[go: up one dir, main page]

WO2015009114A1 - Vitrage en polycarbonate et son procédé de production - Google Patents

Vitrage en polycarbonate et son procédé de production Download PDF

Info

Publication number
WO2015009114A1
WO2015009114A1 PCT/KR2014/006570 KR2014006570W WO2015009114A1 WO 2015009114 A1 WO2015009114 A1 WO 2015009114A1 KR 2014006570 W KR2014006570 W KR 2014006570W WO 2015009114 A1 WO2015009114 A1 WO 2015009114A1
Authority
WO
WIPO (PCT)
Prior art keywords
polycarbonate
coating layer
hard coating
glazing
polycarbonate glazing
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2014/006570
Other languages
English (en)
Korean (ko)
Inventor
김병수
강세영
김중인
이대규
최우석
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
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
Priority claimed from KR1020130101338A external-priority patent/KR20150010540A/ko
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Publication of WO2015009114A1 publication Critical patent/WO2015009114A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • 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
    • C08J7/048—Forming gas barrier 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
    • C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/54—Nitrogen-containing linkages
    • 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
    • C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • the present invention relates to a polycarbonate glazing and a method of manufacturing the same.
  • plastic materials have contributed to the weight reduction of automobiles, improving design and design freedom, granting new functions, and reducing costs. It is preferred as an alternative material for parts that have been difficult to resinize.
  • plastic materials such as polycarbonate (PC) and polymethyl methacrylate (PMMA), etc.
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • Automotive window modules offer new uses for the plastic materials due to various advantages in areas such as styling / design, weight reduction, stability / safety and the like.
  • plastic materials not only differentiate the vehicle from competing vehicles by increasing the overall design and shape complexity, but also provide the automobile manufacturer with the ability to reduce the complexity of the window assembly by integrating functional parts into molded plastic modules.
  • the use of lightweight plastic window modules promotes the vehicle's low center of gravity and fuel economy.
  • the plastic window module can increase the overall stability of the vehicle by strengthening the occupant's support in a rollover accident.
  • plastic materials such as polycarbonate have a problem in that scratch resistance and abrasion resistance are weak.
  • PECVD plasma enhanced chemical vapor deposition
  • CVD chemical vapor deposition
  • sputtering sol-gel, or the like.
  • the PECVD method, the CVD method, and the sputtering method have a problem that the apparatus is expensive and the control for forming a high quality coating film is troublesome.
  • the sol-gel method the required firing temperature is higher than 500 ° C., which makes the process difficult. There is a problem.
  • the problem to be solved by the present invention is to provide a polycarbonate glazing excellent in wear resistance.
  • Another problem to be solved by the present invention is to provide a polycarbonate glazing excellent transparency.
  • Another object of the present invention is to provide a polycarbonate glazing excellent in adhesion between the polycarbonate-based substrate and the hard coating layer.
  • Another object of the present invention is to provide a polycarbonate glazing having low water permeability and excellent gas barrier properties.
  • Another problem to be solved by the present invention is to provide a polycarbonate glazing excellent in pollution resistance.
  • Another problem to be solved by the present invention is to provide a polycarbonate glazing with excellent flexibility to prevent cracking.
  • Another object of the present invention is to provide a method for producing a polycarbonate glazing having a short manufacturing time and excellent processability by enabling non-vacuum wet coating.
  • One aspect of the invention is a polycarbonate-based substrate; And a hard coating layer formed on one surface of the substrate, wherein the hard coating layer is an organic-inorganic mixed layer derived from polysilazane or polysiloxane, and 500 g of CS-10F wear wheel using a taper abraser. It is related to polycarbonate glazing in which the haze difference ( ⁇ Haze) before and after abrasion is about 6.0 or less and the permeability difference ( ⁇ Transmittance) is about 0.8 or less at 500 wear under load conditions.
  • Another aspect of the present invention relates to a method for producing a polycarbonate glazing comprising forming a hard coating layer with a coating liquid containing polysilazane or polysiloxane on one side of a polycarbonate-based substrate.
  • Polycarbonate glazing of the present invention is excellent in wear resistance and transparency, excellent adhesion between the polycarbonate-based substrate and the hard coating layer without a separate primer layer, excellent water barrier properties, low gas permeability, and excellent pollution resistance.
  • the polycarbonate glazing manufacturing method of the present invention is non-vacuum wet coating by a wet process, the manufacturing time is short and excellent processability.
  • FIG. 1 is a cross-sectional view of a polycarbonate glazing in accordance with one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a polycarbonate glazing in accordance with another embodiment of the present invention.
  • the polycarbonate glazing may include a substrate including polycarbonate and at least one coating layer laminated on the substrate.
  • the polycarbonate glazing 100 is a polycarbonate-based substrate 110; And it may include a hard coating layer 120 formed on one surface of the polycarbonate-based substrate 110.
  • the polycarbonate-based substrate 110 includes a polycarbonate-based resin, and the polycarbonate-based resin may be used without limitation within a range capable of achieving the object of the present invention.
  • polycarbonate, polycarbonate copolymer or polycarbonate blending resin may be used, and the blending resin may be polyamide, thermoplastic polyurethane (TPU), acrylonitrile-styrene-acrylonitrile, polymethyl methacrylate.
  • TPU thermoplastic polyurethane
  • a blended polycarbonate with at least one polymer resin selected from the group consisting of polyester and acrylonitrile-butadiene-styrene may be used, but is not limited thereto.
  • 2 or more types can be mixed and used.
  • the polycarbonate may be prepared by reacting a dihydric phenol compound with phosgene in the presence of a molecular weight modifier and a catalyst according to a conventional production method.
  • the polycarbonate may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate.
  • a bisphenol compound may be used as the dihydric phenol compound, and for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used.
  • bisphenol A may be partially or wholly replaced by another type of dihydric phenol compound.
  • the polycarbonate resin has a tensile strength of about 60 MPa or more, a tensile modulus of about 1.5 GPa or more, a Vicat softening point of about 120 ° C. or more, and a total light transmittance. This may be at least about 80%.
  • the thickness of the polycarbonate-based substrate 110 may be about 1 mm to 10 mm. Within this range, mechanical strength, flexibility, transparency, and the like may be excellent as a substrate of the polycarbonate glazing.
  • the hard coating layer 120 may be formed on the polycarbonate-based substrate 110.
  • the hard coat layer 120 may be derived from polysiloxane or polysilazane. Specifically, the hard coating layer 110 is coated with a hydrogenated polysiloxane or polysilazane, and a coating solution containing an organic solvent on one side of the polycarbonate-based substrate 120, the hydrogenated polysilazane or included in the coating solution through a modification process
  • a siloxane compound, such as hydrogenated polysiloxane may be ceramicized to be converted into silicon dioxide (SiO 2 ) to form a coating layer containing silicon oxide (SiO x).
  • the hard coating layer 120 may have a thickness of about 50 to 3,000 nm, specifically about 100 to 1,000 nm. It is possible to secure sufficient wear resistance in the thickness range, it is possible to minimize the occurrence of cracks. In addition, since the hard coating layer 120 is formed by a wet process, it is possible to secure sufficient adhesion or adhesion without forming a separate primer layer on the polycarbonate-based substrate. Therefore, it may be formed directly on the polycarbonate-based substrate 110.
  • Polycarbonate glazing according to an embodiment of the present invention may be excellent in wear resistance by having a hard coating layer derived from polysiloxane or polysilazane.
  • the polycarbonate glazing has a haze difference ( ⁇ Haze) of about 6.0 or less after wear and wear 500 times under a CS-10F wear wheel and 500 g load condition using a taper abraser.
  • the transmittance difference ( ⁇ Transmittance) may be about 0.8 or less.
  • the polycarbonate glazing according to an embodiment of the present invention has a modulus of about 45 to 60 GPa, thereby minimizing the crack of the hard coating layer and ensuring sufficient strength, and has excellent wear resistance.
  • modulus means a value measured at room temperature using a nanoindenter Ti 750 Ubi (manufactured by Hysitron). In the present invention, room temperature means 25 ° C ⁇ 3 ° C unless otherwise specified.
  • the polycarbonate glazing according to an embodiment of the present invention has a water permeability (WVTR) (g / m 2 / day) is measured using the Aquatran Model 1 (Mocon Co., Ltd.) according to ASTM F-1249 standard ( 1.0) g / (m 2 ⁇ day) or less, excellent barrier property against gas and impurities.
  • WVTR water permeability
  • the polycarbonate glazing according to an embodiment of the present invention may have a surface roughness (Ra) of about 1 to 50nm, it is possible to obtain a polycarbonate glazing improved surface flatness due to the hard coating layer.
  • FIG. 2 shows a cross-sectional view of a polycarbonate glazing in accordance with another embodiment of the present invention.
  • the polycarbonate glazing according to another embodiment of the present invention is substantially the same as the polycarbonate glazing according to the embodiment of the present invention except that an intermediate layer is further laminated between the polycarbonate-based substrate and the hard coating layer. The explanation will focus on the middle layer.
  • the intermediate layer 130 may be a laminate structure of a bonding layer, a functional layer or a bonding layer, and a functional layer, and may be a laminate structure of at least one layer.
  • the functional layer may be, for example, an ultraviolet blocking layer, a buffer layer, an abrasion resistant layer, a barrier layer, or the like, and may be a plurality of layers in combination thereof.
  • the intermediate layer 130 may improve the bonding force between the polycarbonate-based substrate 110 and other layers, and selected from amide resin, acrylic resin, urethane resin, siloxane resin, silicone resin or copolymer thereof It may include, but is not limited to, a substance. Specifically, aliphatic polyether thermoplastic polyurethanes, polyester / polyether thermoplastic polyurethanes, anionic fatty polyester based polyurethanes, anionic fatty polyester / polyether polyurethanes, aqueous polyurethanes, polyamides, and polyester acrylics And the like.
  • the intermediate layer 130 may include a material that absorbs light having a wavelength of about 200 to 340 nm, which is an ultraviolet region, as an ultraviolet absorber to protect the polycarbonate-based substrate from ultraviolet rays to improve weather resistance.
  • the ultraviolet absorber may include metal oxide fine particles, an organic compound, and the like, and specifically, may include metal oxide.
  • the metal oxide used as the ultraviolet absorber is a fine particle having an average particle diameter of about 1 to 100 nm, for example, about 5 to 25 nm, selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide, and the like. It may comprise one or more fine particles.
  • the organic compound used as the ultraviolet absorber may include a benzotriazole, triazine, or the like.
  • the ultraviolet absorber may include a HALS agent having an antioxidant function, for example, a hindered amine compound may be used as the HALS agent.
  • the intermediate layer 130 may include a binder resin, and the binder resin may include an acrylate monomer, an acrylate oligomer, a siloxane monomer, a siloxane polymer, a silicone monomer, a silicone polymer, an acrylic resin, or a uritan based resin. Resins and the like can be used.
  • the intermediate layer 130 is a silicon-based having a silica network structure formed by condensation reaction of a hydrolyzed alkoxy silane by a colloidal silica sol by sol-gel synthesis It may be a buffer layer.
  • a trivalent or tetravalent alkoxy silane can be used.
  • the alkoxy silane include vinyltrimethoxysilane, propyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, methyltrimethoxysilane and the like. May be used alone or in combination.
  • the intermediate layer 130 may be an acrylic wear resistant layer including a photocurable resin and silica nanoparticles.
  • the photocurable resin may be formed by curing an ultraviolet curable compound having an acrylate functional group.
  • the ultraviolet curable compound may be a polyfunctional (meth) acrylate compound and the like.
  • polyfunctional acrylate compound ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, di Obtained by esterifying pentaerythritol hexa (meth) acrylate, polyol poly (meth) acrylate, di (meth) acrylate of bisphenol A-diglycidyl ether, polyhydric alcohol and polyhydric carboxylic acid, and its anhydride and acrylic acid Ester (meth) acrylate, a siloxane compound containing an acrylate functional group, urethane (meth) acrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, and the like may be used, but is not limited thereto.
  • the silica nanoparticles may have an average particle diameter (D50) of about 100 nm or less, for example, about 10 to 50 nm, and about 50 wt% or less, for example, about 5 to 40 wt% of the acrylic wear resistant layer.
  • D50 average particle diameter
  • the hardness may be increased to further improve wear resistance.
  • the coating solution for forming a hard coat layer may be hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof; And solvents. Referring to each component constituting the coating solution is as follows.
  • the coating solution of the present invention may include a hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof as a composition for forming a silicon oxide layer.
  • the hydrogenated polysiloxane or hydrogenated polysilazane may be converted to a silicon oxide material by heating and oxidation, and a hard coating layer having excellent wear resistance may be obtained.
  • the hydrogenated polysiloxane may include silicon-oxygen-silicon (Si-O-Si) bonding units in addition to silicon-nitrogen (Si-N) bonding units in the structure.
  • silicon-oxygen-silicon (Si-O-Si) bonding units can alleviate stress upon curing to reduce shrinkage.
  • Hydrogenated polysilazanes have a basic backbone in the structure including silicon-hydrogen (Si-H), nitrogen-hydrogen (N-H) coupling units in addition to silicon-nitrogen (Si-N) coupling units.
  • the (Si-N) bond may be substituted with a (Si-O) bond.
  • the hydrogenated polysiloxane may have a unit represented by Formula 1, a unit represented by Formula 2, and a terminal portion represented by Formula 3 below:
  • R 1 to R 7 are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 Aryl group, substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkene It means a niyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof.
  • substituted means hydrogen, halogen atom, hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, carbonyl group, carbamyl group, thiol group, ester group, Carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphate groups or salts thereof, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and carbon atoms
  • An aryl group having -30, an aryloxy group having 6-30 carbon atoms, a cycloalkyl group having 3-30 carbon atoms, a cycloalkenyl group having 3-30 carbon atoms, a cycloalkynyl group having 3-30 carbon atoms, or a combination thereof is meant.
  • the hydrogenated polysiloxane or hydrogenated polysilazane may have an oxygen content of about 0.2% to 3% by weight.
  • the stress relaxation by the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient to prevent shrinkage during heat treatment and thus prevent the occurrence of cracks in the formed hard coating layer.
  • the oxygen content of the hydrogenated polysiloxane or hydrogenated polysilazane may be about 0.2 to 3% by weight, specifically about 0.5 to 2% by weight.
  • the hydrogenated polysiloxane or polysilazane has a structure in which the terminal portion is capped with hydrogen, and the terminal group represented by Formula 3 is about 15 with respect to the total content of Si—H bonds in the hydrogenated polysiloxaneoxane or hydrogenated polysilazane structure. To 35% by weight.
  • the terminal group of Formula 3 may be included in about 20 to 30% by weight relative to the total content of Si-H bonds in the hydrogenated polysiloxane or hydrogenated polysilazane structure.
  • the hydrogenated polysiloxane or hydrogenated polysilazane of the present invention may have a weight average molecular weight (Mw) of about 1,000 to 5,000 g / mol. In the above range, it is possible to form a dense organic-inorganic mixed layer with a thin film coating while reducing components to evaporate during heat treatment.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) may be about 1,500 to 3,500 g / mol.
  • the hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof may be included in an amount of about 0.1 to 50% by weight based on the total content of the coating solution. When included in the above range can maintain a suitable viscosity and can be formed flat and evenly without bubbles and voids (Void).
  • the solvent may be used as long as it is a solvent which can dissolve them without being reactive with hydrogenated polysiloxane or hydrogenated polysilazane.
  • a solvent containing no -OH group is preferable because it is reactive with the siloxane compound.
  • ethers such as hydrocarbon solvents, such as aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon, halogenated hydrocarbon solvent, aliphatic ether, alicyclic ether, can be used.
  • hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbetso, and taben, halogen hydrocarbons such as methylene chloride and tricholoethane, dibutyl ether, dioxane, tetra hybrido furan and the like Ryu.
  • halogen hydrocarbons such as methylene chloride and tricholoethane, dibutyl ether, dioxane, tetra hybrido furan and the like Ryu.
  • the solubility of a siloxane compound, the evaporation rate of a solvent, etc. may be selected suitably, and a some solvent may be mixed.
  • the coating liquid of the present invention may further include a thermal acid generator (TAG).
  • TAG thermal acid generator
  • the thermal acid generator is an additive for improving the developability of the hydride polysiloxane and the contamination by uncuring, so that the hydride polysiloxane may be developed at a relatively low temperature.
  • the thermal acid generator is not particularly limited as long as it is a compound capable of generating an acid (H +) by heat, but may be selected to have low volatility by being activated at about 90 ° C. or higher to generate sufficient acid.
  • Such thermal acid generators can be selected, for example, from nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonate and combinations thereof.
  • the thermal acid generator may be included in about 25% by weight or less, for example about 0.01 to 20% by weight based on the total content of the coating liquid. When included in the above range, the siloxane compound may be developed at a relatively low temperature.
  • the coating liquid of the present invention may further include a surfactant.
  • the said surfactant is not specifically limited, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether, polyoxyethylene rail ether, polyoxyethylene nonyl phenol ether, etc.
  • Polyoxyethylene sorbitan such as polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate
  • Nonionic surfactants such as fatty acid esters, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megapack F171, F173 (manufactured by Dainippon Ink, Inc.).
  • Fluorine-based surfactants such as Prorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahigara Corporation), or Kano siloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc., etc. are mentioned.
  • the surfactant may be included in about 10% by weight or less, for example, about 0.001 to 5% by weight based on the total content of the coating liquid.
  • Method for producing a polycarbonate glazing may include forming a hard coating layer with a coating liquid containing a hydrogenated polysilazane or a hydrogenated polysiloxane to one side of the substrate. Specifically, it may include forming a hard coat layer by applying a coating solution and then modifying it.
  • a coating liquid containing polysilazane or polysiloxazane is applied onto the polycarbonate-based substrate.
  • the coating solution may be applied by roll coating, spin coating, bar coating, dip coating, flow coating, spray coating, or the like, but is not limited thereto. Do not.
  • the spin coating may be applied to the coating solution for about 10 to 60 seconds at about 500 to 4,000rpm, the coating may be repeated one or more times.
  • the coating thickness of the coating solution may be about 50 to 3,000 nm, and after coating the coating solution may be dried for about 1 to 100 minutes at about 50 to 100 °C and relative humidity about 40 to 90%.
  • the modification to form the hard coat layer refers to a process of converting a siloxane compound such as hydrogenated polysiloxane or hydrogenated polysilazane into silicon dioxide to ceramic.
  • the silazane or polysiloxane compound in order to increase the conversion rate of the silazane or polysiloxane compound to silicon dioxide, it may be ceramicized under ultraviolet irradiation or high temperature, high humidity.
  • the ultraviolet irradiation may be performed using a vacuum ultraviolet. Specifically, about 100 to 200 nm vacuum ultraviolet light may be used. Irradiation intensity and irradiation amount of ultraviolet ray can be set suitably.
  • the ultraviolet radiation may be irradiated at an irradiation intensity of about 10 to 200 mW / cm 2 and an irradiation amount of about 100 to 6,000 mJ / cm 2 for about 0.1 to 5 minutes.
  • the dosage may be about 1,000 to 5,000 mJ / cm 2.
  • the ceramicization under high temperature and high humidity may be, for example, heat treatment at about 300 to 1,500 ° C. for about 1 to 12 hours.
  • the heat treatment may further include a heat treatment for about 40 to 100 minutes at 90% of the conditions.
  • the inside of the 2L reactor equipped with the stirrer and the temperature controller was replaced with dry nitrogen, and 2.0 g of pure water was injected into 1,500 g of dry pyridine, followed by sufficient mixing.
  • 100 g of dichlorosilane was slowly injected over 1 hour, and then 70 g of ammonia was slowly injected over 3 hours with stirring.
  • dry nitrogen was injected for 30 minutes and the ammonia remaining in the reactor was removed.
  • the product on the obtained white slurry was filtered using a 1 ⁇ m Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtrate.
  • a hard coating layer coating solution I was prepared by filtration with a filter made of 0.03 ⁇ m of Teflon filter.
  • the oxygen content of the obtained hydrogenated polysiloxazane is 0.5%, SiH 3 / SiH ( total) is 0.20, a weight average molecular weight of 2,000g / mol.
  • tetraethyl silicate TEOS, Sigma-Aldrich Co., Ltd.
  • MTMS methyltrimethoxysilane
  • the molar ratio of tetraethyl silicate and methyltrimethoxysilane added is 1: 2.
  • silica particles SiO 2 , FUSO Co., Ltd.
  • urethane acrylate resin (UNIDIC RC27-947, DIC CORPORATION) was added to 69.0 g of solvent isopropyl alcohol (IPA, Samjeon Pure Chemical Co., Ltd., KBM503) and stirred, while stirring, and Igacure 184 (Igacure 184, Ciba Co., Ltd.) as a photoinitiator. After adding 3 g additionally, the resin solution was prepared by stirring at 700 rpm for 20 minutes. Thereafter, silica particles (SiO 2 , FUSO Co., Ltd.) were added to 30 parts by weight of the resin solids to prepare a hard coating solution III.
  • solvent isopropyl alcohol IPA, Samjeon Pure Chemical Co., Ltd., KBM503
  • Igacure 184 Igacure 184, Ciba Co., Ltd.
  • Igacure 184 (Igacure 184, Ciba) was added as a photoinitiator, followed by stirring at 700 rpm for 20 minutes, and isopropyl alcohol (IPA, Samjeon Pure Chemical Co., Ltd.) KBM503 ) 57.0 g was added and stirred for 20 minutes, and finally, 0.1 g of polyether-modified polydimethyl siloxane (BYK306) was added as a leveling improving additive, followed by stirring for 10 minutes to prepare a resin solution. Thereafter, silica particles (SiO 2 , FUSO Co., Ltd.) were added at 30 parts by weight based on the resin solid content to prepare a hard coating solution IV.
  • silica particles SiO 2 , FUSO Co., Ltd.
  • the inorganic coating having a thickness of 500 nm was formed by spin coating a hard coating layer coating solution I on one surface of a polycarbonate substrate (LEXAN, GE) having a thickness of 3 mm. At this time, the coating solution was used to dilute the solid content to 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,000rpm for 20 seconds, dried for 3 minutes at 80 °C convection oven, UV irradiation (SMT Co., Ltd.) CR403) was exposed to irradiation intensity of 14mW / cm 2 for 143 seconds, UV irradiation at 2,000mJ / cm 2 , and then left at room temperature for 24 hours to prepare polycarbonate glazing, and the measured values were measured in Table 1 below. Indicated.
  • an inorganic layer having a thickness of 500 nm was formed by spin coating with a hard coating layer coating solution I.
  • the coating solution was used to dilute the solid content to 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,000rpm for 20 seconds, dried for 3 minutes at 80 °C convection oven, UV irradiation (SMT Co., Ltd.) CR403) was exposed to irradiation intensity of 14 mW / cm 2 for 214 seconds, UV irradiation at 4,000 mJ / cm 2 , and then left at room temperature for 24 hours to prepare polycarbonate glazing, and the measured values were measured in Table 1 below. Indicated.
  • an inorganic layer having a thickness of 1,000 nm was formed by spin coating with a hard coating layer coating solution I.
  • the coating solution was diluted with DBE (dibuthyl ether) so that the solid content was 9.5%.
  • the spin coating was coated for 20 seconds at 1,000 rpm, then dried for 3 minutes in an 80 ° C. convection oven, and again for 20 seconds at 1,000 rpm, followed by drying for 3 minutes in an 80 ° C. convection oven.
  • UV irradiation was performed at 14mW / cm 2 for 143 seconds using UV irradiator (SMT CR403) and UV irradiation at 2,000mJ / cm 2 , and then left at room temperature for 24 hours to prepare polycarbonate glazing.
  • SMT CR403 UV irradiator
  • UV irradiation was performed at 14mW / cm 2 for 143 seconds using UV irradiator (SMT CR403) and UV irradiation at 2,000mJ / cm 2 , and then left at room temperature for 24 hours to prepare polycarbonate glazing.
  • SMT CR403 UV irradiator
  • a coating layer having a thickness of 500 nm was formed by spin coating with a hard coating layer coating solution II.
  • the spin coating was coated for 20 seconds at 1,000rpm, dried for 3 minutes at 80 °C convection oven, 2,000mJ / cm 2 by exposure for 14 minutes at 14mW / cm 2 irradiation intensity in a UV irradiator (CR403) SMT
  • UV irradiator CR403 SMT
  • a coating layer having a thickness of 1,000 nm was formed by spin coating the hard coating layer coating solution III. At this time, the spin coating was coated for 20 seconds at 1,000rpm, dried for 3 minutes in an 80 °C convection oven, polycarbonate glazing was prepared by UV irradiation at 350mJ / cm light using a high-pressure mercury lamp, measured physical properties The measured values are shown in Table 1 below.
  • a coating layer having a thickness of 1,000 nm was formed by spin coating with a hard coating layer coating solution IV. At this time, the spin coating was coated for 20 seconds at 1,000rpm, dried for 3 minutes in an 80 °C convection oven, polycarbonate glazing was prepared by UV irradiation at 350mJ / cm light using a high-pressure mercury lamp, measured physical properties The measured values are shown in Table 1 below.
  • Abrasion resistance Haze before and after abrasion with haze meter (NHD 2000N, Nippon Denshoku) when wear 500 times under CS-10F wear wheel and 500g load condition using Taber Abraser Transmittance was measured respectively.
  • Adhesion 100 points were made by making a checkerboard scale by drawing lines on the specimen at 2mm intervals. The number of times where peeling did not occur was carried out by tape-taking and pulling once strongly in a vertical direction.
  • Moisture Permeability (g / m 2 / day): Measured according to ASTM F-1249 standard using Aquatran Model1 (Mocon). Specimen size is 100 * 100mm.
  • the PC glazing of the embodiment including a hard coating layer derived from polysilazane or polysiloxane and formed by a wet process has a haze difference ( ⁇ Haze) and a transmittance difference ( ⁇ Transmittance) before and after wear. ) Is lower than the comparative example, and it can be seen from this that the wear resistance is excellent.
  • the PC glazing of the embodiment is excellent in adhesion between the substrate and the hard coating layer without having a separate primer layer, low moisture permeability (WVTR), excellent barrier properties, low surface roughness, surface flatness of the hard coating layer It can be seen that it is excellent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un vitrage en polycarbonate et son procédé de production, le vitrage en polycarbonate comprenant : un substrat à base de polycarbonate ; et une couche de revêtement dur à base de silicium formée sur un côté du substrat, la couche de revêtement dur étant dérivée de polysilazanes ou de polysiloxazanes et, lorsqu'elle est soumise à une abrasion pendant 500 cycles à l'aide d'un abrasimètre Taber avec une roue abrasive CS-10F sous une charge de 500 g, présente une différence de trouble (△trouble) avant et après l'abrasion d'au plus environ 6,0 et une différence de transmittance (△transmittance) d'au plus environ 0,8. Le vitrage en polycarbonate présente des propriétés supérieures de résistance à l'abrasion et de transparence, une adhérence supérieure entre le substrat à base de polycarbonate et la couche de revêtement dur même sans couche d'apprêt indépendante, d'excellentes propriétés de barrière aux gaz du fait d'une faible perméabilité à l'humidité et une résistance supérieure à l'encrassement. De plus, le procédé de production d'un vitrage en polycarbonate selon la présente invention permet un revêtement humide sans vide dans un procédé par voie humide et présente ainsi un temps de production réduit et une aptitude au traitement supérieure.
PCT/KR2014/006570 2013-07-19 2014-07-18 Vitrage en polycarbonate et son procédé de production Ceased WO2015009114A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0085674 2013-07-19
KR20130085674 2013-07-19
KR1020130101338A KR20150010540A (ko) 2013-07-19 2013-08-26 폴리카보네이트 글래이징 및 그 제조방법
KR10-2013-0101338 2013-08-26

Publications (1)

Publication Number Publication Date
WO2015009114A1 true WO2015009114A1 (fr) 2015-01-22

Family

ID=52346483

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/006570 Ceased WO2015009114A1 (fr) 2013-07-19 2014-07-18 Vitrage en polycarbonate et son procédé de production

Country Status (1)

Country Link
WO (1) WO2015009114A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108574024A (zh) * 2018-02-01 2018-09-25 横店集团东磁股份有限公司 一种用于湿法刻蚀的挤水滚轮
US11307329B1 (en) 2021-07-27 2022-04-19 Racing Optics, Inc. Low reflectance removable lens stack
US11364715B2 (en) 2019-05-21 2022-06-21 Racing Optics, Inc. Polymer safety glazing for vehicles
US11490667B1 (en) 2021-06-08 2022-11-08 Racing Optics, Inc. Low haze UV blocking removable lens stack
US11524493B2 (en) 2019-02-01 2022-12-13 Racing Optics, Inc. Thermoform windshield stack with integrated formable mold
US11548356B2 (en) 2020-03-10 2023-01-10 Racing Optics, Inc. Protective barrier for safety glazing
US11625072B2 (en) 2010-05-14 2023-04-11 Racing Optics, Inc. Touch screen shield
US11622592B2 (en) 2014-06-17 2023-04-11 Racing Optics, Inc. Adhesive mountable stack of removable layers
US11648723B2 (en) 2019-12-03 2023-05-16 Racing Optics, Inc. Method and apparatus for reducing non-normal incidence distortion in glazing films
US11709296B2 (en) 2021-07-27 2023-07-25 Racing Optics, Inc. Low reflectance removable lens stack
US11808952B1 (en) 2022-09-26 2023-11-07 Racing Optics, Inc. Low static optical removable lens stack
US11846788B2 (en) 2019-02-01 2023-12-19 Racing Optics, Inc. Thermoform windshield stack with integrated formable mold
US11933943B2 (en) 2022-06-06 2024-03-19 Laminated Film Llc Stack of sterile peelable lenses with low creep
US12140781B2 (en) 2021-07-27 2024-11-12 Laminated Film Llc Low reflectance removable lens stack
US12162330B2 (en) 2022-02-08 2024-12-10 Ro Technologies, Llc Multi-layer windshield film having progressive thickness layers
US12292205B2 (en) 2020-03-10 2025-05-06 Ro Technologies, Llc Protective barrier for safety glazing
US12358266B2 (en) 2019-12-03 2025-07-15 Ro Technologies, Llc Method and apparatus for reducing non-normal incidence distortion in glazing films

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5919572A (en) * 1992-11-19 1999-07-06 Sri International Temperature-resistant and/or nonwetting coating of cured, silicon-containing polymers
US20030083453A1 (en) * 2001-05-07 2003-05-01 Kion Corporation Thermally stable, moisture curable polysilazanes and polysiloxazanes
KR20070010025A (ko) * 2004-03-09 2007-01-19 엑사테크 엘.엘.씨. 비평면 기재를 위한 플라즈마 코팅 시스템
KR20070043849A (ko) * 2004-08-20 2007-04-25 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 반도체 소자 및 그 제조방법
KR20090047885A (ko) * 2007-11-08 2009-05-13 경북대학교 산학협력단 플라스틱 필름에 투습 방지성이 향상된 보호막의 형성 방법및 이를 이용한 플렉시블 유기 전계 발광 소자
KR20110123306A (ko) * 2010-05-07 2011-11-15 한국세라믹기술원 수분투과 방지막이 코팅된 플라스틱 기판 형성방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5919572A (en) * 1992-11-19 1999-07-06 Sri International Temperature-resistant and/or nonwetting coating of cured, silicon-containing polymers
US20030083453A1 (en) * 2001-05-07 2003-05-01 Kion Corporation Thermally stable, moisture curable polysilazanes and polysiloxazanes
KR20070010025A (ko) * 2004-03-09 2007-01-19 엑사테크 엘.엘.씨. 비평면 기재를 위한 플라즈마 코팅 시스템
KR20070043849A (ko) * 2004-08-20 2007-04-25 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 반도체 소자 및 그 제조방법
KR20090047885A (ko) * 2007-11-08 2009-05-13 경북대학교 산학협력단 플라스틱 필름에 투습 방지성이 향상된 보호막의 형성 방법및 이를 이용한 플렉시블 유기 전계 발광 소자
KR20110123306A (ko) * 2010-05-07 2011-11-15 한국세라믹기술원 수분투과 방지막이 코팅된 플라스틱 기판 형성방법

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11625072B2 (en) 2010-05-14 2023-04-11 Racing Optics, Inc. Touch screen shield
US12038789B2 (en) 2010-05-14 2024-07-16 Ro Technologies, Llc Touch screen shield
US12082638B2 (en) 2014-06-17 2024-09-10 Laminated Film Llc Adhesive mountable stack of removable layers
US11622592B2 (en) 2014-06-17 2023-04-11 Racing Optics, Inc. Adhesive mountable stack of removable layers
CN108574024A (zh) * 2018-02-01 2018-09-25 横店集团东磁股份有限公司 一种用于湿法刻蚀的挤水滚轮
US12085731B2 (en) 2019-02-01 2024-09-10 Ro Technologies, Llc Thermoform windshield stack with integrated formable mold
US11524493B2 (en) 2019-02-01 2022-12-13 Racing Optics, Inc. Thermoform windshield stack with integrated formable mold
US12442958B2 (en) 2019-02-01 2025-10-14 Ro Technologies, Llc Thermoform windshield stack with integrated formable mold
US11845249B2 (en) 2019-02-01 2023-12-19 Racing Optics, Inc. Thermoform windshield stack with integrated formable mold and method
US11846788B2 (en) 2019-02-01 2023-12-19 Racing Optics, Inc. Thermoform windshield stack with integrated formable mold
US12109788B2 (en) 2019-05-21 2024-10-08 Ro Technologies, Llc Polymer safety glazing for vehicles
US11833790B2 (en) 2019-05-21 2023-12-05 Racing Optics, Inc. Polymer safety glazing for vehicles
US11364715B2 (en) 2019-05-21 2022-06-21 Racing Optics, Inc. Polymer safety glazing for vehicles
US12138846B2 (en) 2019-12-03 2024-11-12 Ro Technologies, Llc Method and apparatus for reducing non-normal incidence distortion in glazing films
US12358266B2 (en) 2019-12-03 2025-07-15 Ro Technologies, Llc Method and apparatus for reducing non-normal incidence distortion in glazing films
US12017398B2 (en) 2019-12-03 2024-06-25 Ro Technologies, Llc Method and apparatus for reducing non-normal incidence distortion in glazing films
US11648723B2 (en) 2019-12-03 2023-05-16 Racing Optics, Inc. Method and apparatus for reducing non-normal incidence distortion in glazing films
US11807078B2 (en) 2020-03-10 2023-11-07 Racing Optics, Inc. Protective barrier for safety glazing
US12292205B2 (en) 2020-03-10 2025-05-06 Ro Technologies, Llc Protective barrier for safety glazing
US12077037B2 (en) 2020-03-10 2024-09-03 Ro Technologies, Llc Protective barrier for safety glazing
US11548356B2 (en) 2020-03-10 2023-01-10 Racing Optics, Inc. Protective barrier for safety glazing
US12446637B2 (en) 2021-06-08 2025-10-21 Laminated Film Llc Low haze UV blocking removable lens stack
US11723420B2 (en) 2021-06-08 2023-08-15 Racing Optics, Inc. Low haze UV blocking removable lens stack
US12150503B2 (en) 2021-06-08 2024-11-26 Laminated Film Llc Low haze UV blocking removable lens stack
US11490667B1 (en) 2021-06-08 2022-11-08 Racing Optics, Inc. Low haze UV blocking removable lens stack
US12140781B2 (en) 2021-07-27 2024-11-12 Laminated Film Llc Low reflectance removable lens stack
US12124057B2 (en) 2021-07-27 2024-10-22 Laminated Film Llc Low reflectance removable lens stack
US11624859B2 (en) 2021-07-27 2023-04-11 Racing Optics, Inc. Low reflectance removable lens stack
US12147062B2 (en) 2021-07-27 2024-11-19 Laminated Film Llc Low reflectance removable lens stack
US11307329B1 (en) 2021-07-27 2022-04-19 Racing Optics, Inc. Low reflectance removable lens stack
US11709296B2 (en) 2021-07-27 2023-07-25 Racing Optics, Inc. Low reflectance removable lens stack
US12259566B2 (en) 2021-07-27 2025-03-25 Laminated Film Llc Low reflectance removable lens stack
US11988850B2 (en) 2021-07-27 2024-05-21 Laminated Film Llc Low reflectance removable lens stack
US12162330B2 (en) 2022-02-08 2024-12-10 Ro Technologies, Llc Multi-layer windshield film having progressive thickness layers
US12330483B2 (en) 2022-02-08 2025-06-17 Ro Technologies, Llc Multi-layer windshield film having progressive thickness layers
US11933943B2 (en) 2022-06-06 2024-03-19 Laminated Film Llc Stack of sterile peelable lenses with low creep
US12399304B2 (en) 2022-06-06 2025-08-26 Laminated Film Llc Stack of sterile peelable lenses with low creep
US12153228B2 (en) 2022-09-26 2024-11-26 Laminated Film Llc Low static optical removable lens stack
US11808952B1 (en) 2022-09-26 2023-11-07 Racing Optics, Inc. Low static optical removable lens stack

Similar Documents

Publication Publication Date Title
WO2015009114A1 (fr) Vitrage en polycarbonate et son procédé de production
KR100630433B1 (ko) 수성 수지의 제조방법, 수성 경화성 수지 조성물, 수성 도료 및 그 도막형성방법
JP2015093990A (ja) グレージング用樹脂積層体およびその製造方法
US20020015851A1 (en) Polysilazane composition and coated molded product having its cured material
WO2014104669A1 (fr) Film barrière aux gaz et procédé permettant de fabriquer ce dernier
CN113613904A (zh) 聚酰胺酸组合物及其制造方法、聚酰胺酸溶液、聚酰亚胺、聚酰亚胺膜、层叠体及其制造方法、以及柔性器件及其制造方法
KR20110091869A (ko) 실리콘 조성물과 이를 제조하는 방법
WO2013180531A1 (fr) Film barrière aux gaz et son procédé de fabrication
KR101622001B1 (ko) 하드코팅 필름 및 그 제조방법
CN105377556A (zh) 防雾性物品
KR20160060876A (ko) 코팅 조성물, 이를 포함하는 배리어 필름 및 배리어 필름 제조방법
WO2010140688A1 (fr) Substrat à film stratifié, et procédé de fabrication correspondant
WO2015053500A1 (fr) Vitrage de polycarbonate et son procédé de fabrication
WO2014193199A1 (fr) Film barrière à gaz et son procédé de préparation
US20050182226A1 (en) Paint composition, process for producing transparent protective film using the same, and organic glass provided with transparent protective film
JP2003192987A (ja) 無溶剤型ポリシロキサン系塗剤及び離型フィルム
KR101489959B1 (ko) 가스 배리어 필름, 그 제조방법 및 이를 포함하는 디스플레이 부재
TWI556962B (zh) 聚醯亞胺基板及包含該聚醯亞胺基板的顯示基板模組
WO2019083136A1 (fr) Produit nanohybride durci autoréparant à base de polyurée/sol-gel de silice, et son procédé de préparation
KR101768294B1 (ko) 실록산계 수지 및 이를 포함하는 코팅액 조성물
KR20150010540A (ko) 폴리카보네이트 글래이징 및 그 제조방법
WO2015080397A1 (fr) Film barrière aux gaz et son procédé de fabrication
KR20230129941A (ko) 중합체 조성물 및 코팅 용액
KR102494283B1 (ko) 폴리실라잔계 코팅 소재, 이를 이용한 코팅 필름의 제조 방법 및 이를 통해 제조된 코팅 필름
WO2013176459A1 (fr) Élément d'affichage et son procédé de fabrication

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: 14826465

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: 14826465

Country of ref document: EP

Kind code of ref document: A1