,알킬사이올 H,메타크릴 페닐 페닐 H, F GlyP 페닐 GlyP
8-13 OH,메톡시 H,메틸 GlyP ECHE 비닐,메틸 POMMA 페닐 POMMA
8-14 OH, 아크릴 H,옥틸 POMMA 헥실 H,메틸 아미노프로필 메틸 아미노프로필
8-15 비닐 ,메톡시 H,메틸 아미노프로필 GlyP H, F 페닐 메틸 페닐
8-16 알킬아민 H,메틸 페닐 POMMA CF3,메틸 GlyP 메틸 GlyP
8-17 OH,에틸,메틸 알킬사이올,메틸 옥틸 아미노프로필 H,메틸 POMMA 메틸 POMMA
8-18 아세톡시,메톡시 H,메틸 POMMA 페닐 H, CF3 아미노프로필 GlyP 아미노프로필
8-19 프로폭시,메톡시 H, CF3 ECHE GlyP H,메틸 페닐 GlyP 페닐
8-20 OH, 메톡시 H,메틸 페닐 POMMA H,메틸 옥틸 GlyP 옥틸
8-21 C8F13,메톡시 C8F13,메틸 메틸 아미노프로필 H,메틸 POMMA GlyP POMMA
8-22 OH,아릴 H,프로필 GlyP 페닐 알킬사이올,메틸 ECHE POMMA ECHE
8-23 OH,메톡시 F,메틸 POMMA 옥틸 H,메틸 페닐 POMMA 페닐
8-24 CF3,메타크릴 H,메틸 POMMA POMMA H, CF3 메틸 POMMA 메틸
8-25 OH,메톡시 H,에틸 POMMA ECHE H,메틸 GlyP POMMA GlyP
Table 8
No R1 R2 R6 R7 R8 R9 X, R Y R
8-1 OH, methoxy H, methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol 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 siol, 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 siol H, methacryl 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 siol, 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 siol, methyl ECHE POMMA ECHE
8-23 OH, methoxy F, methyl POMMA Octyl H, methyl Phenyl POMMA Phenyl
8-24 CF 3 , methacryl H, methyl POMMA POMMA H, CF 3 methyl POMMA methyl
8-25 OH, methoxy H, ethyl POMMA ECHE H, methyl GlyP POMMA GlyP
구체적인 예로 상기 화학식 5의 실세스퀴옥산 복합고분자는 하기 표 9 및 10에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Formula 5 may be a polymer described in Tables 9 and 10.
표 9
No R3 R4 R6 R7 R8 R9 X의 R Y의 R
9-1 H,메틸 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
9-2 H,메틸 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
9-3 H,메틸 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
9-4 H,메틸 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
9-5 H,메틸 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
9-6 H,메틸 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
9-7 H,메틸 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
9-8 H,메틸 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
9-9 H,메틸 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
9-10 H,메틸 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
9-11 H,메틸 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
9-12 H,메틸 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
9-13 H,메틸 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
9-14 H,메틸 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
9-15 H,메틸 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
9-16 H,메틸 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
9-17 H,메틸 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
9-18 H,메틸 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
9-19 H,메틸 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
9-20 H,메틸 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
9-21 H,메틸 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
9-22 H,메틸 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
9-23 H,메틸 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
9-24 H,메틸 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
9-25 H,메틸 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 9
No R3 R4 R6 R7 R8 R9 X, R Y 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
표 10
No R3 R4 R6 R7 R8 R9 B의 R D의 R
10-1 H,메틸 CF3,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
10-2 H,에틸 H,메틸 ECHE 페닐 알킬사이올,메틸 헥실 페닐 헥실
10-3 H,아세틸틸 H, CF3 ECHE 메틸 H,메틸 GlyP 메틸 GlyP
10-4 비닐,메틸 H,메틸 페닐 GlyP H, CF3 POMMA GlyP POMMA
10-5 H,메틸 H,메틸 페닐 POMMA H,에틸 아미노프로필 POMMA 아미노프로필
10-6 H, F H,옥틸 페닐 ECHE H, F 페닐 ECHE 페닐
10-7 CF3,메틸 H,메틸 ECHE ECHE 비닐,메틸 GlyP ECHE GlyP
10-8 H,메틸 H,메틸 헥실 ECHE H,메틸 POMMA ECHE POMMA
10-9 H, CF3 알킬사이올,메틸 GlyP ECHE H, F 아미노프로필 ECHE 아미노프로필
10-10 H,메틸 H,메틸 POMMA 페닐 CF3,메틸 페닐 페닐 페닐
10-11 아릴,메틸 H,메틸 아미노프로필 페닐 H,메틸 옥틸 페닐 옥틸
10-12 H,메타크릴 H,메틸 페닐 페닐 H, CF3 POMMA 페닐 POMMA
10-13 H,메틸 알킬사이올,메틸 GlyP ECHE H,메틸 ECHE ECHE ECHE
10-14 H,옥틸 H,메틸 POMMA 헥실 H,메틸 페닐 헥실 페닐
10-15 H,메틸 H, F 아미노프로필 GlyP H,옥틸 메틸 GlyP 메틸
10-16 H,메틸 CF3,메틸 페닐 POMMA H,메틸 GlyP POMMA GlyP
10-17 알킬사이올,메틸 H,메틸 옥틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
10-18 H,메틸 H, CF3 POMMA 페닐 알킬사이올,메틸 아미노프로필 페닐 아미노프로필
10-19 H, CF3 H,메틸 ECHE GlyP H,메틸 페닐 GlyP 페닐
10-20 H,메틸 H,메틸 페닐 POMMA H,메틸 옥틸 POMMA 옥틸
10-21 C8F13,메틸 H,메틸 메틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
10-22 H,프로필 알킬사이올,메틸 GlyP 페닐 알킬사이올,메틸 ECHE 페닐 ECHE
10-23 F,메틸 H,메틸 POMMA 옥틸 H,메틸 페닐 옥틸 페닐
10-24 H,메틸 H, CF3 POMMA POMMA H, CF3 메틸 POMMA 메틸
10-25 H,에틸 H,메틸 POMMA ECHE H,메틸 GlyP ECHE GlyP
Table 10
No R3 R4 R6 R7 R8 R9 B, R D, R
10-1 H, methyl CF 3 , methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol ECHE
10-2 H, ethyl H, methyl ECHE Phenyl Alkyl siol, 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 siol, 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, methacryl H, methyl Phenyl Phenyl H, CF 3 POMMA Phenyl POMMA
10-13 H, methyl Alkyl siol, 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 siol, methyl H, methyl Octyl Aminopropyl H, methyl POMMA Aminopropyl POMMA
10-18 H, methyl H, CF 3 POMMA Phenyl Alkyl siol, 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 siol, methyl GlyP Phenyl Alkyl siol, 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
구체적인 예로 상기 화학식 6의 실세스퀴옥산 복합고분자는 하기 표 11 및 12에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 6 may be a polymer described in Tables 11 and 12 below.
표 11
No R6 R7 R8 R9 R10 X의 R Y의 R E의 R
11-1 ECHE ECHE H,메틸 ECHE ECHE ECHE ECHE ECHE
11-2 페닐 페닐 H,메틸 페닐 페닐 페닐 페닐 페닐
11-3 메틸 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
11-4 GlyP EGCDX H,메틸 EGCDX GlyP EGCDX EGCDX GlyP
11-5 POMMA POMMA H,메틸 POMMA POMMA POMMA POMMA POMMA
11-6 ECHE ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
11-7 ECHE ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
11-8 ECHE ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
11-9 ECHE ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
11-10 ECHE 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
11-11 ECHE 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
11-12 ECHE GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
11-13 ECHE POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
11-14 페닐 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
11-15 페닐 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
11-16 페닐 페닐 H,메틸 페닐 EGDCX 페닐 페닐 EGDCX
11-17 페닐 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
11-18 페닐 ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
11-19 페닐 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
11-20 페닐 GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
11-21 페닐 POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
11-22 메틸 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
11-23 메틸 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
11-24 메틸 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
11-25 메틸 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
11-26 메틸 ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
11-27 메틸 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
11-28 메틸 GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
11-29 메틸 POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
11-30 GlyP GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
11-31 GlyP GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
11-32 GlyP GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
11-33 GlyP GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
11-34 GlyP ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
11-35 GlyP 페닐 H,메틸 페닐 GlyP 페닐 페닐 GlyP
11-36 GlyP 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
11-37 GlyP POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
11-38 POMMA POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
11-39 POMMA POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
11-40 POMMA POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
11-41 POMMA POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
11-42 POMMA ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
11-43 POMMA 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
11-44 POMMA 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
11-45 POMMA GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
Table 11
No R6 R7 R8 R9 R10 X, R Y R E, 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
표 12
No R6 R7 R8 R9 R10 X의 R Y의 R E의 R
12-1 ECHE POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
12-2 페닐 POMMA H,에틸 페닐 POMMA POMMA 페닐 POMMA
12-3 POMMA ECHE H,아세틸틸 메틸 ECHE ECHE 메틸 ECHE
12-4 메틸 ECHE 비닐,메틸 EGCDX ECHE ECHE EGCDX ECHE
12-5 POMMA F H,메틸 POMMA F F POMMA F
12-6 프로필 아미노프로필 CF3,메틸 ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
12-7 페닐 페닐 H,메틸 ECHE 페닐 페닐 ECHE 페닐
12-8 메틸 알킬사이올 H,아세틸틸 ECHE 알킬사이올 알킬사이올 ECHE 알킬사이올
12-9 GlyP 페닐 비닐,메틸 ECHE 페닐 페닐 ECHE 페닐
12-10 ECHE 옥틸 H,메틸 페닐 옥틸 옥틸 페닐 옥틸
12-11 알킬사이올 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
12-12 페닐 옥틸 비닐,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
12-13 옥틸 옥틸 H,메틸 POMMA 옥틸 옥틸 POMMA 옥틸
12-14 메틸 메틸 H, F 페닐 메틸 메틸 페닐 메틸
12-15 옥틸 GlyP CF3,메틸 페닐 ECHE GlyP 페닐 ECHE
12-16 옥틸 GlyP 비닐,메틸 페닐 페닐 GlyP 페닐 페닐
12-17 메틸 아미노프로필 H,메틸 페닐 POMMA 아미노프로필 페닐 POMMA
12-18 GlyP GlyP H, F ECHE 메틸 GlyP ECHE 메틸
12-19 GlyP POMMA CF3,메틸 메틸 POMMA POMMA 메틸 POMMA
12-20 아미노프로필 메틸 H,메틸 GlyP 프로필 메틸 GlyP 프로필
12-21 GlyP POMMA 알킬사이올,메틸 POMMA 페닐 POMMA POMMA 페닐
12-22 POMMA 프로필 H,아세틸틸 메틸 메틸 프로필 메틸 메틸
12-23 POMMA 메틸 비닐,메틸 메틸 GlyP 메틸 메틸 GlyP
12-24 GlyP GlyP 비닐,메틸 메틸 ECHE GlyP 메틸 ECHE
12-25 아미노프로필 GlyP H,메틸 메틸 GlyP GlyP 메틸 GlyP
12-26 메틸 아미노프로필 H, F ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
12-27 메틸 GlyP CF3,메틸 페닐 GlyP GlyP 페닐 GlyP
12-28 메틸 옥틸 H,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
12-29 메틸 메틸 H,아세틸틸 POMMA 메틸 메틸 POMMA 메틸
12-30 아미노프로필 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
12-31 GlyP GlyP H,메틸 GlyP GlyP GlyP GlyP GlyP
12-32 POMMA 아미노프로필 H,메틸 GlyP 아미노프로필 아미노프로필 GlyP 아미노프로필
12-33 메틸 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
12-34 POMMA POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
12-35 프로필 POMMA H, F 페닐 POMMA POMMA 페닐 POMMA
12-36 메틸 GlyP CF3,메틸 메틸 GlyP GlyP 메틸 GlyP
12-37 GlyP 아미노프로필 비닐,메틸 POMMA 아미노프로필 아미노프로필 POMMA 아미노프로필
12-38 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
12-39 아미노프로필 메틸 H, F POMMA 메틸 메틸 POMMA 메틸
12-40 아미노프로필 메틸 CF3,메틸 POMMA 메틸 메틸 POMMA 메틸
12-41 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
12-42 POMMA GlyP 알킬사이올,메틸 ECHE GlyP GlyP ECHE GlyP
12-43 POMMA 아미노프로필 H,아세틸틸 페닐 아미노프로필 아미노프로필 페닐 아미노프로필
12-44 POMMA GlyP 비닐,메틸 메틸 GlyP GlyP 메틸 GlyP
12-45 POMMA POMMA H,메틸 GlyP POMMA POMMA GlyP POMMA
Table 12
No R6 R7 R8 R9 R10 X, R Y R E, 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 siol H, acetyltyl ECHE Alkyl siol Alkyl siol ECHE Alkyl siol
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 siol 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 siol, 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 siol, 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
구체적인 예로 상기 화학식 7의 실세스퀴옥산 복합고분자는 하기 표 13 및 14에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
표 13
No R1 R2 R6 R7 R8 R9 X의R Y의R
13-1 OH,메톡시 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
13-2 OH,메톡시 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
13-3 OH,메톡시 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
13-4 OH,메톡시 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
13-5 OH,메톡시 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
13-6 OH,메톡시 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
13-7 OH,메톡시 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
13-8 OH,메톡시 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
13-9 OH,메톡시 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
13-10 OH,메톡시 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
13-11 OH,메톡시 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
13-12 OH,메톡시 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
13-13 OH,메톡시 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
13-14 OH,메톡시 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
13-15 OH,메톡시 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
13-16 OH,메톡시 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
13-17 OH,메톡시 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
13-18 OH,메톡시 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
13-19 OH,메톡시 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
13-20 OH,메톡시 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
13-21 OH,메톡시 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
13-22 OH,메톡시 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
13-23 OH,메톡시 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
13-24 OH,메톡시 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
13-25 OH,메톡시 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 13
No R1 R2 R6 R7 R8 R9 X, R Y, 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
표 14
No R1 R2 R6 R7 R8 R9 X의R Y의R
14-1 OH,메톡시 H,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
14-2 OH, CF3 H,에틸 ECHE 페닐 H,에틸 페닐 페닐 페닐
14-3 OH,메톡시 H,아세틸틸 ECHE 메틸 H,아세틸틸 메틸 메틸 메틸
14-4 CF3,메톡시 비닐,메틸 페닐 GlyP 비닐,메틸 GlyP GlyP GlyP
14-5 OH,메톡시 H,메틸 페닐 POMMA H,메틸 POMMA POMMA POMMA
14-6 OH, C8F13 H, F 페닐 ECHE H, F 페닐 ECHE 페닐
14-7 OH, CF3 CF3,메틸 ECHE ECHE CF3,메틸 메틸 ECHE 메틸
14-8 OH, C8F13 H,메틸 헥실 ECHE H,메틸 GlyP ECHE GlyP
14-9 OH,메톡시 H, CF3 GlyP ECHE H, CF3 POMMA ECHE POMMA
14-10 OH,메톡시 H,메틸 POMMA 페닐 H,메틸 ECHE 페닐 ECHE
14-11 OH, C8F13 아릴,메틸 아미노프로필 페닐 아릴,메틸 헥실 페닐 헥실
14-12 OH,알킬사이올 H,메타크릴 페닐 페닐 H,메타크릴 GlyP 페닐 GlyP
14-13 OH,메톡시 H,메틸 GlyP ECHE H,메틸 POMMA ECHE POMMA
14-14 OH, 아크릴 H,옥틸 POMMA 헥실 H,옥틸 아미노프로필 헥실 아미노프로필
14-15 비닐 ,메톡시 H,메틸 아미노프로필 GlyP H,메틸 페닐 GlyP 페닐
14-16 알킬아민 H,메틸 페닐 POMMA H,메틸 GlyP POMMA GlyP
14-17 OH,에틸,메틸 알킬사이올,메틸 옥틸 아미노프로필 알킬사이올,메틸 POMMA 아미노프로필 POMMA
14-18 아세톡시,메톡시 H,메틸 POMMA 페닐 H,메틸 아미노프로필 페닐 아미노프로필
14-19 프로폭시,메톡시 H, CF3 ECHE GlyP H, CF3 페닐 GlyP 페닐
14-20 OH, 메톡시 H,메틸 페닐 POMMA H,메틸 옥틸 POMMA 옥틸
14-21 C8F13,메톡시 C8F13,메틸 메틸 아미노프로필 C8F13,메틸 POMMA 아미노프로필 POMMA
14-22 OH,아릴 H,프로필 GlyP 페닐 H,프로필 ECHE 페닐 ECHE
14-23 OH,메톡시 F,메틸 POMMA 옥틸 F,메틸 페닐 옥틸 페닐
14-24 CF3,메타크릴 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
14-25 OH,메톡시 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 14
No R1 R2 R6 R7 R8 R9 X, R Y, R
14-1 OH, methoxy H, methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol 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 siol H, methacryl Phenyl Phenyl H, methacryl 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 siol, methyl Octyl Aminopropyl Alkyl siol, 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 , methacryl H, methyl POMMA POMMA H, methyl methyl POMMA methyl
14-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP
구체적인 예로 상기 화학식 8의 실세스퀴옥산 복합고분자는 하기 표 15 및 16에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
표 15
No R3 R4 R6 R7 R8 R9 X의R Y의 R
15-1 H,메틸 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
15-2 H,메틸 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
15-3 H,메틸 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
15-4 H,메틸 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
15-5 H,메틸 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
15-6 H,메틸 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
15-7 H,메틸 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
15-8 H,메틸 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
15-9 H,메틸 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
15-10 H,메틸 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
15-11 H,메틸 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
15-12 H,메틸 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
15-13 H,메틸 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
15-14 H,메틸 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
15-15 H,메틸 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
15-16 H,메틸 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
15-17 H,메틸 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
15-18 H,메틸 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
15-19 H,메틸 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
15-20 H,메틸 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
15-21 H,메틸 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
15-22 H,메틸 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
15-23 H,메틸 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
15-24 H,메틸 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
15-25 H,메틸 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 15
No R3 R4 R6 R7 R8 R9 X, R Y 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
표 16
No R3 R4 R6 R7 R8 R9 X의R Y의 R
16-1 H,메틸 CF3,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
16-2 H,에틸 H,메틸 ECHE 페닐 알킬사이올,메틸 헥실 페닐 헥실
16-3 H,아세틸틸 H, CF3 ECHE 메틸 H,메틸 GlyP 메틸 GlyP
16-4 비닐,메틸 H,메틸 페닐 GlyP H, CF3 POMMA GlyP POMMA
16-5 H,메틸 H,메틸 페닐 POMMA H,에틸 아미노프로필 POMMA 아미노프로필
16-6 H, F H,옥틸 페닐 ECHE H, F 페닐 ECHE 페닐
16-7 CF3,메틸 H,메틸 ECHE ECHE 비닐,메틸 GlyP ECHE GlyP
16-8 H,메틸 H,메틸 헥실 ECHE H,메틸 POMMA ECHE POMMA
16-9 H, CF3 알킬사이올,메틸 GlyP ECHE H, F 아미노프로필 ECHE 아미노프로필
16-10 H,메틸 H,메틸 POMMA 페닐 CF3,메틸 페닐 페닐 페닐
16-11 아릴,메틸 H,메틸 아미노프로필 페닐 H,메틸 옥틸 페닐 옥틸
16-12 H,메타크릴 H,메틸 페닐 페닐 H, CF3 POMMA 페닐 POMMA
16-13 H,메틸 알킬사이올,메틸 GlyP ECHE H,메틸 ECHE ECHE ECHE
16-14 H,옥틸 H,메틸 POMMA 헥실 H,메틸 페닐 헥실 페닐
16-15 H,메틸 H, F 아미노프로필 GlyP H,옥틸 메틸 GlyP 메틸
16-16 H,메틸 CF3,메틸 페닐 POMMA H,메틸 GlyP POMMA GlyP
16-17 알킬사이올,메틸 H,메틸 옥틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
16-18 H,메틸 H, CF3 POMMA 페닐 알킬사이올,메틸 아미노프로필 페닐 아미노프로필
16-19 H, CF3 H,메틸 ECHE GlyP H,메틸 페닐 GlyP 페닐
16-20 H,메틸 H,메틸 페닐 POMMA H,메틸 옥틸 POMMA 옥틸
16-21 C8F13,메틸 H,메틸 메틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
16-22 H,프로필 알킬사이올,메틸 GlyP 페닐 알킬사이올,메틸 ECHE 페닐 ECHE
16-23 F,메틸 H,메틸 POMMA 옥틸 H,메틸 페닐 옥틸 페닐
16-24 H,메틸 H, CF3 POMMA POMMA H, CF3 메틸 POMMA 메틸
16-25 H,에틸 H,메틸 POMMA ECHE H,메틸 GlyP ECHE GlyP
Table 16
No R3 R4 R6 R7 R8 R9 X, R Y R
16-1 H, methyl CF 3 , methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol ECHE
16-2 H, ethyl H, methyl ECHE Phenyl Alkyl siol, 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 siol, 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, methacryl H, methyl Phenyl Phenyl H, CF 3 POMMA Phenyl POMMA
16-13 H, methyl Alkyl siol, 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 siol, methyl H, methyl Octyl Aminopropyl H, methyl POMMA Aminopropyl POMMA
16-18 H, methyl H, CF 3 POMMA Phenyl Alkyl siol, 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 siol, methyl GlyP Phenyl Alkyl siol, 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
구체적인 예로 상기 화학식 9의 실세스퀴옥산 복합고분자는 하기 표 17 및 18에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
표 17
No R6 R7 R8 R9 R10 X의 R Y의 R E의 말단 R
17-1 ECHE ECHE H,메틸 ECHE ECHE ECHE ECHE ECHE
17-2 페닐 페닐 H,메틸 페닐 페닐 페닐 페닐 페닐
17-3 메틸 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
17-4 GlyP EGCDX H,메틸 EGCDX GlyP EGCDX EGCDX GlyP
17-5 POMMA POMMA H,메틸 POMMA POMMA POMMA POMMA POMMA
17-6 ECHE ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
17-7 ECHE ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
17-8 ECHE ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
17-9 ECHE ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
17-10 ECHE 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
17-11 ECHE 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
17-12 ECHE GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
17-13 ECHE POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
17-14 페닐 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
17-15 페닐 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
17-16 페닐 페닐 H,메틸 페닐 EGDCX 페닐 페닐 EGDCX
17-17 페닐 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
17-18 페닐 ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
17-19 페닐 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
17-20 페닐 GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
17-21 페닐 POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
17-22 메틸 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
17-23 메틸 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
17-24 메틸 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
17-25 메틸 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
17-26 메틸 ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
17-27 메틸 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
17-28 메틸 GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
17-29 메틸 POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
17-30 GlyP GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
17-31 GlyP GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
17-32 GlyP GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
17-33 GlyP GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
17-34 GlyP ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
17-35 GlyP 페닐 H,메틸 페닐 GlyP 페닐 페닐 GlyP
17-36 GlyP 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
17-37 GlyP POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
17-38 POMMA POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
17-39 POMMA POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
17-40 POMMA POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
17-41 POMMA POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
17-42 POMMA ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
17-43 POMMA 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
17-44 POMMA 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
17-45 POMMA GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
Table 17
No R6 R7 R8 R9 R10 X, R Y R Terminal R 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
표 18
No R6 R7 R8 R9 R10 X의 R Y의 R E의 말단R
18-1 ECHE POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
18-2 페닐 POMMA H,에틸 페닐 POMMA POMMA 페닐 POMMA
18-3 POMMA ECHE H,아세틸틸 메틸 ECHE ECHE 메틸 ECHE
18-4 메틸 ECHE 비닐,메틸 EGCDX ECHE ECHE EGCDX ECHE
18-5 POMMA F H,메틸 POMMA F F POMMA F
18-6 프로필 아미노프로필 CF3,메틸 ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
18-7 페닐 페닐 H,메틸 ECHE 페닐 페닐 ECHE 페닐
18-8 메틸 알킬사이올 H,아세틸틸 ECHE 알킬사이올 알킬사이올 ECHE 알킬사이올
18-9 GlyP 페닐 비닐,메틸 ECHE 페닐 페닐 ECHE 페닐
18-10 ECHE 옥틸 H,메틸 페닐 옥틸 옥틸 페닐 옥틸
18-11 알킬사이올 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
18-12 페닐 옥틸 비닐,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
18-13 옥틸 옥틸 H,메틸 POMMA 옥틸 옥틸 POMMA 옥틸
18-14 메틸 메틸 H, F 페닐 메틸 메틸 페닐 메틸
18-15 옥틸 GlyP CF3,메틸 페닐 ECHE GlyP 페닐 ECHE
18-16 옥틸 GlyP 비닐,메틸 페닐 페닐 GlyP 페닐 페닐
18-17 메틸 아미노프로필 H,메틸 페닐 POMMA 아미노프로필 페닐 POMMA
18-18 GlyP GlyP H, F ECHE 메틸 GlyP ECHE 메틸
18-19 GlyP POMMA CF3,메틸 메틸 POMMA POMMA 메틸 POMMA
18-20 아미노프로필 메틸 H,메틸 GlyP 프로필 메틸 GlyP 프로필
18-21 GlyP POMMA 알킬사이올,메틸 POMMA 페닐 POMMA POMMA 페닐
18-22 POMMA 프로필 H,아세틸틸 메틸 메틸 프로필 메틸 메틸
18-23 POMMA 메틸 비닐,메틸 메틸 GlyP 메틸 메틸 GlyP
18-24 GlyP GlyP 비닐,메틸 메틸 ECHE GlyP 메틸 ECHE
18-25 아미노프로필 GlyP H,메틸 메틸 GlyP GlyP 메틸 GlyP
18-26 메틸 아미노프로필 H, F ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
18-27 메틸 GlyP CF3,메틸 페닐 GlyP GlyP 페닐 GlyP
18-28 메틸 옥틸 H,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
18-29 메틸 메틸 H,아세틸틸 POMMA 메틸 메틸 POMMA 메틸
18-30 아미노프로필 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
18-31 GlyP GlyP H,메틸 GlyP GlyP GlyP GlyP GlyP
18-32 POMMA 아미노프로필 H,메틸 GlyP 아미노프로필 아미노프로필 GlyP 아미노프로필
18-33 메틸 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
18-34 POMMA POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
18-35 프로필 POMMA H, F 페닐 POMMA POMMA 페닐 POMMA
18-36 메틸 GlyP CF3,메틸 메틸 GlyP GlyP 메틸 GlyP
18-37 GlyP 아미노프로필 비닐,메틸 POMMA 아미노프로필 아미노프로필 POMMA 아미노프로필
18-38 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
18-39 아미노프로필 메틸 H, F POMMA 메틸 메틸 POMMA 메틸
18-40 아미노프로필 메틸 CF3,메틸 POMMA 메틸 메틸 POMMA 메틸
18-41 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
18-42 POMMA GlyP 알킬사이올,메틸 ECHE GlyP GlyP ECHE GlyP
18-43 POMMA 아미노프로필 H,아세틸틸 페닐 아미노프로필 아미노프로필 페닐 아미노프로필
18-44 POMMA GlyP 비닐,메틸 메틸 GlyP GlyP 메틸 GlyP
18-45 POMMA POMMA H,메틸 GlyP POMMA POMMA GlyP POMMA
Table 18
No R6 R7 R8 R9 R10 X, R Y R Terminal R of E
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 siol H, acetyltyl ECHE Alkyl siol Alkyl siol ECHE Alkyl siol
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 siol 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 siol, 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 siol, 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
본 발명의 상기 실세스퀴옥산 복합 고분자는 우수한 보관 안정성을 확보하여 폭넓은 응용성을 얻기 위해, 축합도가 1 내지 99.9% 이상으로 조절될 수 있다. 즉, 말단 및 중앙의 Si에 결합된 알콕시 그룹의 함량이 전체 고분자의 결합기에 대해 50%에서 0.01%까지 조절될 수 있다.The silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
또한 본 발명에 실세스퀴옥산 복합 고분자의 중량평균분자량은 1,000 내지 1,000,000, 바람직하게는 5,000 내지 100,000이며, 더욱 바람직하게는 7,000 내지 50,000일 수 있다. 이 경우 실세스퀴옥산의 가공성 및 물리적 특성을 동시에 향상시킬 수 있다.In addition, the weight average molecular weight of the silsesquioxane composite polymer according to 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 the silsesquioxane can be improved simultaneously.
본 발명에서 투명기판 위에 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자의 경화물을 적층시키는 방법은 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 투명기판에 코팅 후 경화시켜 형성할 수 있다. 2종 이상의 복합 고분자가 사용하는 것도 가능하며, 바람직하기로는 화학식 3 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 사용하는 것이 좋다. 이 경우 반복단위 [B]b 또는 [E]e를 포함함으로써 표면경도를 포함한 투명기판의 물성을 더욱 향상시킬 수 있다.In the present invention, the method for laminating the cured product of the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 on a transparent substrate includes a coating composition comprising the silsesquioxane composite polymer represented by any one of Formulas 1 to 9. It may be formed by coating and curing the transparent substrate. It is also possible to use two or more composite polymers, and it is preferable to use the silsesquioxane composite polymer represented by any one of Formulas 3 to 9. In this case, the physical properties of the transparent substrate including the surface hardness can be further improved by including the repeating unit [B] b or [E] e.
상기 코팅 조성물은 실세스퀴옥산 복합 고분자가 액상인 경우 무용제 타입으로 단독으로 코팅이 가능하며, 고상인 경우 유기용매를 포함하여 구성될 수 있다. 또한 코팅 조성물은 개시제 또는 경화제를 더욱 포함할 수 있다.The coating composition may be coated alone as a solvent-free type when the silsesquioxane composite polymer is a liquid, and may be configured to include an organic solvent in the case of a solid phase. In addition, the coating composition may further include an initiator or a curing agent.
바람직하기로 상기 코팅조성물은 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자, 상기 복합 고분자와 상용성이 있는 당분야에서 통상적으로 사용하는 유기용매, 개시제를 포함하는 것을 특징으로 하며, 선택적으로 경화제, 가소제, 자외선 차단제, 기타 기능성 첨가제 등의 첨가제를 추가로 포함하여 경화성, 내열특성, 자외선차단, 가소 효과 등을 향상시킬 수 있다.Preferably, the coating composition is characterized in that it 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, the initiator It may optionally further include additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
본 발명의 코팅 조성물에 있어서 상기 실세스퀴옥산 복합 고분자는 코팅 조성물 100 중량부에 대하여 적어도 5 중량부 이상으로 포함되는 것이 좋으며, 바람직하게는 5 내지 90 중량부, 더욱 바람직하게는 10 내지 50 중량부의 양으로 포함되는 것이 바람직하다. 상기 범위 내인 경우 코팅 조성물의 경화막의 기계적 물성을 더욱 향상시킬 수 있다.In the coating composition of the present invention, the silsesquioxane composite polymer may be included at least 5 parts by weight or more, based on 100 parts by weight of the coating composition, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight. It is preferably included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
상기 유기용매로는 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜 류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 이용할 수 있으나, 이에 제한되지는 않는다. 상기 유기용매의 양은 복합고분자, 개시제, 및 선택적으로 추가되는 첨가제를 제외한 잔량으로 포함된다.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, In addition to polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the composite polymer, the initiator, and optionally added additives.
또한 본 발명의 코팅 조성물에 있어서 상기 개시제 또는 경화제는 실세스퀴옥산 복합 고분자에 포함된 유기관능기에 따라 적절히 선택하여 사용할 수 있다.In the coating composition of the present invention, the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.
구체적인 예로서 상기 유기관능기에 불포화 탄화수소, 사이올계, 에폭시계, 아민계, 이소시아네이트계 등의 후경화가 가능한 유기계가 도입될 경우, 열 또는 광을 이용한 다양한 경화가 가능하다. 이때 열 또는 광에 의한 변화를 고분자 자체 내에서 도모할 수 있지만, 바람직하게는 상기와 같은 유기용매에 희석함으로써 경화공정을 도모할 수 있다. As a specific example, when an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.
또한 본 발명에서는 복합 고분자의 경화 및 후 반응을 위하여, 다양한 개시제를 사용할 수 있으며, 상기 개시제는 조성물 총중량 100 증량부에 대하여 0.1-10 중량부로 포함되는 것이 바람직하며, 상기 범위 내의 함량으로 포함될 때, 경화 후 투과도 및 코팅안정성을 동시에 만족시킬 수 있다.In addition, in the present invention, for curing and post-reaction of the composite polymer, various initiators may be used, and the initiator may be included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, After curing, the transmittance and coating stability can be satisfied at the same time.
또한 상기 유기관능기에 불포화 탄화수소 등이 도입될 경우에는 라디칼 개시제를 사용할 수 있으며, 상기 라디칼 개시제로는 트리클로로 아세토페논(trichloro acetophenone), 디에톡시 아세토페논(diethoxy acetophenone), 1-페닐-2-히드록시-2-메틸프로판-1-온(1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-히드록시사이클로헥실페닐케톤, 2-메틸-1-(4-메틸 티오페닐)-2-모르폴리노프로판-1-온(2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-one), 2,4,6-트리메틸 벤조일 디페닐포스핀 옥사이드(trimethyl benzoyl diphenylphosphine oxide), 캠퍼 퀴논(camphor quinine), 2,2’-아조비스(2-메틸부티로니트릴), 디메틸-2,2’-아조비스(2-메틸 부틸레이트), 3,3-디메틸-4-메톡시-벤조페논, p-메톡시벤조페논, 2,2-디에톡시 아세토페논, 2,2-디메톡시-1,2-디페닐 에탄-1-온 등의 광 래디컬 개시제, t-부틸파옥시 말레인산, t-부틸하이드로퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, N-부틸-4,4’-디(t-부틸퍼옥시)발레레이트 등의 열 라디칼 개시제 및 이들의 다양한 혼합물 등이 사용될 수 있다. In addition, when an unsaturated hydrocarbon or the like is introduced into the organic functional group, a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride. Hydroxy-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 quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl- Optical radical initiators such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t- Butylpaoxy maleic acid, t-part Hydroperoxide, 2,4-dichlorobenzoylperoxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butyl Thermal radical initiators such as peroxy) valerate and various mixtures thereof and the like can be used.
또한, 상기 유기관능기에 에폭시 등이 포함되는 경우에는, 광중합 개시제(양이온)로서 트리페닐술포늄, 디페닐-4-(페닐티오)페닐술포늄 등의 술포늄계, 디페닐요오드늄이나 비스(도데실페닐)요오드늄 등의 요오드늄, 페닐디아조늄 등의 디아조늄, 1-벤질-2-시아노피리니늄이나 1-(나프틸메틸)-2-시아노프리디늄 등의 암모늄, (4-메틸페닐)[4-(2-메틸프로필)페닐]-헥사플루오로포스페이트 요오드늄, 비스(4-t-부틸페닐)헥사플루오로포스페이트 요오드늄, 디페닐헥사플루오로포스페이트 요오드늄, 디페닐트리플루오로메탄술포네이트 요오드늄, 트리페닐술포늄 테트라풀루오로보레이트, 트리-p-토일술포늄 헥사풀루오로포스페이트, 트리-p-토일술포늄 트리풀루오로메탄술포네이트 및 (2,4-시클로펜타디엔-1-일)[(1-메틸에틸)벤젠]-Fe 등의 Fe 양이온들과 BF4 -, PF6 -, SbF6 - 등의 [BQ4]- 오늄염 조합을 이용할 수 있다(여기서, Q는 적어도 2개 이상의 불소 또는 트리플루오로메틸기로 치환된 페닐기이다.). When the organic functional group contains an epoxy or the like, sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations). Iodonium, such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopentadiene-1-yl) s Fe cations such as [(1-methylethyl) benzene] -Fe and BF 4 -, PF 6 -, SbF 6 - [BQ 4 ] , such as-may be used in combination with onium salts (here, Q is a phenyl group substituted with at least a group of two or more fluorine or a trifluoromethyl group.).
또한, 열에 의해 작용하는 양이온 개시제로는 트리플산염, 3불화 붕소 에테르착화합물, 3불화 붕소 등과 같은 양이온계 또는 프로톤산 촉매, 암모늄염, 포스포늄염 및 술포늄염 등의 각종 오늄염 및 메틸트리페닐포스포늄 브롬화물, 에틸트리페닐포스포늄 브롬화물, 페닐트리페닐포스포늄 브롬화물 등을 제한 없이 사용할 수 있으며, 이들 개시제 또한 다양한 혼합형태로 첨가할 수 있으며, 상기에 명시한 다양한 라디칼 개시제들과의 혼용도 가능하다. In addition, the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like 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.
또한, 상기 유기관능기의 종류에 따라, 아민 경화제류인 에틸렌디아민, 트리에틸렌 테트라민, 테트라에틸렌 펜타민, 1,3-디아미노프로판, 디프로필렌트리아민, 3-(2-아미노에틸)아미노-프로필아민, N,N’-비스(3-아미노프로필)-에틸렌디아민, 4,9-디옥사도테칸-1,12-디아민, 4,7,10-트리옥사트리데칸-1,13-디아민, 헥사메틸렌디아민, 2-메틸펜타메틸렌디아민, 1,3-비스아미노메틸시클로헥산, 비스(4-아니모시클로헥실)메탄, 노르보르넨디아민, 1,2-디아미노시클로헥산 등을 이용할 수 있다. Moreover, according to the kind of said organic functional group, amine diamine, ethylenediamine, triethylene tetramine, tetraethylene pentamine, 1, 3- diamino propane, dipropylene triamine, 3- (2-amino ethyl) amino-propyl Amines, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadotecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, Hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-animocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane and the like can be used. .
또한 상기 경화작용을 촉진하기 위한 경화 촉진제로, 아세토구아나민, 벤조구아나민, 2,4-디아미노-6-비닐-s-트리아진 등의 트리아진계 화합물, 이미다졸, 2-메틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 비닐이미다졸, 1-메틸이미다졸 등의 이미다졸계 화합물, 1,5-디아자비시클로[4.3.0]논엔-5,1,8-디아자비시클로[5.4.0]운데센-7, 트리페닐포스핀, 디페닐(p-트릴)포스핀, 트리스(알킬페닐)포스핀, 트리스(알콕시페닐)포스핀, 에틸트리페닐포스포늄포스페이트, 테트라부틸포스포늄히드록시드, 테트라부틸포스포늄아세테이트, 테트라부틸포스포늄하이드로젠디플루오라이드, 테트라부틸포스포늄디하이드로젠트리플루오르 등도 사용될 수 있다.In addition, as a curing accelerator for promoting the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogendifluoride, tetrabutylphosphonium dihydrogen tree Fluorine and the like can also be used.
아울러, 무수프탈산, 무수트리멜리트산, 무수피로멜리트산, 무수말레산, 테트라히드로 무수프탈산, 메틸헥사히드로 무수프탈산, 메틸테트라히드로 무수프탈산, 메틸나드산 무수물, 수소화메틸나드산 무수물, 트리알킬테트라히드로 무수프탈산, 도데세닐 무수숙신산, 무수2,4-디에틸글루타르산 등의 산무수경화제류도 폭넓게 사용될 수 있다.In addition, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
상기 경화제는 조성물 100 중량부에 대하여 0.1-10 중량부로 포함되는 것이 좋다.The curing agent is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the composition.
본 발명에서는 또한 경화공정 또는 후반응을 통한 경도, 강도, 내구성, 성형성 등을 개선하는 목적으로 자외선 흡수제, 산화 방지제, 소포제, 레벨링제, 발수제, 난연제, 접착개선제 등의 첨가제를 추가로 포함할 수 있다. 이러한 첨가제는 그 사용에 있어 특별하게 제한은 없으나 기판의 특성 즉, 유연성, 투광성, 내열성, 경도, 강도 등의 물성을 해치지 않는 범위 내에서 적절히 첨가할 수 있다. 상기 첨가제는 각각 독립적으로 조성물 100 중량부에 대하여 0.1-10 중량부로 포함되는 것이 좋다.The present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction. Can be. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength. Each of the additives may be independently included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition.
본 발명에서 사용가능한 첨가제로는 폴리에테르 디메틸폴리실록산계 (Polyether-modified polydimethylsiloxane, 예를 들어, BYK 사 제품인 BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310 등), 폴리에테르 하이드록시 폴리디메틸실록산계 (Polyether modified hydroxyfunctional poly-dimethyl-siloxane, 예를 들어, BYK 사의 BYK-308, BYK-373 등), 폴리메틸알킬실록산계 (Methylalkylpolysiloxane, 예를 들어, BYK-077, BYK-085 등), 폴리에테르 폴리메틸알킬실록산계 (Polyether modified methylalkylpolysiloxane, 예를 들어, BYK-320, BYK-325 등), 폴리에스테르 폴리메틸알킬실록산계 (Polyester modified poly-methyl-alkyl-siloxane, 예를 들어, BYK-315 등), 알랄킬 폴리메틸알킬실록산계 (Aralkyl modified methylalkyl polysiloxane, 예를 들어, BYK-322, BYK-323 등), 폴리에스테르 하이드록시 폴리디메틸실록산계 (Polyester modified hydroxy functional polydimethylsiloxane, 예를 들어, BYK-370 등), 폴리에스테르 아크릴 폴리디메틸실록산계 (Acrylic functional polyester modified polydimethylsiloxane, 예를 들어, BYK-371, BYK-UV 3570 등), 폴리에테르-폴리에스테르 하이드록시 폴리디메틸실록산계 (Polyeher-polyester modified hydroxy functional polydimethylsiloxane, 예를 들어, BYK-375 등), 폴리에테르 폴리디메틸실록산계 (Polyether modified dimethylpolysiloxane, 예를 들어, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337 등), 비이온 폴리아크릴계 (Non-ionic acrylic copolymer, 예를 들어, BYK-380 등), 이온성 폴리아크릴계 (Ionic acrylic copolymer, 예를 들어, BYK-381 등), 폴리아크릴레이트계 (Polyacrylate, 예를 들어, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 등), 폴리메타아크릴레이트계 (Polymethacrylate, 예를 들어, BYK-390 등), 폴리에테르 아크릴 폴리디메틸실록산계 (Polyether modified acryl functional polydimethylsiloxane, 예를 들어, BYK-UV 3500, BYK-UV3530 등), 폴리에테르 실록산계 (Polyether modified siloxane, 예를 들어, BYK-347 등), 알코올 알콕시레이트계 (Alcohol alkoxylates, 예를 들어, BYK-DYNWET 800 등), 아크릴레이트계 (Acrylate, 예를 들어, BYK-392 등), 하이드록시 실리콘 폴리아크릴레이트계 (Silicone modified polyacrylate (OH-functional), 예를 들어, BYK-Silclean 3700 등) 등을 들 수 있다.Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aralkyl modified methylalkyl polysiloxane, e.g. For example, BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc.), polyacrylates (e.g., BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 etc.), polymethacrylate type (Polymethacrylate, for example, BYK-390 etc.), polyether Polyether modified acryl functional polydimethylsiloxane (eg, BYK-UV 3500, BYK-UV3530, etc.), polyether siloxane (polyether modified siloxane, eg, BYK-347, etc.), alcohol alkoxylates (Alcohol alkoxylates, eg BYK-DYNWET 800, etc.), acrylates (Acrylate, eg, BYK-392, etc.), hydroxy silicone polyacrylates (Silicone modified polyacrylate (OH-functional), eg BYK-Silclean 3700, etc. are mentioned, for example.
또한 본 발명의 표면강화 투명기판에 사용될 수 있는 투명기판은 플라스틱 투명기판 및 유리가 사용될 수 있으며, 투명기판이라 함은 500 ㎚ 파장의 광원에서 투과율이 적어도 80 % 이상인 기판이며, 구체적인 플라스틱 투명기판의 예로는 COC(Cyclic olefin copolymer), PAc(Polyacrylate), PC(Polycarbonate), PE(Polyethylene), PEEK (Polyetheretherketone), PEI(Polyetherimide), PEN(Polyethylenenaphthalate), PES(Polyethersulfone), PET(Polyethyleneterephtalate), PI(Polyimide), PO(Polyolefin), PMMA(Polymethylmethacrylate), PSF(Polysulfone), PVA(Polyvinylalcohol), PVCi(Polyvinylcinnamate), TAC(Triacetylcellulose), 폴리실리콘(Poly Silicone), 폴리우레탄(Polyurethane) 및 에폭시 수지(Epoxy Resin)로 이루어진 군으로부터 선택되는 소재의 기판을 사용할 수 있다. 상기 소재로 단층 또는 동일 소재의 특성이 다른 2층 이상으로 구성될 수 있으며, 또한 공압출을 통하여 2종 이상의 플라스틱이 혼합된 투명기판일 수도 있다.In addition, a transparent substrate that can be used for the surface-reinforced transparent substrate of the present invention may be a plastic transparent substrate and glass, the transparent substrate is a substrate having a transmittance of at least 80% or more in a light source of 500 nm wavelength, the specific plastic transparent substrate Examples include Cyclic olefin copolymer (COC), Polyacrylate (PAc), Polycarbonate (PC), Polyethylene (PE), Polyetheretherketone (PEEK), Polyetherimide (PEI), Polyethylenenaphthalate (PEN), Polyethersulfone (PES), Polyethyleneterephtalate (PE), and PI (Polyimide), PO (Polyolefin), PMMA (Polymethylmethacrylate), PSF (Polysulfone), PVA (Polyvinylalcohol), PVCi (Polyvinylcinnamate), TAC (Triacetylcellulose), Polysilicon (Poly Silicone), Polyurethane (Polyurethane) and Epoxy Resin ( Epoxy Resin) can be used a substrate of a material selected from the group consisting of. The material may be composed of a single layer or two or more layers having different characteristics of the same material, and may also be a transparent substrate in which two or more kinds of plastics are mixed through coextrusion.
본 발명에 있어서, 상기 코팅 조성물을 투명기판 위에 코팅하는 방법은 스핀코팅, 바코팅, 슬릿코팅, 딥 코팅, 내츄럴 코팅, 리버스 코팅, 롤 코팅, 스핀코팅, 커텐코팅, 스프레이 코팅, 그라비어 코팅 등 공지된 방법 중에서 당업자가 임의로 선택하여 적용할 수 있음은 물론이며, 경화방법에 있어도 광경화 또는 열경화를 복합고분자의 관능기에 따라 적절하게 선택하여 적용할 수 있음은 물론이다. 바람직하기로 열경화의 경우 경화온도는 80 내지 120 ℃이다.In the present invention, a method of coating the coating composition on a transparent substrate is known as spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, and the like. Of course, those skilled in the art can arbitrarily select and apply, and of course, even in the curing method, the photocuring or thermosetting 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 ℃.
본 발명에서 상기 코팅 조성물의 코팅 두께는 임의로 조절 가능하며, 바람직하게는 0.01 내지 500 um이며, 더욱 바람직하게는 0.1 내지 300 um, 더더욱 바람직하기로는 1 내지 100 um 범위가 좋다. 상기 범위 내인 경우 7H 이상의 표면경도를 안정적으로 확보할 수 있을 뿐만 아니라 기판 표면 특성에 있어서도 우수한 물성을 나타낸다. 특히 5 um 이상의 두께로 코팅층이 적층된 경우 표면경도가 9H를 안정적으로 나타낼 수 있어 유리의 대체품으로도 적용될 수 있다.In the present invention, the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, even more preferably 1 to 100 um. Within the above range, not only can the surface hardness of 7H or more be stably secured, but also excellent physical properties of the substrate surface properties. In particular, when the coating layer is laminated to a thickness of 5 um or more can be applied as a substitute for glass because the surface hardness can be represented stably 9H.
본 발명은 또한 상기 표면강화 투명기판을 포함하는 전자제품을 제공하는 바, 바람직하기로 상기 전자제품은 디스플레이 기기이며, 구체적인 예로는 스마트폰, 테블릿 PC, 노트북 PC, AIO(All-In-One) PC, LCD 모니터, TV, 광고판 또는 터치패널일 수 있으며, 기판의 유연성을 요구하는 플렉시블 스마트 기기(웨어러블 스마트 기기)일 수도 있다.  The present invention also provides an electronic product including the surface-reinforced transparent substrate, preferably, the electronic product is a display device, and specific examples thereof include a smartphone, a tablet PC, a notebook PC, and an AIO (All-In-One). ) It may be a PC, an LCD monitor, a TV, a billboard or a touch panel, or a flexible smart device (wearable smart device) that requires flexibility of a substrate.
상기 전자제품에 포함되는 상기 표면강화 투명기판의 형태는 특별히 한정되지 않으며, 일예로 윈도우 커버 기판 또는 보호필름의 형태일 수 있다. 본 발명에 따른 전자제품은 하나의 단일층 만으로 투명기판의 표면경도가 현저히 개선되고, 동시에 내지문성, 내스크레치성, 내오염성, 내열성, 투과도 및 헤이즈 특성이 우수하다.The shape of the surface-reinforced transparent substrate included in the electronic product is not particularly limited and may be, for example, in the form of a window cover substrate or a protective film. The electronic product according to the present invention significantly improves the surface hardness of the transparent substrate with only one single layer, and at the same time, has excellent anti-fingerprint, scratch resistance, contamination resistance, heat resistance, permeability and haze characteristics.
또한 본 발명은 상기 표면강화 투명기판을 포함하는 보호판을 제공하는 바, 상기 보호판은 투명하여 내부를 들여다 볼 수 있거나 내부의 전자제품(디스플레이기기)를 보호하는 기판일 수 있으며, 일예로 공공건물(기차 역사, 공항, 버스터미널 등)의 디스플레이 설치물에 디스플레이 기기를 보호하는 투명 보호판일 수 있다. In another aspect, the present invention provides a protective plate comprising the surface-reinforced transparent substrate, the protective plate may be transparent to look inside or protect the electronics (display device) therein, for example, public buildings ( It may be a transparent protective plate that protects display devices in display installations of train stations, airports, bus terminals, etc.).
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 하기 본 발명의 실시예에서 ECHETMS는 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, GPTMS는 Glycidoxypropytrimethoxysilane, MAPTMS는 (methacryloyloxy)propyltrimethoxysilane, PTMS는 Phenyltrimethoxysilane, MTMS는 Methyltrimethoxysilane, ECHETMDS는 Di(epoxycyclohexyethyl) tetramethoxy disiloxane, GPTMDS는 Di(glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS는 Di(methacryloyloxy)propy, PTMDS는 Di(phenyl) tetramethoxy disiloxane, MTMDS는 Di(Methyl) tetramethoxy disiloxane을 의미한다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples. In the embodiment of the present invention, ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy) propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, and ECHETMDS is Di (epoxycyclohexyethyl) 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.
[실시예 1] 공중합체 1 및 9을 포함하는 코팅조성물의 제조Example 1 Preparation of a Coating Composition Comprising Copolymers 1 and 9
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하였다. In the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows.
[실시예 1-a] 촉매의 제조Example 1-a Preparation of Catalyst
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 중량% 수용액에 10 중량% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 1-b] 선형 실세스퀴옥산 구조의 합성Example 1-b Synthesis of Linear Silsesquioxane Structure
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 15 중량부, 상기 실시예 1-a에서 제조된 촉매 1 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 20중량부를 적가하고, 다시 테트라하이드로류란을 15 중량부 적가하여 5시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 화학식 4구조와 같은 선형구조의 실세스퀴옥산이 8,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
[실시예 1-c] 연속적 cage 구조의 생성Example 1-c Generation of a continuous cage structure
상기 실시예 1-b 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 20% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 1과 같은 A-D 고분자가 50% 이상 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 11,000으로 측정되었으며, 평균 n값은 4.6이었다. 29Si-NMR (CDCl3) δ To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. 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 in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 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 cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, a portion was collected and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced by using a phenyl group appeared as two sharp forms, and 50% of the AD polymer of Formula 1 without remaining by-products remained. It was confirmed that the above was manufactured. In addition, the styrene reduced molecular weight was measured to 11,000, the average n value was 4.6. 29 Si-NMR (CDCl 3 ) δ
[실시예 1-d] 광경화형 수지 조성물 제조Example 1-d Photocurable Resin Composition
상기 실시예 1-c에서 수득한 실세스퀴옥산 복합 고분자 30 g을 메틸아이소부틸케톤에 30 wt%로 녹여 100 g의 코팅조성물을 제조하였다. 이후, 코팅 조성물 100 중량부에 클로로 아세토페논(chloro acetophenone) 3 중량부와 BYK-347 1 중량부, BYK-UV 3500 1 중량부를 각각 첨가하고 10분간 교반하여 광경화형 코팅 조성물을 제조하였다.30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30 wt% to prepare a coating composition of 100 g. 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 of the coating composition, and stirred for 10 minutes to prepare a photocurable coating composition.
[실시예 1-e] 열경화형 수지 조성물의 제조Example 1-e Preparation of Thermosetting Resin Composition
상기 실시예 1-c에서 수득한 실세스퀴옥산 복합 고분자 50 g을 메틸에틸케톤에 50 중량%로 녹여 100 g의 코팅조성물을 제조하였다. 이후, 준비된 코팅 조성물 100 중량부에 1,3-디아미노프로판 3 중량부와 BYK-357 및 BYK-348을 각 1 중량부씩 첨가하고 10분간 교반하여 열경화형 코팅 조성물을 제조하였다.50 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
[실시예 1-f] 고분자 자체로 구성된 코팅 조성물Example 1-f Coating composition composed of polymer itself
실시예 1-c 만으로 별도의 조성 없이 코팅 조성물을 구성하였다.Example 1-c alone constitute a coating composition without a separate composition.
또한, 하기 표 19에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 1-b, 1-c, 1-d, 1-e 및 1-f에서 사용한 방법을 대등하게 적용하였다.In addition, by applying the monomers described in Table 19 to prepare a silsesquioxane composite polymer and to prepare a coating composition. In this case, the method used in Examples 1-b, 1-c, 1-d, 1-e, and 1-f was equally applied.
표 19
실시방법 1-b 방법적용 단량체 1-c 방법적용 단량체 분자량(Mw)
전구체 cage도입
1 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
Table 19
Method of implementation 1-b Method Applicable Monomer 1-c method applied 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
실시예 2Example 2 : 실세스퀴옥산 D-A-D 구조 복합 고분자의 합성Synthesis of Silsesquioxane D-A-D Structured Polymer
D-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1에 기재된 방법과 대응한 방법으로 코팅 조성물을 제조하였다. 촉매 및 선형구조의 제조는 실시예 1-a 및 1-b의 방법을 동일하게 사용하였으며, 이후 연속적 D-A-D 구조를 생성하기 위하여 아래의 방법으로 제조를 실시하였다.In order to manufacture a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method corresponding to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.
[실시예 2-a] 과량의 연속적 cage 구조의 생성Example 2-a Generation of Excess Continuous Cage Structure
상기 실시예 1-b 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 실시예 1-b에서 사용된 Diphenyltetramethoxydisiloxane의 5배인 25 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 20% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 1과 같은 A-D 고분자가 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 14,000으로 측정되었으며, 평균 n값은 4.6이었다. 또한, Si-NMR 분석에서 A-D구조와는 달리 A구조의 말단에서 보이던 -68ppm 근방의 피크가 사라져, A구조의 말단이 D구조로 모두 변환되어 D-A-D구조로 생성됨을 확인 하였다. 29Si-NMR (CDCl3) δ -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad)To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one 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. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 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 cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was analyzed and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the AD polymer of Formula 1 was prepared without any remaining by-products. I could confirm it. In addition, the styrene reduced molecular weight was measured as 14,000, the average n value was 4.6. In addition, unlike the AD structure in the Si-NMR analysis, the peak around -68ppm, which was seen at the end of the A structure, disappeared, and the end of the A structure was converted into the D structure, thereby confirming that the DAD structure was generated. 29 Si-NMR (CDCl 3 ) δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 20에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 2에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition 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.
표 20
실시방법 1-b 방법적용 단량체 2-a 방법적용 단량체 분자량(Mw)
전구체 cage도입
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
Table 20
Method of implementation 1-b Method Applicable Monomer 2-a method applied 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
실시예 3Example 3 : 실세스퀴옥산 E-A-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-D Structured Composite Polymer
E-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1에 기재된 방법과 대응한 방법으로 코팅 조성물을 제조하였다. 촉매 및 선형구조의 제조는 실시예 1의 방법을 동일하게 사용하였으며, 이후 E-A-D 구조를 생성하기 위하여 아래의 방법으로 제조를 실시하였다.In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method corresponding to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.
[실시예 3-a] 사슬 말단 E구조의 생성Example 3-a Generation of Chain Terminal E Structure
실시예 1-c 에서 얻어진 A-D 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 ° C at a temperature of 4 ° C. Stirred for a minute. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 3-b] 말단 E 구조에 cage 도입Example 3-b Introduction of a Cage to the Terminal E Structure
상기 실시예 3-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 3-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 1-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 3과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a 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. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 3-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 3-c] Removal of By-products by Precipitation and Recrystallization, Obtaining the Result
상기 실시예 3-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. After the reaction mixture was obtained 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 by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 3의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 17,000이었으며, n의 평균값은 4.6이었으며, 특히 화학식 3의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, the average value of n was 4.6, in particular, the results of formula (3) are as follows.
29Si-NMR (CDCl3) δ -68.2, -71.8(sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 21에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 3에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. In this case, the method used in Example 3 was equally applied.
표 21
실시방법 1-b 방법적용 단량체 1-c 방법적용 단량체 3-a방법적용 단량체 3-b방법적용단량체 Mw
전구체 cage도입
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
Table 21
Method of implementation 1-b Method Applicable Monomer 1-c method applied monomer 3-a method applied monomer 3-b method applied 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
실시예 4Example 4 : A-B-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of A-B-D Structured Composite Silsesquioxane Polymer
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하여 E-A-D구조의 복합 고분자를 제조하였으며, 상기 실시예 1에 기재된 방법과 대응한 방법으로 코팅 조성물을 제조하였다.였다.In the synthesis step, a continuous hydrolysis and condensation were carried out step by step to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method corresponding to that described in Example 1.
[실시예 4-a] 가수분해 및 축합 반응을 위한 촉매의 제조Example 4-a Preparation of Catalysts for Hydrolysis and Condensation Reactions
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 wt% 수용액에 10 wt% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.To adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 4-b] 선형 실세스퀴옥산 구조의 합성 (A-B전구체의 합성)Example 4-b Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 40 중량부, 상기 실시예 4-a에서 제조된 촉매 0.5 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 10 중량부를 적가하고, 다시 테트라하이드로류란을 20 중량부 적가하여 2시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, 1H-NMR 분석을 통하여 잔존하는 alkoxy group이 0.1 mmol/g 이하로 잔존하고 있는 선형 실세스퀴옥산을 얻어 내었고, 이는 이후 cage를 연속반응으로 도입하는데 이용되는 부분이다. 선형 구조의 형태 분석은 XRD 분석을 통해 전체적인 구조가 선형구조체임을 확인하였다. 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 6,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다. To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
1H-NMR (CDCl3) δ 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 1 H-NMR (CDCl 3 ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.
[실시예 4-c] 사슬 내 cage 구조의 생성을 위한 pH 변환 반응 (B,D 구조의 도입)[Example 4-c] pH conversion reaction for generation of cage structure in chain (introduction of B, D structure)
반응이 진행 중인 실시예 4-b 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 DiPhenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 1시간 교반 후 실시예 4-a에서 제조된 촉매를 5 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형구조체와는 별도로 cage 형태의 구조체가 생성되어 고분자 사슬에 도입됨을 확인 할 수 있었으며, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.025 mmol/g으로 변화되어 B 와 D의 반복단위가 약 5:5 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 10,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, 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 in a basic state. At this time, it could be confirmed that the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by 29 Si-NMR and 1 H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although 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, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) δ 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 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)
[실시예 4-d] B 구조내 X도입 (B,D 구조의 도입)[Example 4-d] X introduction into B structure (introduction of B and D structure)
상기 실시예 4-c에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 4-c에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 4-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 4와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 4-c without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 4-e] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 4-e] Removal of By-products by Precipitation and Recrystallization, Obtained Result
상기 실시예 4-d에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 4-d, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 4의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 12,000의 값을 얻을 수 있었으며, X의 n의 평균값은 4.6이었으며, Y의 n의 평균값은 4.6이었으며, 특히 화학식 4의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 12,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula 4 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 22에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 4에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. In this case, the method used in Example 4 was equally applied.
표 22
실시방법 4-b 방법적용 단량체 4-c 방법적용 단량체 4-d 방법적용 단량체 분자량(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
Table 22
Method of implementation 4-b method applied monomer 4-c method applied monomer 4-d method applied 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
실시예 5Example 5 : D-A-B-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of D-A-B-D Structured Composite Silsesquioxane Polymer
D-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 방법을 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
[실시예 5-a] D구조의 과량 생성을 위한 pH 변환 반응 (B,D 구조의 도입)Example 5-a pH Conversion Reaction for Excess Production of D Structure (Introduction of B, D Structure)
반응이 진행 중인 실시예 4-b 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane의 양을 실시예 4-b의 5배인 25 중량부로 준비하여 한번에 적가하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 5 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 반응 완료 후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.012 mmol/g으로 변화되고 B 와 D의 반복단위가 약 1:9 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 24,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by 29 Si-NMR and 1 H-NMR. The amount of alkoxy groups in the B structure was changed to 0.012 mmol / g and the repeating units of B and D were about It was confirmed that the 1: 9 ratio was introduced. In addition, styrene conversion molecular weight was measured as 24,000. In addition, although 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, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) δ 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 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)
[실시예 5-b] B 구조내 X도입 (B,D 구조의 도입)[Example 5-b] X Introduction in B Structure (Introduction of B, D Structure)
상기 실시예 5-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 5-a에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 4-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 5와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 5-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 5-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 5-b에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 5-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 5의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 16,000의 값을 얻을 수 있었으며, X의 n의 평균값은 4.6이었으며, Y의 n의 평균값은 4.6이었으며, 특히 화학식 5의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 16,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula (5) is as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 23에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 5에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition 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.
표 23
실시방법 4-b 방법적용 단량체 4-a 방법적용 단량체 5-b 방법적용 단량체 분자량(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
Table 23
Method of implementation 4-b method applied monomer 4-a method applied monomer 5-b method applied 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
실시예 6Example 6 : 실세스퀴옥산 E-A-B-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-B-D Structured Composite Polymer
E-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 아래의 방법을 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.The following method was used to prepare the composite polymer having the E-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
[실시예 6-a] 사슬 말단 E구조의 생성Example 6-a Generation of Chain Terminal E Structure
실시예 4-c 에서 얻어진 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. 20 parts by weight of methylene chloride was added dropwise to the mixture obtained in Example 4-c, 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 6-b] B구조 및 말단 E 구조의 X에 cage 도입[Example 6-b] Cage introduction into X of B structure and terminal E structure
상기 실시예 6-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 6-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 1-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 6과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. 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. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 6-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 6-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 6-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. In Example 6-b, the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 6의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 21,000의 값을 얻을 수 있었으며, X의 n의 평균값은 4.6이었으며, Y의 n의 평균값은 4.6이었으며, 특히 화학식 6의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 21,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula (6) is as follows.
29Si-NMR (CDCl3) δ -68.2, -71.8(sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 24에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 6에서 사용한 방법을 대등하게 적용하였다.In addition, the 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.
표 24
실시방법 4-b 방법적용 단량체 4-c 방법적용 단량체 6-a방법적용 단량체 6-b방법적용단량체 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
Table 24
Method of implementation 4-b method applied monomer 4-c method applied monomer 6-a method applied monomer 6-b method applied 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
실시예 7Example 7 : 실세스퀴옥산 A-B-A-D 구조 복합 고분자의 합성Synthesis of Silsesquioxane A-B-A-D Structured Polymer
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하였으며, 상기 실시예 1과 같은 방법을 코팅 조성물을 제조하였다.Synthesis step was carried out step by step, continuous hydrolysis and condensation step, the same method as in Example 1 to prepare a coating composition.
[실시예 7-a] 촉매의 제조Example 7-a Preparation of Catalyst
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 중량% 수용액에 10 중량% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 7-b] 선형 실세스퀴옥산 합성 (A 전구체)Example 7-b Linear Silsesquioxane Synthesis (A Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 15 중량부, 상기 실시예 7-a에서 제조된 촉매 1 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 20 중량부를 적가하고, 다시 테트라하이드로류란을 15 중량부 적가하여 5시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 6,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
[실시예 7-c] 선형 실세스퀴옥산 구조의 합성 (A-B전구체의 합성)Example 7-c Synthesis of Linear Silsesquioxane Structures (Synthesis of A-B Precursors)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 40 중량부, 상기 실시예 7-a에서 제조된 촉매 0.5 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 10 중량부를 적가하고, 다시 테트라하이드로류란을 20 중량부 적가하여 2시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, 1H-NMR 분석을 통하여 잔존하는 alkoxy group이 0.1 mmol/g 이하로 잔존하고 있는 선형 실세스퀴옥산을 얻어 내었고, 이는 이후 cage를 연속반응으로 도입하는데 이용되는 부분이다. 선형 구조의 형태 분석은 XRD 분석을 통해 전체적인 구조가 선형구조체임을 확인하였다. 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 8,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다. To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the 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.
[실시예 7-d] 선형 실세스퀴옥산 구조의 합성 (A-B-A전구체의 합성)Example 7-d Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B-A Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 5 중량부, 제조된 실시예 7-a 촉매를 10 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 실시예 7-b 전구체와 7-c 전구체를 20 중량부씩 각각 적가하고, 다시 테트라하이드로류란을 10 중량부 적가하여 24시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 15,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, 10 parts by weight of the prepared Example 7-a catalyst were added dropwise and stirred at room temperature for 1 hour, followed by Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.
1H-NMR (CDCl3) δ 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 1 H-NMR (CDCl 3 ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.
[실시예 7-e] 연속적 cage 구조의 생성 (D 구조의 도입)Example 7-e Generation of Continuous Cage Structure (Introduction of D Structure)
상기 실시예 7-d 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 7-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 10% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 7과 같은 고분자가 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 18,000으로 측정되었다.To the mixed solution of Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. 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 in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 10%, 10 parts by weight of 0.36 wt% aqueous HCl solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 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 cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was collected and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the polymer of formula 7 was prepared without any remaining by-products. Could. In addition, styrene conversion molecular weight was measured as 18,000.
29Si-NMR (CDCl3) δ -68.2, -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
[실시예 7-f] B 구조내 X도입 (A-B-A-D구조의 완성)[Example 7-f] X introduction in B structure (completion of A-B-A-D structure)
상기 실시예 7-e에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 7-e에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 7과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 7-e without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 7-g] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 7-g] Removal of by-products by precipitation and recrystallization, yield of the result
상기 실시예 7-f에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 7-f, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 7의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 24,000의 값이었으며, X의 n의 평균값은 4.6이었으며, Y의 n의 평균값은 4.6이었다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was a styrene conversion value of 24,000, the average value of n of X was 4.6, the average value of n of Y was 4.6.
또한, 하기 표 25에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 7에서 사용한 방법을 대등하게 적용하였다.In addition, the 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.
표 25
실시방법 7-b,c 방법적용 단량체 7-e 방법적용 단량체 7-f 방법적용 단량체 분자량(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
Table 25
Method of implementation 7-b, c method applied monomer 7-e method applied monomer 7-f method applied 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
실시예 8Example 8 : D-A-B-A-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of D-A-B-A-D Structured Composite Silsesquioxane Polymers
D-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1과 같은 방법으로 코팅 조성물을 제조하였다.In order to prepare a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared in the same manner as in Example 1.
[실시예 8-a] D구조의 과량 생성을 위한 pH 변환 반응 Example 8-a pH Conversion Reaction for Excess Production of D Structure
반응이 진행 중인 실시예 7-d 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 15 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane의 양을 실시예 7-e의 5배인 25 중량부로 준비하여 한번에 적가하고, 1시간 교반 후 실시예 7-a에서 제조된 촉매를 20 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 반응 완료 후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.006 mmol/g으로 변화되고 B 와 D의 반복단위가 약 5:5 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 32,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.15 parts by weight of a 0.36 wt% HCl aqueous solution was added 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. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by 29 Si-NMR and 1 H-NMR. The amount of alkoxy groups in the B structure was changed to 0.006 mmol / g and the repeating units of B and D were about It was confirmed that the ratio was introduced at 5: 5. In addition, styrene conversion molecular weight was measured as 32,000. In addition, although 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, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) δ 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 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)
[실시예 8-b] B 구조내 X도입Example 8-b Introducing X in B Structure
상기 실시예 8-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 8-a에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 8와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 8-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were 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 in a basic state. At this time, the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (8). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 8-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 8-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 8-b에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 8-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 1의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 36,000의 값을 얻을 수 있었으며, X의 n의 평균값은 4.6이었으며, Y의 n의 평균값은 4.6이었으며, 특히 화학식 8의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 36,000, the average value of n of X was 4.6, the average value of n of Y was 4.6, in particular in the formula 8 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 26에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 8에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition 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.
표 26
실시방법 7-b,c 방법적용 단량체 8-a 방법적용 단량체 8-b 방법적용 단량체 분자량(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
Table 26
Method of implementation 7-b, c method applied 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
실시예 9Example 9 : 실세스퀴옥산 E-A-B-A-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-B-A-D Structured Polymer
E-A-B-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
[실시예 9-a] 사슬 말단 E구조의 생성Example 9-a Generation of Chain Terminal E Structure
실시예 7-g 에서 얻어진 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 9-b] B구조 및 말단 E 구조의 X에 cage 도입Example 9-b Introducing cage to X of B structure and terminal E structure
상기 실시예 9-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 9-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 9과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time 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 give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 9-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 9-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 9-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. After the reaction mixture was obtained 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 by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent 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 the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 9의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 28,000의 값을 얻을 수 있었으며, X의 n의 평균값은 4.6이었으며, Y의 n의 평균값은 4.6이었다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in a styrene conversion value of 28,000, the average value of n of X was 4.6, the average value of n of Y was 4.6.
또한, 하기 표 27에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 9에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. In this case, the method used in Example 9 was equally applied.
표 27
실시방법 7-b,c 방법적용 단량체 7-e 방법적용 단량체 9-a방법적용 단량체 9-b방법적용단량체 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
Table 27
Method of implementation 7-b, c method applied monomer 7-e method applied monomer 9-a method applied monomer 9-b method applied 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
[실험] [Experiment]
PC, PET 및 PMMA 투명기판에 상기 실시예 1 내지 9에서 제조한 코팅 조성물을 코팅하고, 경화시켜 표면특성을 측정하였다.The coating composition prepared in Examples 1 to 9 was coated on PC, PET and PMMA transparent substrates, and cured to measure surface properties.
- 표면경도측정 : 일반적으로 연필경도법(JIS 5600-5-4)은 일반적으로 500 g 하중으로 평가하는데 이보다 가혹조건인 1 kgf 하중으로 코팅면에 45도 각도로 연필을 매초 0.5 mm의 속도로 수평으로 3 mm 이동해서 코팅막을 긁어서 긁힌 흔적으로 평가하였다. 5회 실험으로 2회 이상 긁힌 흔적이 확인되지 않으면 상위의 경도의 연필을 선택하고 , 긁힌 흔적이 2회 이상 되면 연필을 선정하고 그 연필경도보다 한단 하위의 연필경도가 해당 코팅막의 연필경도로 평가하여 하기 표 28에 나타내었다. 평가 결과는 10 um 이상의 코팅 두께에서 기판 종류에 상관없이 유리수준의 9H 경도를 확인하였다.-Surface hardness measurement In general, the pencil hardness method (JIS 5600-5-4) is generally rated at 500 g load, which is 3 kg horizontally at a rate of 0.5 mm per second at a 45-degree angle to the coating surface under a more severe 1 kgf load. The coating film was moved to evaluate the scratches. If no traces of scratches are found in five experiments, select a pencil with a higher hardness.If more than two scratches are found, select a pencil and the pencil hardness lower than the pencil hardness is evaluated as pencil hardness of the coating It is shown in Table 28 below. The evaluation results confirmed the 9H hardness of the glass level regardless of the substrate type at a coating thickness of 10 um or more.
표 28
실시예(코팅두께 10 um) PET PC PMMA
코팅전 코팅후 코팅전 코팅후 코팅전 코팅 후
실시예 1의 광경화코팅조성물 2B 9H 6B 9H 2H 9H
실시예 2의 열경화코팅조성물 9H 9H 9H
실시예 3의 광경화코팅조성물 9H 9H 9H
실시예 4의 열경화코팅조성물 9H 9H 9H
실시예 5의 광경화코팅조성물 9H 9H 9H
실시예 6의 열경화코팅조성물 9H 9H 9H
실시예 6의 고분자자체코팅조성물 9H 9H 9H
실시예 7의 열경화코팅조성물 9H 9H 9H
실시예 8의 광경화코팅조성물 9H 9H 9H
실시예 9의 열경화코팅조성물 9H 9H 9H
Table 28
Example (Coating Thickness 10um) PET PC PMMA
Before coating After coating Before coating After coating Before coating After coating
Photocuring coating composition of Example 1 2B 9H 6B 9H 2H 9H
Thermosetting Coating Composition of Example 2 9H 9H 9H
Photocuring coating composition of Example 3 9H 9H 9H
Thermosetting Coating Composition of Example 4 9H 9H 9H
Photocuring 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
Photocuring coating composition of Example 8 9H 9H 9H
Thermosetting Coating Composition of Example 9 9H 9H 9H
- 신뢰성 평가 : 85%, 85℃ 신뢰성 챔버에 240시간 보관하고 휨 특성 평가하였으며, 그 결과를 하기 표 29에 나타내었다. -Reliability Evaluation: Storing at 85%, 85 ℃ reliability chamber for 240 hours and evaluated the bending characteristics, the results are shown in Table 29 below.
휨평가 기준은 신뢰성 평가전 ±0.1 mm이내, 신뢰성평가 후 ±0.3 mm 이내이다.Flexural evaluation criteria are within ± 0.1 mm before reliability evaluation and within ± 0.3 mm after reliability evaluation.
평가 결과는 PET, PC, PMMA 모든 기재에 있어서 우수하였다.The evaluation result was excellent in all the PET, PC, and PMMA base materials.
표 29
실시예(코팅두께 10 um)YI(ASTMD1925) PET PC PMMA
코팅전 코팅후 코팅전 코팅후 코팅전 코팅 후
실시예 1-1의 광경화코팅조성물 0.38 -0.11 -0.15 0.04 0.14 0.22
실시예 2-2의 열경화코팅조성물 -0.11 0.04 0.21
실시예 3-3의 광경화코팅조성물 -0.10 0.03 0.20
실시예 4-4의 열경화코팅조성물 -0.11 0.05 0.18
실시예 5-5의 광경화코팅조성물 -0.11 0.04 0.17
실시예 6의 열경화코팅조성물 -0.05 0.02 0.15
실시예 6의 고분자자체코팅조성물 -0.14 0.06 0.18
실시예 7-7의 열경화코팅조성물 -0.11 0.05 0.19
실시예 8-8의 광경화코팅조성물 -0.11 0.04 0.18
실시예 9-9의 열경화코팅조성물 -0.09 0.05 0.18
Table 29
Example (Coating Thickness 10um) YI (ASTMD1925) PET PC PMMA
Before coating After coating Before coating After coating Before coating After coating
Photocuring coating composition of Example 1-1 0.38 -0.11 -0.15 0.04 0.14 0.22
Thermosetting Coating Composition of Example 2-2 -0.11 0.04 0.21
Photocuring coating composition of Example 3-3 -0.10 0.03 0.20
Thermosetting Coating Composition of Example 4-4 -0.11 0.05 0.18
Photocuring coating composition of Example 5-5 -0.11 0.04 0.17
Thermosetting Coating Composition of Example 6 -0.05 0.02 0.15
Polymer self coating composition of Example 6 -0.14 0.06 0.18
Thermosetting Coating Composition of Example 7-7 -0.11 0.05 0.19
Photocuring coating composition of Example 8-8 -0.11 0.04 0.18
Thermosetting Coating Composition of Example 9-9 -0.09 0.05 0.18
- Scratch test 측정: Steel wool #0000을 1 kgf로 400회 평가 Steel wool에 의한 마모 평가법(JIS K5600-5-9)은 1kg 정도 무게의 쇠망치의 선단에 #0000의 Steel wool을 감아서 15회 왕복 시험편을 문지르고 그 헤이즈를 값을 측정하는데 이보다 가혹한 조건인 400회 시험편을 문지르고 헤이즈 측정 및 현미경으로 육안 평가 진행하였으며, 실시예 6의 광경화성 코팅 조성물에 대한 결과는 하기 표 30에 나타내었다. 표 30에 기재되지 않았지만 본 발명의 다른 실시예의 코팅 조성물들은 코팅두께가 5 um 이상의 코팅에서는 표면에 발생되는 스크래치에 대한 내성이 우수한 것을 확인하였다.-Scratch test measurement: Steel wool # 0000 is evaluated 400 times at 1 kgf The wear evaluation method by steel wool (JIS K5600-5-9) is wound 15 times by winding # 0000 steel wool at the tip of the iron hammer weighing about 1kg. The reciprocating test piece was rubbed, and the haze value was measured. Rubbing was performed 400 times, which was a more severe condition, and was visually evaluated by haze measurement and a microscope. The results of the photocurable coating composition of Example 6 are shown in Table 30 below. Although not shown in Table 30, the coating compositions of other examples of the present invention were found to have excellent resistance to scratches occurring on the surface when the coating thickness is 5 um or more.
- 접착력 평가(JIS K5600-5-6) : 코팅막을 1-5 mm간격으로 컷터날로 긁어서 그 위에 셀로판테이프를 붙이고 붙인 테입을 잡아당겼을 때 이탈된 갯수로 접착성 판단하는데 이때 컷터날로 100개의 칸을 만들어 100개 중 떨어지는 개수로 접착성 판단 시행하였으며, 실시예 6의 광경화성 코팅 조성물에 대한 결과는 하기 표 30에 나타내었다. 표기는 100개중 떨어지지 않은 개수로 "(떨어지지 않은 개수/100)"로 표기 예제로 100개가 떨어지지 않으면 "(100/100)"로 표기 하였다. 접착성은 매우 우수한 것을 확인하였다. 표 30에 기재되지 않았지만 본 발명의 다른 실시예의 코팅 조성물들은 평가결과 접착성은 매우 우수한 것을 확인하였다. -Evaluation of adhesive force (JIS K5600-5-6): When the coating film is scratched with a cutter blade at intervals of 1-5 mm, the cellophane tape is attached on it, and the adhesive tape is judged for its adhesiveness when the tape is pulled out. Adhesive determination was made by the number of falling made of 100, the results for the photocurable coating composition of Example 6 are shown in Table 30 below. The notation is "(100/100) not falling out of the number of 100" In the example of not falling 100 ("100/100)". It was confirmed that the adhesiveness was very excellent. Although not shown in Table 30, the coating compositions of other examples of the present invention were evaluated to have excellent adhesion.
표 30
평가항목 PET PC PMMA
코팅전 코팅후 코팅전 코팅후 코팅전 코팅후
코팅두께 - 10㎛ - 10㎛ - 10㎛
접착력 - pass(100/100) - pass(100/100) - pass(100/100)
투과율(%) UV-vis-400nm 91.0 91.7 89.2 88.5 90.4 89.5
UV-vis-450nm 91.5 93.1 90.1 90.2 91.5 91.2
UV-vis-500nm 92.4 93.8 91.4 91.6 91.9 91.6
Scrath test(Steel wool, 1kgf하중,400회) Fail pass Fail pass Fail pass
Haze(%) 0.15 0.14 0.15 0.12 0.05 0.03
Table 30
Evaluation item PET PC PMMA
Before coating After coating Before coating After coating Before coating After coating
Coating thickness - 10 μm - 10 μm - 10 μm
Adhesion - pass (100/100) - pass (100/100) - pass (100/100)
Transmittance (%) UV-vis-400nm 91.0 91.7 89.2 88.5 90.4 89.5
UV-vis-450nm 91.5 93.1 90.1 90.2 91.5 91.2
UV-vis-500nm 92.4 93.8 91.4 91.6 91.9 91.6
Scrath test (Steel wool, 1kg f load, 400 times) Fail pass Fail pass Fail pass
Haze (%) 0.15 0.14 0.15 0.12 0.05 0.03
상기 표 30에 나타난 바와 같이 본 발명의 표면강화 투명기판은 매우 우수한 표면경도와 광학적 특성을 보일 뿐만 아니라 기타 물성에 있어서도 동시에 우수함을 확인할 수 있다.As shown in Table 30, the surface-reinforced transparent substrate of the present invention not only shows very excellent surface hardness and optical properties, but also excellent in other physical properties.
본 발명에 따른 표면강화 투명기판은 특정구조의 실세스퀴옥산 복합 고분자의 경화체를 코팅층으로 포함함으로써 투명기판의 표면경도를 현저히 개선하고, 동시에 내지문성, 내스크레치성, 내오염성, 내열성, 투과도 및 헤이즈 특성이 향상되어 전자제품의 윈도우 커버기판, 보호필름 또는 보호판에 매우 유용하게 사용할 수 있다.The surface-reinforced transparent substrate according to the present invention significantly improves the surface hardness of the transparent substrate by including the cured product of the silsesquioxane composite polymer having a specific structure as a coating layer, and at the same time, the fingerprint resistance, scratch resistance, contamination resistance, heat resistance, permeability and The haze characteristics are improved, which makes it very useful for window cover substrates, protective films or protective plates of electronic products.

Claims (17)

  1. 투명기판 위에 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자의 경화물이 적층된 것을 특징으로 하는 표면강화 투명기판:Surface-reinforced transparent substrate, characterized in that the cured product of the silsesquioxane composite polymer represented by any one of the following formulas 1 to 9 laminated on the transparent substrate:
    [화학식 1][Formula 1]
    Figure PCTKR2015001971-appb-I000030
    Figure PCTKR2015001971-appb-I000030
    [화학식 2][Formula 2]
    Figure PCTKR2015001971-appb-I000031
    Figure PCTKR2015001971-appb-I000031
    [화학식 3][Formula 3]
    Figure PCTKR2015001971-appb-I000032
    Figure PCTKR2015001971-appb-I000032
    [화학식 4][Formula 4]
    Figure PCTKR2015001971-appb-I000033
    Figure PCTKR2015001971-appb-I000033
    [화학식 5][Formula 5]
    Figure PCTKR2015001971-appb-I000034
    Figure PCTKR2015001971-appb-I000034
    [화학식 6][Formula 6]
    Figure PCTKR2015001971-appb-I000035
    Figure PCTKR2015001971-appb-I000035
    [화학식 7][Formula 7]
    Figure PCTKR2015001971-appb-I000036
    Figure PCTKR2015001971-appb-I000036
    [화학식 8][Formula 8]
    Figure PCTKR2015001971-appb-I000037
    Figure PCTKR2015001971-appb-I000037
    [화학식 9][Formula 9]
    Figure PCTKR2015001971-appb-I000038
    Figure PCTKR2015001971-appb-I000038
    상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,
    A는
    Figure PCTKR2015001971-appb-I000039
    이고, B는
    Figure PCTKR2015001971-appb-I000040
    이고, D는
    Figure PCTKR2015001971-appb-I000041
    이고, E는
    Figure PCTKR2015001971-appb-I000042
    이며,    A is
    Figure PCTKR2015001971-appb-I000039
    And B is
    Figure PCTKR2015001971-appb-I000040
    And D is
    Figure PCTKR2015001971-appb-I000041
    And E is
    Figure PCTKR2015001971-appb-I000042
    Is,
    Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
    X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,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, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 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 groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; 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; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or an C 3 ~ C 40 aryl siol group,
    a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고,a and d are each independently an integer of 1 to 100,000,
    b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
    e는 각각 독립적으로 1 또는 2이며,e are each independently 1 or 2,
    n은 각각 독립적으로 1 내지 20의 정수이다.n is independently an integer of 1-20.
  2. 제1항에 있어서,The method of claim 1,
    a는 3 내지 1000이고, b는 1 내지 500, d는 1 내지 500인 것을 특징으로 하는 표면강화 투명기판.a is 3 to 1000, b is 1 to 500, d is 1 to 500, the surface-reinforced transparent substrate.
  3. 제1항에 있어서,The method of claim 1,
    d는 2 내지 100인 것을 특징으로 하는 표면강화 투명기판.d is 2 to 100, the surface hardened transparent substrate.
  4. 제1항에 있어서,The method of claim 1,
    n 값의 평균이 4 내지 5인 것을 특징으로 하는 표면강화 투명기판.Surface-reinforced transparent substrate, characterized in that the average value of n is 4 to 5.
  5. 제1항에 있어서,The method of claim 1,
    상기 실세스퀴옥산 복합 고분자의 중량평균분자량이 1,000 내지 1,000,000인 것을 특징으로 하는 표면강화 투명기판.Surface-reinforced transparent substrate, characterized in that the weight average molecular weight of the silsesquioxane composite polymer is 1,000 to 1,000,000.
  6. 제1항에 있어서,The method of claim 1,
    상기 투명기판은 500 ㎚ 파장의 광원에서 투과율이 적어도 80 % 이상인 것을 특징으로 하는 표면강화 투명기판.And the transparent substrate has a transmittance of at least 80% or more in a light source having a wavelength of 500 nm.
  7. 제1항에 있어서,The method of claim 1,
    상기 기판은 COC(Cyclic olefin copolymer), PAc(Polyacrylate), PC(Polycarbonate), PE(Polyethylene), PEEK (Polyetheretherketone), PEI(Polyetherimide), PEN(Polyethylenenaphthalate), PES(Polyethersulfone), PET(Polyethyleneterephtalate), PI(Polyimide), PO(Polyolefin), PMMA(Polymethylmethacrylate), PSF(Polysulfone), PVA(Polyvinylalcohol), PVCi(Polyvinylcinnamate), TAC(Triacetylcellulose), 폴리실리콘(Poly Silicone), 폴리우레탄(Polyurethane) 및 에폭시 수지(Epoxy Resin)로 이루어진 군으로부터 선택되는 소재의 기판인 것을 특징으로 하는 표면강화 투명기판.The substrate is a cyclic olefin copolymer (COC), polyacrylate (PAc), polycarbonate (PC), polyethylene (PE), polyetheretherketone (PEEK), polyetherimide (PEI), polyethylenenaphthalate (PEN), polyethersulfone (PES), polyethylene terephtalate (PET), Polyimide (PI), Polyolefin (PO), Polymethylmethacrylate (PMMA), Polysulfone (PSF), Polyvinylalcohol (PVA), Polyvinylcinnamate (PVC), Triacetylcellulose (TAC), Polysilicon (Poly Silicone), Polyurethane (Polyurethane) and epoxy resins Surface-reinforced transparent substrate, characterized in that the substrate of the material selected from the group consisting of (Epoxy Resin).
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 기판은 2종 이상의 플라스틱 소재를 공압출하여 형성한 것을 특징으로 하는 표면강화 투명기판.The substrate is a surface-reinforced transparent substrate, characterized in that formed by co-extrusion of two or more plastic materials.
  9. 제1항에 있어서,The method of claim 1,
    상기 경화물의 두께는 0.01 내지 500 um인 것을 특징으로 하는 표면강화 투명기판.The thickness of the cured product is a surface-reinforced transparent substrate, characterized in that 0.01 to 500 um.
  10. 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅 조성물을 투명기판 위에 코팅하고 경화시키는 것을 특징으로 하는 투명기판의 표면강화방법.A method for strengthening the surface of a transparent substrate, comprising coating and curing a coating composition comprising a silsesquioxane composite polymer represented by any one of Formulas 1 to 9 on a transparent substrate.
  11. 제10항에 있어서,The method of claim 10,
    상기 코팅 조성물은 무용제 타입인 것을 특징으로 하는 투명기판의 표면강화방법.The coating composition is a surface strengthening method of the transparent substrate, characterized in that the solvent-free type.
  12. 제10항에 있어서,The method of claim 10,
    제1항에 따른 실세스퀴옥산 복합 고분자;Silsesquioxane composite polymer according to claim 1;
    개시제; 및Initiator; And
    유기용매;Organic solvents;
    를 포함하는 것을 특징으로 투명기판의 표면강화방법.Surface strengthening method of the transparent substrate comprising a.
  13. 제12항에 있어서,The method of claim 12,
    상기 실세스퀴옥산 복합 고분자가 코팅 조성물 100 중량부에 대하여 5 내지 90 중량부인 것을 특징으로 투명기판의 표면강화방법.The silsesquioxane composite polymer is a surface strengthening method of the transparent substrate, characterized in that 5 to 90 parts by weight based on 100 parts by weight of the coating composition.
  14. 제1항 기재의 표면강화 투명기판을 포함하는 전자제품.An electronic product comprising the surface hardened transparent substrate of claim 1.
  15. 제14항에 있어서,The method of claim 14,
    상기 전자제품은 스마트폰, 테블릿 PC, 노트북 PC, AIO(All-In-One) PC, LCD 모니터, TV, 광고판 또는 터치패널, 기판의 유연성을 요구하는 플렉시블 스마트 기기인 것을 특징으로 전자제품.The electronic product is a smartphone, a tablet PC, a notebook PC, an AIO (All-In-One) PC, an LCD monitor, a TV, an advertising board or a touch panel, an electronic product, which is a flexible smart device requiring flexibility of a board.
  16. 제14항에 있어서,The method of claim 14,
    상기 표면강화 투명기판은 윈도우 커버 기판 또는 보호필름으로 사용되는 것을 특징으로 전자제품.The surface strengthening transparent substrate is an electronic product, characterized in that used as a window cover substrate or a protective film.
  17. 제1항 기재의 표면강화 투명기판을 포함하는 보호판.A protective plate comprising the surface-reinforced transparent substrate of claim 1.
PCT/KR2015/001971 2014-02-28 2015-02-27 Transparent substrate having reinforced surfaces and method for manufacturing same WO2015130146A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580011148.8A CN106062053B (en) 2014-02-28 2015-02-27 Surface-enhanced transparent substrate and method for manufacturing same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0024507 2014-02-28
KR20140024507 2014-02-28
KR10-2015-0028601 2015-02-27
KR1020150028601A KR102367120B1 (en) 2014-02-28 2015-02-27 A surface enhanced transparent substrate and method for manufacturing thereof

Publications (1)

Publication Number Publication Date
WO2015130146A1 true WO2015130146A1 (en) 2015-09-03

Family

ID=54009387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/001971 WO2015130146A1 (en) 2014-02-28 2015-02-27 Transparent substrate having reinforced surfaces and method for manufacturing same

Country Status (1)

Country Link
WO (1) WO2015130146A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080007118A (en) * 2006-07-13 2008-01-17 신닛테츠가가쿠 가부시키가이샤 Film laminate and method of manufacturing the same
KR20130003491A (en) * 2011-06-30 2013-01-09 삼성디스플레이 주식회사 Protective window and display device comprising protective window
KR20130016069A (en) * 2011-08-03 2013-02-14 주식회사 동진쎄미켐 Photocurable organic-inorganic hybrid resin composition
KR20130081576A (en) * 2012-01-09 2013-07-17 삼성디스플레이 주식회사 Transparent laminate, window panel for display device and display device including the window panel
KR20130110018A (en) * 2012-03-27 2013-10-08 주식회사 동진쎄미켐 Ladder-like silsesquioxane polymer and resin composition for optical film comprising the same
KR20130118069A (en) * 2012-04-19 2013-10-29 제일모직주식회사 Window sheet and displaying apparatus comprising the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080007118A (en) * 2006-07-13 2008-01-17 신닛테츠가가쿠 가부시키가이샤 Film laminate and method of manufacturing the same
KR20130003491A (en) * 2011-06-30 2013-01-09 삼성디스플레이 주식회사 Protective window and display device comprising protective window
KR20130016069A (en) * 2011-08-03 2013-02-14 주식회사 동진쎄미켐 Photocurable organic-inorganic hybrid resin composition
KR20130081576A (en) * 2012-01-09 2013-07-17 삼성디스플레이 주식회사 Transparent laminate, window panel for display device and display device including the window panel
KR20130110018A (en) * 2012-03-27 2013-10-08 주식회사 동진쎄미켐 Ladder-like silsesquioxane polymer and resin composition for optical film comprising the same
KR20130118069A (en) * 2012-04-19 2013-10-29 제일모직주식회사 Window sheet and displaying apparatus comprising the same

Similar Documents

Publication Publication Date Title
WO2017034357A1 (en) Laminate and method for producing same
WO2013012274A2 (en) Touch panel
WO2018038436A1 (en) Diamine compound and method for producing same
WO2015016456A1 (en) Retardation film and image display device having same
WO2015133875A1 (en) Method for coating lumber and pulp using silsesquioxane composite polymer
WO2016085087A9 (en) (meth)acrylic compounds having high refractive index, preparation method therefor, optical sheet comprising same, and optical display device comprising same
WO2015133874A1 (en) Method for coating ceramic using silsesquioxane composite polymer
WO2015133876A1 (en) Method for coating fiber using silsesquioxane composite polymer
WO2016122191A1 (en) Coated product, and high-hardness curved surface hard coating method
WO2015152617A1 (en) Coating method for preventing bending phenomenon of substrate
WO2017043873A1 (en) Blue light absorption film
WO2015130146A1 (en) Transparent substrate having reinforced surfaces and method for manufacturing same
WO2020130261A1 (en) Crosslinking agent compound, photosensitive composition including same, and photosensitive material using same
WO2019093805A1 (en) Nitrogenous cyclic compound and color changing film comprising same
WO2015133873A1 (en) Method for coating plastic using silsesquioxane composite polymer
WO2015133857A1 (en) Method for coating metal using silsesquioxane composite polymer
WO2021221374A1 (en) Polyamide-based composite film and display device comprising same
WO2021060961A1 (en) Optical laminate and flexible display device comprising same
WO2015133864A1 (en) Thermoplastic resin composition comprising silsesquioxane composite polymer
WO2022055235A1 (en) Polyimide-based polymer film, and substrate for display device and optical device, each using same
WO2020130552A1 (en) Diamine compound, polyimide precursor using same, and polyimide film
WO2022203284A1 (en) Antibacterial monomer, antibacterial polymer composition including the antibacterial monomer, antibacterial film obtained from the antibacterial polymer composition, and article including the antibacterial film
WO2016122160A1 (en) Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same
WO2023153586A1 (en) Novel meta-polyhedral oligomeric silsesquioxane (meta-poss) compound, production method therefor, and composition comprising meta-poss compound produced thereby
WO2019054707A1 (en) Novel triazine derivative and photosensitive composition comprising same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15754788

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15754788

Country of ref document: EP

Kind code of ref document: A1