WO2015152617A1 - Procede de revêtement pour la prevention de phenomene de flexion de substrat - Google Patents

Procede de revêtement pour la prevention de phenomene de flexion de substrat Download PDF

Info

Publication number
WO2015152617A1
WO2015152617A1 PCT/KR2015/003192 KR2015003192W WO2015152617A1 WO 2015152617 A1 WO2015152617 A1 WO 2015152617A1 KR 2015003192 W KR2015003192 W KR 2015003192W WO 2015152617 A1 WO2015152617 A1 WO 2015152617A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
pomma
glyp
phenyl
eche
Prior art date
Application number
PCT/KR2015/003192
Other languages
English (en)
Korean (ko)
Inventor
신규순
정희정
최승석
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 US15/129,416 priority Critical patent/US10280336B2/en
Priority claimed from KR1020150044976A external-priority patent/KR102367173B1/ko
Publication of WO2015152617A1 publication Critical patent/WO2015152617A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/10—Applying the material on both sides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat

Definitions

  • the present invention relates to a method for preventing warpage coating of a substrate, and more particularly, to a method for preventing warpage coating of a substrate to form a coating layer having different densities on the surface of the substrate to form two or more coating layers, wherein the two or more coating layers At least one layer of the coating composition comprising a silsesquioxane composite polymer represented by a specific chemical formula and the coating can be cured not only to prevent warpage of the substrate, but also at the same time high surface hardness, excellent transparency, scratch resistance
  • the present invention relates to a coating method for preventing warpage of a substrate capable of imparting water repellency, antifouling properties, fingerprint resistance, thermal stability, and gloss property.
  • Substrates such as plastic, glass, wood or paper are used for various purposes.
  • the above substrates are warped as the area becomes larger.
  • the flatness was excellent as shown in FIG. 1, but as time goes by, the warpage may occur as shown in the thick line of FIG. 1, and even when the functional material is coated on the surface of the substrate to provide functionality. It may occur.
  • Such a warpage phenomenon of the substrate may act as a cause of a device defect, or there is a problem that degrades the utility of the overall product by aesthetics.
  • the present invention can not only prevent the warpage of the substrate through a simple coating process on the surface of the substrate, but also at the same time high surface hardness, excellent transparency, scratch resistance, water repellency,
  • An object of the present invention is to provide a coating method for preventing warpage of a substrate which can impart antifouling properties, anti-fingerprint properties, thermal stability, and gloss properties, and a substrate for preventing warpage.
  • the present invention provides a coating method for preventing warpage of the substrate
  • At least one of the two or more coating layers provides a coating method for preventing warpage of the substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
  • 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 is provided with a coating layer of two or more layers formed by coating a coating composition having a different density on the surface, at least one of the coating layer is a coating comprising a silsesquioxane composite polymer represented by any one of the formulas (1) to (9)
  • a warpage preventing substrate characterized in that formed in the composition.
  • the present invention also provides an article comprising the warpage preventing substrate.
  • the warpage prevention coating method of the substrate according to the present invention can not only prevent the warpage of the substrate through a simple coating process but at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint on the surface of the substrate By imparting heat stability and glossiness, the durability and utility value of the product can be greatly increased.
  • FIG. 1 is a schematic diagram showing a base material exhibiting the bending phenomenon according to the prior art.
  • 2 to 5 are schematic views showing the warpage phenomenon preventing substrate according to the present invention, respectively.
  • Figure 6 shows an imaginary reference point of the coating surface used in the warpage measurement method in the present invention.
  • the present invention is a coating method for preventing warpage of the substrate
  • At least one of the two or more coating layers provides a coating method for preventing warpage of the substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
  • 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.
  • R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
  • 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, and then 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.
  • 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 3 may be a polymer described in Table 5 or 6 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 coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, and preferably, the yarn represented by any one of Formulas 3 to 9 It is preferable to use sesquioxane composite polymer.
  • 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 solventless type when the silsesquioxane composite polymer is in a liquid state, and may 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 0.1-20 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.
  • 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 hardener is preferably included in 0.1-20 parts by weight based on 100 parts by weight of the composition.
  • 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
  • the coating composition may further include a pigment.
  • the silsesquioxane composite polymer represented by any one of Chemical Formulas 1 to 9 of the present invention may improve dispersibility of the pigment and have excellent compatibility with the pigment, and thus may have an excellent coloring effect.
  • the pigment may be a well-known pigment can be used, the content of the pigment can be selected and used by those skilled in the art in the appropriate range.
  • 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 is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.
  • Additives usable in the present invention include polyether-modified polydimethylsiloxane (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
  • the base material includes all of the conventional base materials in which warpage occurs, and concrete examples thereof include plastic, glass, metal thin film, wood, or pulp, and in particular, plastic (polyethylene, PE) , Polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET, PET), polyamides (PA), polyester (PES), polyvinyl chloride , PVC), polyurethane (PU), polycarbonate (PC), high hardness polycarbonate (PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE) ), Polyetheretherketone (PEEK), epoxy, polyacrylonitrile (PAN), silicone polymer, polyethylene oxide (pol) two or more plastic materials as well as a single plastic material such as yethylen oxide (PEO), polymethylen oxide (PMO), polyimide (PI), bioplastics, and polyetherimide (PEI), acrylic May be mixed, and may be a composite plastic mixed with plastic and inorganic plastic (poly
  • the substrate can be applied to all types of products, including sheets, films, injection moldings, moldings and beads because the solution process is also used in the form.
  • specific articles include a window cover substrate, a protective film, a protective plate of the display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Corrugated or paper coated products; Glass of the car; glasses; Or optical products, electronic products, glass used in solar cells, and the like, but are not limited thereto.
  • the coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, and preferably, the yarn represented by any one of Formulas 1 to 9 In the sesquioxane composite polymer, it is good to synthesize different materials with different densities by varying substituents, and coat the coating composition with the silsesquioxane composite polymer having different densities.
  • At least one coating composition used for forming two or more coating layers in the present invention is a coating composition containing a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, and the other coating layer (single layer or a plurality of layers) Can be used as a coating composition having a different density from the coating composition containing the silsesquioxane composite polymer or a silsesquioxane represented by any one of Formulas 1 to 9 above. It may be a coating composition containing a composite polymer. The coating composition having different densities is coated on the substrate to correct the warpage of the substrate.
  • At least one of the coating compositions including the silsesquioxane composite polymer may be used to increase the surface stability, thereby allowing the substrate to have excellent flatness.
  • all of the coating layers may be formed using a coating composition containing the silsesquioxane composite polymer represented by any one of Formulas 1 to 9.
  • the number of layers of the coating layer may be appropriately selected and applied by those skilled in the art as two or more layers, preferably 2 to 10 layers, and more preferably 2 to 6 layers. In this case, the productivity and the warpage prevention effect can be satisfied at the same time.
  • two or more coating layers may be formed on one surface of the substrate as shown in FIG. 2, or may be formed on both sides of the substrate as illustrated in FIGS. 3 and 4.
  • the second coating layer and the fourth coating layer of Figure 5 may be formed, and preferably, the outermost layer of the coating layer may be a coating composition containing a silsesquioxane composite polymer.
  • the polymer density difference of coating compositions having different densities is preferably 0.001 g / cm 3 or more, and more preferably 0.01 to 2 g / cm 3 .
  • the method of coating the coating composition on the surface of the substrate is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, dipping method
  • a person skilled in the art can arbitrarily select and apply a well-known method, such as a method of impregnation, gravure coating, and of course, in the curing method, the photocuring or thermal curing can be appropriately selected and applied according to the functional group of the composite polymer. to be.
  • the curing temperature in the case of thermosetting is 80 to 120.
  • the other coating layer may be formed thereon while one coating layer is finished until the curing process, and after coating and drying the first coating composition, the second coating composition on the dried coating layer After coating and drying, two coating layers may be formed through one curing process.
  • the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, still more preferably 1 to 100 um.
  • the coating thickness of the outermost layer is preferably 1 to 100um.
  • the surface hardness of 7H or more be stably secured to the outermost surface, but also excellent coating properties.
  • the surface hardness of the coating layer can stably exhibit 9H.
  • the present invention is provided with a coating layer of two or more layers formed by coating a coating composition having a different density on the surface, at least one of the coating layer is a coating comprising a silsesquioxane composite polymer represented by any one of the formulas (1) to (9)
  • the warpage preventing substrate can be prepared by the warpage preventing coating method of the substrate.
  • the warpage preventing substrate according to the present invention has a flatness within 0.1 mm based on a 100 mm ⁇ 300 mm substrate, and in the case of a substrate having a coating layer on both sides of the substrate (FIGS. 3 and 4), the warpage prevention effect is more excellent.
  • the coating layer When the coating layer is formed of a coating composition containing a silsesquioxane composite polymer in the outermost layer, the coating layer has a very high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, and It has the properties of moonshine, heat stability and gloss.
  • An article including the warpage preventing substrate according to the present invention is not particularly limited, and as a specific example, a window cover substrate, a protective film, a protective plate of a display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Corrugated or paper coated products; Glass of the car; glasses; Or glass used for optical products, electronic products, and solar cells.
  • 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% by weight 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 prepare a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method similar 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 similar 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
  • n value 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 stepwise to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method equivalent 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 n value of X was 4-6, the n value 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 n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are 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 To prepare a composite polymer having an E-A-B-D structure, the following method was used, and a coating composition was prepared by the same method as in Example 1.
  • Example 4-c To the mixture obtained in Example 4-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 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 n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 6 results are 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, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as 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 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 n value of X was 4-6
  • the n value 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 manufacture a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared by the same method 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 n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 8 results are as follows.
  • 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 0.36% by weight aqueous HCl solution was added dropwise, and 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 the styrene conversion value of 28,000, the n value of X was 4-6, the n value 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.
  • 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.
  • the base material was evaluated for the anti-bending properties of plastic PC (i-components, Glastic 0.5T), glass (Asahi, soda lime 0.5T) and natural wood (wood and human non-conveyor), and the results are shown in Table 28 (Plastic 28). ), Table 29 (glass) and Table 30 (wood).
  • Tables 28 to 30 the structure shown in FIG. 2 in the case of two-layer lamination, the structure shown in FIG. 5 in the case of four-layer lamination, and the structure shown in FIG.
  • the coating thickness is 10 um for single layer, 5 um for each layer (2 um for total thickness 10 um for two layers, 20 um for four layers), and for each layer. Coated to a thickness of 10 um.
  • Evaluation method was stored in 85%, 85 °C reliability chamber for 240 hours and evaluated the bending characteristics.
  • the evaluation method measured the degree of warp using a three-dimensional warpage measuring instrument, and as shown in Figure 6, the front part is divided into nine, and after designating the points 1, 3, 7 and 9 as the virtual reference plane, all 1 to 9 The height of the point was measured. At this time, the maximum (+ height) and the minimum (-height) value of the distance away from the reference plane was obtained and expressed.
  • the negative value of warp means downward warp, and the positive value of warp means upward warp.
  • Examples 1 to 9 refer to thermosetting coating compositions prepared in Examples 1 to 9, respectively, where a single layer is a single layer and a two layer layer is stacked as shown in FIG. It becomes the 1st coating layer of FIG. 2, the layer described later becomes a 2nd coating layer, and a 4-layer lamination is laminated
  • the first coating layer, the 2nd coating layer, the 3rd coating layer, A fourth coating layer is formed, and both surfaces are stacked as shown in FIG. 3, and the coating layer described first constitutes the first coating layer, and the coating layer described later constitutes the second coating layer.
  • Example 1 (single) 0.401 2
  • Example 2 (single) 0.310 3
  • Example 3 (single) 0.300 4
  • Example 4 (single) 0.502 5
  • Example 5 (single) -0.525 6
  • Example 6 (single) -0.301 7
  • Example 7 (single) -0.505 8
  • Example 8 (single) -0.355 9
  • Example 9 (single) -0.404 10
  • Example 1 Example 9 (two-layer lamination) 0.150 11
  • Example 2 + Example 8 (two-layer lamination) 0.195 12
  • Example 3 Example 7 (Lamination Layer) 0.181 13
  • Example 5 Example 1 (two-layer lamination) 0.181 15
  • Example 6 (Lamination Layer) 0.138 16
  • Example 7 + Example 3 (two-layer lamination) 0.145 17
  • Example 9 + Example 5 (two-layer
  • Example 9 (Glass material) Coating Layer No Coating layer composition Warp Measurement (mm) One Example 1 (single) 0.201 2 Example 2 (single) 0.160 3 Example 3 (single) 0.180 4 Example 4 (single) 0.152 5 Example 5 (single) -0.255 6 Example 6 (single) -0.151 7 Example 7 (single) -0.205 8 Example 8 (single) -0.175 9 Example 9 (single) -0.104 10 Example 1 + Example 9 (two-layer lamination) 0.115 11 Example 2 + Example 8 (two-layer lamination) 0.114 12 Example 3 + Example 7 (Lamination Layer) 0.104 13 Example 4 + Example 6 (Layer Layers) 0.103 14 Example 5 + Example 1 (two-layer lamination) 0.113 15 Example 6 + Example 2 (Lamination Layer) 0.115 16 Example 7 + Example 3 (two-layer lamination) 0.108 17 Example 8 + Example 6 (two-layer lamination) 0.112 18 Example 9 + Example 5 (two-layer lamination) 0.114 19
  • Example 9 Coating Layer No Coating layer composition Warp Measurement (mm) One Example 1 (single) 0.311 2 Example 2 (single) 0.350 3 Example 3 (single) 0.300 4 Example 4 (single) 0.352 5 Example 5 (single) -0.355 6 Example 6 (single) -0.451 7 Example 7 (single) -0.325 8 Example 8 (single) -0.305 9 Example 9 (single) -0.354 10 Example 1 + Example 9 (two-layer lamination) 0.180 11 Example 2 + Example 8 (two-layer lamination) 0.175 12 Example 3 + Example 7 (Lamination Layer) 0.191 13 Example 4 + Example 6 (Layer Layers) 0.170 14 Example 5 + Example 1 (two-layer lamination) 0.191 15 Example 6 + Example 2 (Lamination Layer) 0.165 16 Example 7 + Example 3 (two-layer lamination) 0.175 17 Example 8 + Example 6 (two-layer lamination) 0.171 18 Example 9 + Example 5 (two-layer lamination)
  • the anti-bending substrate of the present invention exhibited significantly improved excellent anti-bending properties when the material of the laminate is properly adjusted.
  • the double-sided coating showed very good bending resistance.
  • thermosetting coating composition in Tables 28 to 30, the results of the photocurable resin composition also showed comparable results with the thermosetting resin composition.
  • the pencil hardness method (JIS 5600-5-4) is generally rated at 750 g load, which is 10 mm horizontal at a rate of 0.5 mm per second at a 45-degree angle to the coating surface at a more severe 1 kgf load.
  • the coating film was moved to evaluate the scratches. If more than 3 mm of scratches are not found more than 2 times in 5 experiments, the pencil of the higher hardness is selected and evaluated. To evaluate the results are shown in Table 31 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.
  • the anti-bending substrate of the present invention showed excellent physical properties of the coating layers, and even in the case of four-layer lamination, the phenomenon of lifting due to excellent adhesion between the coating layers did not occur.
  • the warpage prevention coating method of the substrate according to the present invention can not only prevent the warpage of the substrate through a simple coating process but at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint on the surface of the substrate By imparting heat stability and glossiness, the durability and utility value of the product can be greatly increased.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un procédé de revêtement pour empêcher le phénomène de flexion d'un substrat et, plus particulièrement, un procédé de revêtement pour empêcher le phénomène de flexion d'un substrat, comprenant la formation d'au moins deux couches de revêtement par le revêtement de la surface d'un substrat avec des compositions de revêtement ayant des densités différentes, et la formation d'au moins une couche parmi lesdites au moins deux couches de revêtement par le revêtement d'une composition de revêtement contenant un polymère composite de silsesquioxane représenté par une formule chimique spécifique et le durcissement du produit revêtu, permettant ainsi d'empêcher le phénomène de flexion d'un substrat, et fournissant en même temps, à la surface du substrat, une dureté de surface élevée, une excellente transparence, une résistance à la rayure, des caractéristiques hydrofuges, des caractéristiques anti-salissures, une propriété anti-empreintes digitales et des caractéristiques de stabilité thermique et de brillant.
PCT/KR2015/003192 2014-03-31 2015-03-31 Procede de revêtement pour la prevention de phenomene de flexion de substrat WO2015152617A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/129,416 US10280336B2 (en) 2014-03-31 2015-03-31 Coating method for preventing bending phenomenon of substrate

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20140038126 2014-03-31
KR10-2014-0038126 2014-03-31
KR10-2015-0044976 2015-03-31
KR1020150044976A KR102367173B1 (ko) 2014-03-31 2015-03-31 기재의 휨현상 방지 코팅방법

Publications (1)

Publication Number Publication Date
WO2015152617A1 true WO2015152617A1 (fr) 2015-10-08

Family

ID=54240857

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/003192 WO2015152617A1 (fr) 2014-03-31 2015-03-31 Procede de revêtement pour la prevention de phenomene de flexion de substrat

Country Status (1)

Country Link
WO (1) WO2015152617A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180113383A1 (en) * 2016-10-25 2018-04-26 Tokyo Ohka Kogyo Co., Ltd. Coloring agent dispersion, photosensitive resin composition, cured product, organic el element, method for forming pattern, and method for producing photosensitive resin composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5746814A (en) * 1997-05-07 1998-05-05 Xerox Corporation Decurling compositions
WO2010058987A2 (fr) * 2008-11-19 2010-05-27 주식회사 엘지화학 Film multicouche et son procédé de production
US20120058333A1 (en) * 2009-03-27 2012-03-08 Asahi Glass Company, Limited Organo polysiloxane, hard coating composition, and resin substrate having hard coating layer
US20130072609A1 (en) * 2011-09-21 2013-03-21 Government Of The United States As Represented By The Secretary Of The Air Force Sythesis of functional fluorinated polyhedral oligomeric silsesquioxane (f-poss)
KR101249798B1 (ko) * 2010-08-18 2013-04-03 한국과학기술연구원 선택적으로 구조가 제어된 폴리실세스퀴옥산의 제조방법 및 이로부터 제조된 폴리실세스퀴옥산

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5746814A (en) * 1997-05-07 1998-05-05 Xerox Corporation Decurling compositions
WO2010058987A2 (fr) * 2008-11-19 2010-05-27 주식회사 엘지화학 Film multicouche et son procédé de production
US20120058333A1 (en) * 2009-03-27 2012-03-08 Asahi Glass Company, Limited Organo polysiloxane, hard coating composition, and resin substrate having hard coating layer
KR101249798B1 (ko) * 2010-08-18 2013-04-03 한국과학기술연구원 선택적으로 구조가 제어된 폴리실세스퀴옥산의 제조방법 및 이로부터 제조된 폴리실세스퀴옥산
US20130072609A1 (en) * 2011-09-21 2013-03-21 Government Of The United States As Represented By The Secretary Of The Air Force Sythesis of functional fluorinated polyhedral oligomeric silsesquioxane (f-poss)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180113383A1 (en) * 2016-10-25 2018-04-26 Tokyo Ohka Kogyo Co., Ltd. Coloring agent dispersion, photosensitive resin composition, cured product, organic el element, method for forming pattern, and method for producing photosensitive resin composition
JP2018070695A (ja) * 2016-10-25 2018-05-10 東京応化工業株式会社 着色剤分散液、感光性樹脂組成物、硬化物、有機ｅｌ素子、パターンの形成方法、及び感光性樹脂組成物の製造方法
US10416560B2 (en) * 2016-10-25 2019-09-17 Tokyo Ohka Kogyo Co, Ltd. Coloring agent dispersion, photosensitive resin composition, cured product, organic el element, method for forming pattern, and method for producing photosensitive resin composition
TWI746671B (zh) * 2016-10-25 2021-11-21 日商東京應化工業股份有限公司 著色劑分散液、感光性樹脂組合物、硬化物、有機el元件、圖案之形成方法、及感光性樹脂組合物之製造方法

Similar Documents

Publication Publication Date Title
WO2017034357A1 (fr) Stratifié et son procédé de production
KR20150113916A (ko) 기재의 휨현상 방지 코팅방법
WO2013012274A2 (fr) Écran tactile
WO2015133875A1 (fr) Procédé de revêtement du bois de charpente et d'un matériau à base de pâte à papier à l'aide d'un polymère composite de silsesquioxane
WO2015133874A1 (fr) Procédé de revêtement d'une céramique à l'aide d'un polymère composite de silsesquioxane
WO2015152617A1 (fr) Procede de revêtement pour la prevention de phenomene de flexion de substrat
WO2015133876A1 (fr) Procédé de revêtement d'une fibre à l'aide d'un polymère composite de silsesquioxane
WO2016085087A2 (fr) Composés (méth)acryliques ayant un indice de réfraction élevé, leur procédé de préparation, feuille optique les comprenant, et dispositif d'affichage optique l'utilisant
WO2022092465A1 (fr) Composition d'encre pour dispositif d'électrophorèse et appareil d'affichage l'utilisant
WO2016122191A1 (fr) Produit revêtu, et procédé de revêtement dur de surface courbée à dureté élevée
WO2017043873A1 (fr) Film d'absorption de lumière bleue
WO2015133873A1 (fr) Procede de revetement de plastique utilisant un polymere composite de silsesquioxane
WO2019093805A1 (fr) Composé cyclique azoté et film changeant de couleur comprenant celui-ci
WO2015130146A1 (fr) Substrat transparent ayant des surfaces renforcées et son procédé de fabrication
WO2020130261A1 (fr) Composé d'agent de réticulation, composition photosensible le comprenant, et matériau photosensible l'utilisant
WO2015133857A1 (fr) Procédé de revêtement du métal à l'aide d'un polymère composite de silsesquioxane
WO2022075673A1 (fr) Résine, composition de résine et dispositif d'affichage l'utilisant
KR20150102745A (ko) 표면강화 투명기판 및 이의 제조방법
WO2015133864A1 (fr) Composition de résine thermoplastique contenant un polymère composite de silsesquioxane
KR20150105611A (ko) 실세스퀴옥산 복합 고분자를 이용한 플라스틱코팅방법
WO2020153771A1 (fr) Composé diamine, et précurseur de polyimide et film de polyimide l'utilisant
WO2020184972A1 (fr) Copolymère de polyimide, procédé de production de copolymère de polyimide, et composition de résine photosensible, film de résine photosensible et dispositif optique l'utilisant
WO2022065886A1 (fr) Composition thermodurcissable à faible indice de réfraction, élément optique formé à partir de cette dernière et appareil d'affichage
WO2022055235A1 (fr) Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, chacun utilisant ce dernier
WO2022203284A1 (fr) Monomère antibactérien, composition de polymère antibactérien comprenant le monomère antibactérien, film antibactérien obtenu à partir de la composition de polymère antibactérien, et article comprenant le film antibactérien

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: 15773217

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15129416

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 15773217

Country of ref document: EP

Kind code of ref document: A1