WO2011028075A2 - Composition de revêtement dur, procédé de production et film de revêtement dur obtenu au moyen de la composition de revêtement dur - Google Patents

Composition de revêtement dur, procédé de production et film de revêtement dur obtenu au moyen de la composition de revêtement dur Download PDF

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WO2011028075A2
WO2011028075A2 PCT/KR2010/006047 KR2010006047W WO2011028075A2 WO 2011028075 A2 WO2011028075 A2 WO 2011028075A2 KR 2010006047 W KR2010006047 W KR 2010006047W WO 2011028075 A2 WO2011028075 A2 WO 2011028075A2
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acrylate
compound
hard coating
coating composition
methacrylate
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PCT/KR2010/006047
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English (en)
Korean (ko)
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WO2011028075A9 (fr
WO2011028075A3 (fr
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강문식
김지은
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위더스케미칼 주식회사
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Priority to CN201080038926XA priority Critical patent/CN102482534A/zh
Priority to JP2012526671A priority patent/JP2013502504A/ja
Priority claimed from KR1020100087017A external-priority patent/KR101144932B1/ko
Publication of WO2011028075A2 publication Critical patent/WO2011028075A2/fr
Publication of WO2011028075A3 publication Critical patent/WO2011028075A3/fr
Publication of WO2011028075A9 publication Critical patent/WO2011028075A9/fr

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    • 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
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • a hard coating composition, a method for preparing the same, and a hard coating film formed using the hard coating composition are disclosed.
  • the substrate exposed on the surface of the display used a glass substrate in the past, but the glass substrate is fragile and easily broken, and a transparent film is used instead of glass.
  • the transparent film is lighter than glass, has excellent transparency and impact resistance, but has a weak surface resistance and scratch resistance, scratch resistance, and the like.
  • such a display is mainly used in an environment in which external light is incident, and it is inevitable that an image is formed on the screen display device by the reflection of the external light. Therefore, when exposed to light, the reflected light causes eye fatigue or headache, and the screen display device has a problem such as deterioration of visibility.
  • a hard coating composition comprising the result of a sol-gel reaction and a polymerization reaction of a mixture containing a reactive alkoxysilane compound, an acrylic compound, a fluorine compound, an initiator and a solvent is provided.
  • the mixture may include 100 to 500 parts by weight of acrylic compound, 1 to 100 parts by weight of fluorine compound, 0.1 to 10 parts by weight of initiator, and 0.1 to 5,000 parts by weight of solvent based on 100 parts by weight of the reactive alkoxysilane compound.
  • Forming a mixture comprising a reactive alkoxysilane compound, an acrylic compound, a fluorine compound, an initiator and a solvent; And it provides a method for producing a hard coating composition comprising the step of simultaneously performing a sol-gel reaction and a polymerization reaction to the mixture.
  • It provides a hard coating film formed by applying the hard coating composition on one or both sides of the support.
  • a coating composition comprising an organic-inorganic hybrid for hard coating in which a sol-gel process and a polymer polymerization process are simultaneously performed, and a mesh structure of an organic material and a mesh structure of an inorganic material are covalently bonded to each other, and the
  • the refractive index is low, the reflectance is low, the luminance is improved, and an antistatic function and a hard coating film having a hardness of 2H or more can be provided.
  • Example 1 (A) acrylic acid, (B) vinyl triethoxysilane, (C) fluorooctaethyl methacrylate, (D) The FT-IR graph of Example 1-7 is shown.
  • a hard coating composition comprising the result of a sol-gel reaction and a polymerization reaction of a mixture containing a reactive alkoxysilane compound, an acrylic compound, a fluorine compound, an initiator and a solvent.
  • the sol-gel reaction is a technique of manufacturing ceramics by controlling particles in molecular units using solution chemistry.
  • By using the advantages of the process it is possible to manufacture ceramic particles at low temperature, so that organic materials such as polymers can be added and organic-inorganic composite material called hybridization can be manufactured by controlling organic-inorganic molecular unit particles. .
  • organic-inorganic intrinsic properties can be realized without loss by adjusting the organic-inorganic composite material by molecular unit using a sol-gel reaction. It is possible to distribute uniformly.
  • a three-dimensional oxide mesh structure is formed by hydrolysis and condensation reaction using an alkoxysilane used as a starting material.
  • the alkoxysilane has a reactive group such as epoxy group, vinyl group, acryloyl group, methacryloyl group, etc.
  • a new organic mesh structure can be formed by polymerization with acrylate compound added together with heat or ultraviolet rays. Will be.
  • the organic-inorganic hybrid material has characteristics such as light transmittance, flexibility, toughness, and mechanical strength and thermal stability, which are characteristics of organic polymer materials.
  • the network structure of the material is connected to each other by chemical bonds, so that no phase separation occurs, and each component is uniformly distributed in molecular units to realize new functionality.
  • the hard coating composition according to an embodiment of the present invention is to prepare an organic material (acrylic compound) and an inorganic material (reactive alkoxysilane) in a single process to chemically bond to each other in a molecular unit using a sol-gel reaction and a polymer polymerization reaction can do.
  • the refractive index is low, the reflectance is low, the brightness is improved, it can provide a hard coating composition having an antistatic function and a hardness of 2H or more.
  • the reactive alkoxysilane compound may be any compound known as long as it has reactivity with an acryl-based compound, but non-limiting examples may be an alkoxysilane group substituted with at least one vinyl group, acryloyl group, methacryloyl group or epoxy group. have.
  • the reactive alkoxysilane compound examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinylbutylenetriethoxysilane, vinyltri (beta-methoxy) silane, vinyltri (beta-ethoxy) silane, and acryl Roxypropyltrimethoxysilane, Acryloxypropyltriethoxysilane, Acryloxypropylmethyldimethoxysilane, Gamma-methacryloxypropyltrimethoxysilane, Gamma-methacryloxypropyltriethoxysilane, Gamma-methacryloxy At least one day selected from the group consisting of propylmethyldimethoxysilane, and gamma-methacryloxypropylmethyldiisopropoxysilane, gamma-glycidylpropylpropyl methoxysilane, gamma-glycidyloxypropyltriethoxysilane Can be
  • the mixture may further add an alkoxysilane compound having no reactive group, in addition to the reactive alkoxysilane compound.
  • the alkoxysilane compound which does not have such a reactive group may form a more dense network structure by siloxane bond with the reactive alkoxysilane compound, and the hardness and refractive index of the hard coat film may be controlled according to the added content thereof.
  • Non-limiting examples of alkoxy silane compounds include ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, tetraethylolsosilicate, methyltrimethoxysilane, and propyltriethoxy Silane, gamma-aminopropyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, propyltrimethoxy Silane, gamma-aminopropyltriethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane
  • the acrylic compound may be any compound known as long as it can react with the reactive alkoxy silane, but non-limiting examples include a polyfunctional acrylic compound, polyacrylic acid, polymethacrylic acid, acrylic acid, and methacrylic acid. It may be one or more selected from the group.
  • the polyfunctional acrylic compound, acrylic acid, methacrylic acid, and the like cause crosslinking polymerization reaction with a vinyl group, acryloyl group, methacryloyl group, etc. of the reactive alkoxysilane compound, and also polyacrylic acid, polymethacrylic acid, acrylic acid
  • the hydroxy group and the carboxyl group of the acrylic compound such as methacrylic acid may form a sol-gel reaction with the reactive alkoxysilane compound.
  • the coating composition according to an embodiment of the present invention includes the organic-inorganic hybrid chemically bonded at the molecular unit level, it is possible to implement the properties of organic and inorganic without loss.
  • This chemically bonded organic-inorganic hybrid exhibits excellent adhesion on any substrate of organic or inorganic materials, and at the same time, unlike organic-inorganic composites that are simply mixed in the past, the characteristics of organic materials and inorganic materials are uniform and permanent. It is possible to give reliable characteristics.
  • examples of the multifunctional acrylic compound include methyl acrylate, lauryl acrylate, ethoxy diethylene glycol acrylate, methoxy triethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acryl Lane, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxy acrylate, nenopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylol Propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropaneacrylic acid benzoic acid ester, trimethylolpropanebenzoic acid ester, methyl methacrylate, 2-ethylhexyl methacrylate, n-stearyl meth
  • the content of the acrylic compound is, for example, 100 to 500 parts by weight, 130 to 450 parts by weight, 150 to 400 parts by weight based on 100 parts by weight of the reactive alkoxysilane compound.
  • the fluorine compound refers to a compound in which at least one hydrogen of the polymerizable compound capable of causing a polymerization reaction with an acrylic compound is substituted with fluorine.
  • the fluorine-based compound Since the fluorine-based compound has a property of small intermolecular attraction and low surface energy, it exhibits excellent water / oil repelling effect during surface coating, and also lowers the refractive index of the hard coating film, and provides slip, scratch resistance, and antifouling property. Do it.
  • Non-limiting examples of the fluorine-based compound may be at least one selected from the group consisting of fluoride acrylate, fluoride methacrylate and ethylene fluoride.
  • the fluorine-based compound is poly- (trifluoromethyl methacrylate), poly- (hexafluoroisopropyl-2-fluoroacrylate), perfluorohexaethyl acrylate, perfluorooctaethyl acryl Laterate, perfluorodecaethylacrylate, perfluorododecaethylacrylate, perfluorohexaethyl methacrylate, perfluorooctaethyl methacrylate, perfluorodecaethyl methacrylate, perfluorododecaethyl At least one selected from the group consisting of methacrylate, perfluorohexaethylene, perfluorooctaethylene, perfluorodecaethylethylene, and perfluorododecaethylene.
  • the content of the fluorine-based compound is, for example, 1 to 100 parts by weight, 10 to 80 parts by weight, 20 to 60 parts by weight based on 100 parts by weight of the reactive alkoxysilane compound.
  • Any initiator may be used as long as the initiator is suitable for the polymerization reaction of the acrylic compound.
  • Non-limiting examples of such initiators include persulfate; Azo compounds; peroxide; It may be at least one selected from the group consisting of an acetophenone compound, a bezoin ether compound, a benzophenone compound, and a thioxane compound.
  • the initiator may include sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyl nitryl, benzoyl peroxide, acetyl peroxide, dilauryl peroxide, cumyl hydroperoxide, hydrogen peroxide, Potassium peroxide, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholine ( Benzoin ethers such as acetophenones such as 4-thiomethylphenyl) propan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, benzophenone and olso-benzo Methyl benzoate, 4-phenylbenzophenone, 4-benzoyl per
  • the content of the initiator is, for example, 0.1 to 10 parts by weight, 0.5 to 8 parts by weight, 1 to 6 parts by weight based on 100 parts by weight of the reactive alkoxysilane compound.
  • the film When the content of the initiator satisfies this range, the film may be easily formed and a smooth coating surface may be formed.
  • the solvent is not particularly limited, but for example, a solvent having a boiling point of 200 ° C. or lower at normal pressure may be used, and in particular, water or a mixture of water and an organic solvent may be used.
  • the organic solvent may be at least one selected from the group consisting of alcohol compounds, ketone compounds, ether compounds, ester compounds, aromatic compounds and amide compounds.
  • the solvent particularly water, hydrolyzes the reactive alkoxysilane compound to promote the sol-gel reaction, and the organic solvent acts as a medium during the polymerization reaction to help uniform dispersion of the original raw materials, Serves to prevent temperature rise and to provide a uniform coating to the film.
  • Examples of the alcohol compound include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, t-butanol, ethoxyethanol, butoxyethanol, ethylene glycol monoethyl ether, benzyl alcohol, pen Ethyl alcohol, 1-methoxy-2-propanol, and the like.
  • Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are mentioned as an example of a ketone compound.
  • Dibutyl ether, propylene glycol monoethyl ether acetate, etc. are mentioned as an example of an ether compound.
  • ester compound ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, ethyl acetoacetate, 1-methoxy-2-propanol acetate, etc. are mentioned.
  • Toluene, xylene, etc. are mentioned as an example of an aromatic compound.
  • the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
  • the content of the solvent is, for example, 0.1 to 5,000 parts by weight, 100 to 3,500 parts by weight, and 300 to 2,000 parts by weight based on 100 parts by weight of the reactive alkoxysilane compound.
  • the mixture may further comprise a catalyst capable of catalyzing the sol-gel reaction of the reactive alkoxysilane.
  • the group catalyst may be at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, sodium hydroxide.
  • the content of the catalyst is, for example, 0.1 to 10 parts by weight, 0.5 to 8 parts by weight, 1 to 6 parts by weight based on 100 parts by weight of the reactive alkoxysilane compound.
  • the effect of promoting the hydrolysis reaction may be clear, the storage property of the coating composition may be improved, and the viscosity may be controlled.
  • the coating composition may include an antistatic agent, a crosslinking agent, a dye, a fluorescent brightener, a light diffusing agent, a pH adjusting agent, an antioxidant, an antifoaming agent, and an antifoaming agent as necessary to reinforce the surface and mechanical properties of the coating film and to improve coating properties.
  • Additives such as leveling agents, lubricants, anti-curling agents, surface conditioners, thickeners, ultraviolet absorbers, antidegradants, ozone deterioration inhibitors, and preservatives may be introduced in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total coating composition.
  • the additive content is less than 0.01 parts by weight, the effect of addition is small, and if it is 5 parts by weight or more, these components act as an impurity and may lower the physical properties of the coating film, it is preferable to use within the above range.
  • forming a mixture comprising a reactive alkoxysilane compound, an acrylic compound, a fluorine compound, an initiator and a solvent; And it provides a method for producing a hard coating composition comprising the step of simultaneously performing a sol-gel reaction and a polymerization reaction to the mixture.
  • sol-gel reaction and the polymerization reaction are continued for 1 to 24 hours, followed by cooling to terminate the reaction.
  • the sol-gel reaction and the polymerization reaction occur simultaneously. That is, a sol-gel reaction between a reactive alkoxysilane and an acrylic compound (especially an acrylic compound having a hydroxy group or a carboxyl group), a polymerization reaction between an acrylic compound, and a polymerization reaction between a reactive alkoxysilane and an acrylic compound occur simultaneously to form a three-dimensional network structure. .
  • an acrylic compound especially an acrylic compound having a hydroxy group or a carboxyl group
  • a polymerization reaction between an acrylic compound, and a polymerization reaction between a reactive alkoxysilane and an acrylic compound occur simultaneously to form a three-dimensional network structure.
  • the polymerization reaction for example, has a conversion of 30 to 95%, 50 to 93%, 60 to 90%. As a result, it can be controlled to be partly a polymerization reaction in which unreacted material is present. In other words, a part of the polymerizable reactor of the acrylic compound, the reactive alkoxysilane, and the fluorine-based compound participating in the polymerization reaction is maintained so as not to be converted into a polymer.
  • the conversion rate means that the ratio of the mass of the solid content in the hard coating composition that terminated the polymerization reaction to the total mass of the reactive alkoxysilane compound, the acrylic compound, and the fluorine compound, which is initially added at the time of preparing the hard coating composition, is expressed as a percentage. do.
  • the mixture is based on 100 parts by weight of the reactive alkoxysilane compound, 100 to 500 parts by weight of the acrylic compound, 1 to 100 parts by weight of the fluorine-based compound, 0.1 to 10 parts by weight of the initiator, and 0.1 to 5,000 parts by weight of the solvent Include.
  • a hard coating film formed by applying the hard coating composition according to any one of claims 1 to 12 on one or both sides of the support.
  • the support examples include inorganic substrates such as glass, quartz, glass wafers, silicon wafers, polyethylene sulfonate (PES) films, polyethylene terephthalate (PET) films, polycarbonate (PC) and polymethyl methacrylate (PMMA) panels, It can be coated on various transparent substrates such as an organic synthetic resin film such as Surlyn (BFGoodrich, USA).
  • inorganic substrates such as glass, quartz, glass wafers, silicon wafers, polyethylene sulfonate (PES) films, polyethylene terephthalate (PET) films, polycarbonate (PC) and polymethyl methacrylate (PMMA) panels
  • PES polyethylene sulfonate
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • the hard coating composition according to an embodiment of the present invention is a plastic liquid crystal display material surface and a flat panel liquid crystal display surface, computer monitor screen and safety glasses surface, other glass, polycarbonate and acrylic plate, polyethylene phthalate or PES film, etc. Transparent substrate surface and the like.
  • the coating composition may be applied on one or both sides of the support by any one of spraying, dip coating, spin coating, screen coating, inkjet printing, pad printing, knife coating, kiss coating, bar coating and gravure coating.
  • the coating can be made by.
  • the hard coat film according to an embodiment of the present invention may have a refractive index of 1.30 to 1.50, a luminance of 6,000 to 6,200 cd / m 2 , and a hardness of 1H to 4H.
  • the refractive index was measured at a wavelength of 632.8 nm with a prism coupler, and the luminance was measured with a BM7 luminance meter using BLU (Samsung Electronics) for 13-inch monitor, and pencil hardness was measured under 1 kg by the method specified in JIS K5400.
  • the specific composition was prepared in the same manner as in Example 1-1 except for following Table 1.
  • the conversion rate of the polymerization reaction of the obtained hard coating composition is shown in Table 1 below.
  • Example 1-1 Example 1-2
  • Example 1-3 Example 1-4
  • Example 1-5 Example 1-5
  • Example 1-7 Example 1-8
  • Alkoxysilane 5 5 5
  • 10 10
  • Acrylic acid 20 10 25 15 20 10 25 15 15 Methacrylic acid 0 10 0 10 0 10 0 10
  • Perfluorooctaethyl methacrylate 3 One 3 One 3 3 3 3 3 3
  • FIG. 1 compares the FT-IR graph of (A) acrylic acid, (B) vinyl triethoxysilane, (C) fluorooctaethyl methacrylate, and (D) the hard coat composition of Example 1-7
  • the stretching vibration 1638 cm -1 of C C disappeared
  • the stretching vibration peaks of the CF2, CF3 780,680cm -1 appeared
  • Si-O Absorption by stretching movement shows that the band shows wide band at 1100 ⁇ 1040 cm -1 .
  • the hard coating composition of Example 1-7 is made of a composition in which the polymerization reaction proceeds considerably, unlike the coating composition including the conventional simple complex, because the double bond of acrylic acid is lost.
  • Example 1-1 to 1-9 After stirring the hard coating composition prepared in Examples 1-1 to 1-9 for about 1 hour, the coating was applied with a bar coater on a polyethylene terephthalate (PET) film at a dry thickness of 5 to 80 to 140 ° C.
  • PET polyethylene terephthalate
  • the hard coating films of Examples 2-1 to 2-9 were each prepared by treating in an oven for about 30 seconds to 3 minutes.
  • the refractive index, brightness, hardness, and adhesion of the hard coat films prepared in Examples 2-1 to 2-9 were measured and shown in Table 2 below, and the hard prepared in Examples 2-1 to 2-9.
  • the friction resistance of the coating film was measured and shown in Table 3 below.
  • the refractive index was measured at a wavelength of 632.8 nm with a prism coupler, and the luminance was measured with a BM7 luminance meter using BLU (Samsung Electronics) for 13-inch monitor, and hardness was measured under 1 kg by the method specified in JIS K5400.
  • Adhesion test is based on ASTM D 3359 to make a hardened coating layer with a cross-hatch cutter (Elcometer 107) to form a check groove, then adhere the adhesive (Elcometer Adhesive Tape) on the well, peel off with a constant force to the coating layer The degree of adhesion to the substrate was observed. 100 squares were made by cutting a cross 11 ⁇ 11 at 1 mm intervals on the surface of the coated support, and a tape (Elcometer Adhesive Tape) was attached thereon for about 90 seconds, and the surface was pulled at an angle of 180 degrees. If the number of remaining eyes is 100, 5B, 95 or more, 4B, 85 or more, 3B, 65 or more, 2B, 35 or more, 1B, less than 0B.
  • the friction resistance test was performed by using a steel wool measuring instrument (steel trade) and steelwool on the coated side of the hard coating film, rubbing back and forth until a wound trace occurred under a load of 100 g. It was confirmed.
  • a commercially available coating solution for thermosetting was purchased and selected as a comparative example to check the friction resistance.
  • Example 2-1 Example 2-2 Example 2-3
  • Example 2-4 Example 2-5
  • Example 2-6 Example 2-7
  • Example 2-8 Example 2-9 Refractive index 1.43 1.44 1.40 1.45 1.40 1.38 1.41 1.39 1.43
  • Luminance (cd / cm 2 ) 6092 6080 6104 6013 6013 6135 6104 6117 6092 Hardness 2H 3H 2.5H 3H 2H 2.5H 2H 2.5H 2H Adhesion 4B 5B 5B 5B 5B 4B 5B 5B 5B 5B 5B
  • Example 2-1 Example 2-2 Example 2-3
  • Example 2-4 Example 2-5
  • Example 2-6 Example 2-7
  • Example 2-8 Example 2-9 Comparative example Friction Resistance (Number) 105 115 110 120 105 100 105 105 100 70
  • the heart-coated films according to Examples 2-1 to 2-9 have low refractive index, improved brightness, hardness of 2H or more, and improved adhesion and friction resistance. .

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Abstract

L'invention concerne une composition de revêtement dur qui contient le produit d'une réaction sol-gel et d'une réaction de polymérisation d'un mélange contenant un composé d'alcoxysilane réactif, un composé acrylique, un composé fluoré, un initiateur et un solvant. Par ailleurs, l'invention concerne un procédé de production de la composition de revêtement dur ainsi qu'un film de revêtement dur obtenu au moyen de cette composition.
PCT/KR2010/006047 2009-09-04 2010-09-06 Composition de revêtement dur, procédé de production et film de revêtement dur obtenu au moyen de la composition de revêtement dur WO2011028075A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017142174A1 (fr) * 2016-02-18 2017-08-24 삼성에스디아이 주식회사 Composition pour film de fenêtre et film de fenêtre flexible formé à partir de celle-ci
KR20170107441A (ko) * 2015-01-20 2017-09-25 미쓰비시 마테리알 가부시키가이샤 저굴절률막 형성용 액 조성물
WO2018070695A1 (fr) * 2016-10-11 2018-04-19 삼성에스디아이 주식회사 Composition pour film fenêtre et film fenêtre souple formé à partir de celle-ci
WO2018080034A1 (fr) * 2016-10-28 2018-05-03 삼성에스디아이 주식회사 Composition pour film fenêtre et film fenêtre souple formé à partir de celle-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080078801A (ko) * 2005-12-27 2008-08-28 니폰 가야꾸 가부시끼가이샤 반사 방지성 광학필름 및 그의 제조방법
KR20090049519A (ko) * 2007-11-13 2009-05-18 주식회사 엘지화학 반사방지 코팅 조성물 및 이것을 이용하여 제조된 반사방지필름
KR100905606B1 (ko) * 2001-06-29 2009-07-02 제이에스알 가부시끼가이샤 반사 방지막 적층체 및 그 제조 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100905606B1 (ko) * 2001-06-29 2009-07-02 제이에스알 가부시끼가이샤 반사 방지막 적층체 및 그 제조 방법
KR20080078801A (ko) * 2005-12-27 2008-08-28 니폰 가야꾸 가부시끼가이샤 반사 방지성 광학필름 및 그의 제조방법
KR20090049519A (ko) * 2007-11-13 2009-05-18 주식회사 엘지화학 반사방지 코팅 조성물 및 이것을 이용하여 제조된 반사방지필름

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170107441A (ko) * 2015-01-20 2017-09-25 미쓰비시 마테리알 가부시키가이샤 저굴절률막 형성용 액 조성물
KR102237333B1 (ko) 2015-01-20 2021-04-06 미쓰비시 마테리알 가부시키가이샤 저굴절률막 형성용 액 조성물
WO2017142174A1 (fr) * 2016-02-18 2017-08-24 삼성에스디아이 주식회사 Composition pour film de fenêtre et film de fenêtre flexible formé à partir de celle-ci
WO2018070695A1 (fr) * 2016-10-11 2018-04-19 삼성에스디아이 주식회사 Composition pour film fenêtre et film fenêtre souple formé à partir de celle-ci
WO2018080034A1 (fr) * 2016-10-28 2018-05-03 삼성에스디아이 주식회사 Composition pour film fenêtre et film fenêtre souple formé à partir de celle-ci

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