WO2019240408A1 - Oligomère de siloxane ayant un métal organique, procédé de préparation d'oligomère de siloxane, composition de revêtement dur contenant un oligomère de siloxane, film de revêtement dur et dispositif d'affichage - Google Patents

Oligomère de siloxane ayant un métal organique, procédé de préparation d'oligomère de siloxane, composition de revêtement dur contenant un oligomère de siloxane, film de revêtement dur et dispositif d'affichage Download PDF

Info

Publication number
WO2019240408A1
WO2019240408A1 PCT/KR2019/006505 KR2019006505W WO2019240408A1 WO 2019240408 A1 WO2019240408 A1 WO 2019240408A1 KR 2019006505 W KR2019006505 W KR 2019006505W WO 2019240408 A1 WO2019240408 A1 WO 2019240408A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
hard coating
bis
groups
Prior art date
Application number
PCT/KR2019/006505
Other languages
English (en)
Korean (ko)
Inventor
신수철
백성균
홍지현
Original Assignee
㈜켐텍인터내셔날
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 ㈜켐텍인터내셔날 filed Critical ㈜켐텍인터내셔날
Publication of WO2019240408A1 publication Critical patent/WO2019240408A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/089—Treatments not covered by a preceding group
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a siloxane oligomer, and more particularly, to a siloxane oligomer containing an organic metal and improved physical properties, a method for preparing the same, a hard coating composition, a hard coating film and a display device.
  • a flat panel display device represented by a liquid crystal display (LCD) or an organic light emitting diode (OLED) display is widely used in TVs, computer monitors, mobile phone screens, and the like.
  • LCD liquid crystal display
  • OLED organic light emitting diode
  • a touch type display device that allows a user to manipulate a display screen by touching a panel has been widely used.
  • a touch type display device commonly touches the outermost surface of the display device using a user or touch-pen. Therefore, since the outermost surface of the touch type display device needs to control the light incident on the display device and at the same time have a certain hardness, it adopts an optical film such as a hard coat film.
  • tempered glass is used for a hard coating film applied to a display device
  • the tempered glass may be damaged even with slight bending because the tempered glass has a very low elasticity.
  • the problem of breaking the hard coating film made of tempered glass becomes more serious.
  • Plastic covers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI) have been proposed in place of tempered glass in order to secure the flexibility and impact resistance of the hard coating film.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • a hard coating film made of a binder of a polymer in place of the tempered glass has been proposed.
  • the polymer binder adds a polymerization initiator to the hard coating composition present in the monomer or oligomer form to apply heat or irradiate ultraviolet rays to form a polymer to impart hard coating properties.
  • the hard coat film positioned on the surface of the conventional display device lacked physical properties such as impact resistance and surface strength.
  • Various methods have been proposed for solving the physical properties lacking in the hard coating film made of a binder resin.
  • International Publication No. WO 2013/187699 proposes a high hardness siloxane resin composition containing an alicyclic epoxy group, a method for producing the same, and an optical film including the cured product.
  • the optical film according to the international patent achieves a high hardness of 9H, using a single monomer and a cationic initiator, weather resistance may be a problem, there is still a problem that curling may occur. Therefore, there is a need to develop a hard coating film having improved durability to be applied to a display device.
  • the present invention provides a siloxane oligomer represented by the following formula (1).
  • R 1 is directly connected to a silicon atom or silicon via a C 1 to C 10 aliphatic linking group, C 3 to C 10 cycloaliphatic linking group, C 6 to C 20 aromatic linking group or C 6 to C 20 heteroaromatic linking group Silicon directly connected to a glycidoxy group or silicon atom linked to an atom, or via a C 1 to C 10 aliphatic linking group, a C 3 to C 10 cycloaliphatic linking group, a C 6 to C 20 aromatic linking group or a C 6 to C 20 heteroaromatic linking group
  • R 2 is an unsubstituted or substituted C 1 to C 10 alkylene group or an unsubstituted or substituted C 5 to C 30 arylene group, which may be substituted with the alkylene group and the arylene group
  • Substituents include C 1 to C 30 straight or branched chain alkyl groups, C 1 to C 20 alkoxy groups, amino groups,
  • R 1 may be a gamma-glycidoxy group, a gamma-glycidoxy group-containing functional group, 2- (3,4-epoxycyclohexyl group), and / or 2- (3,4-epoxycyclohex). It may be selected from the group consisting of a group) -containing alicyclic epoxy group.
  • M (acac) o of Formula 1 may be selected from the group consisting of aluminum acetyl acetone, titanium acetyl acetone, titanium ethyl acetyl acetone, zirconium monoacetyl acetone, zirconium tetraacetyl acetone, zinc acetyl acetone and combinations thereof have.
  • the weight average molecular weight of the siloxane oligomer may be 1,000 to 100,000.
  • the present invention is a method for producing a siloxane oligomer represented by the following formula (1), the first siloxane monomer represented by the formula (2), the second siloxane monomer represented by the formula (3), It provides a method comprising the step of reacting the third siloxane monomer represented by and the organic metal represented by the formula (5).
  • R 1 is directly connected to a silicon atom or is C 1 ⁇ C 10 aliphatic linking group, C 3 ⁇ C 10 cycloaliphatic linking group, C 6 ⁇ C 20 aromatic linking group or C 6 ⁇ C 20 heteroaromatic linking group Glycidoxy or C 1 to C 10 aliphatic linking group, C 3 to C 10 cycloaliphatic linking group, C 6 to C 20 aromatic linking group or C 6 to C 20 heteroaromatic linking group directly connected to silicon atom or silicon atom via an alicyclic that is connected to a silicon atom through an epoxy group being;
  • formula (I) and the formula from 4 R 2 is unsubstituted or substituted C 1 ⁇ C 10 alkyl group or unsubstituted or substituted C 5 ⁇ C as 30 aryl group, said alkyl Substituents which may be substituted with the ethylene group and the arylene group may be C 1 to C 30 straight or branched alkyl group, C 1 to C 20 alkoxy
  • the siloxane oligomer may be synthesized by a hydrocondensation reaction under an acid catalyst or a base catalyst in the reacting step.
  • the first siloxane monomer represented by Formula 2 is gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimeth Methoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- It can be selected from the group consisting of (3,4-epoxycyclohexyl) ethyltripropoxysilane and combinations thereof.
  • the second siloxane monomer represented by the formula (3) is tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate And C 1 ⁇ C 4 tetraalkyl orthosilicate of straight or branched chain selected from the group consisting of a combination thereof may be included.
  • TMOS tetramethyl orthosilicate
  • TEOS tetraethyl orthosilicate
  • tetrapropyl orthosilicate tetraisopropyl orthosilicate
  • C 1 ⁇ C 4 tetraalkyl orthosilicate of straight or branched chain selected from the group consisting of a combination thereof may be included.
  • the third siloxane monomer represented by the formula (4) is 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,2-bis (trimethoxysilyl) ethane (1,2-bis (trimethoxysilyl) ethane), 1,6-bis (triethoxysilyl) hexane (1,6-bis (triethoxysilyl) hexane), 1,6-bis (trimethoxysilyl) hexane (1 , 6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane (1,8-bis (triethoxysilyl) octane), 1,8-bis (trimethoxysilyl) octane (1,8 -bis (trimethoxysilyl) octane), 1,4-bis (triethoxysilyl)
  • the present invention provides a hard coating composition comprising a siloxane oligomer represented by the above formula (1).
  • the hard coating composition may further include a crosslinking agent.
  • the crosslinking agent may be selected from the group consisting of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated hydrocarbon epoxy monomer, a monomer having an oxetane group, and a combination thereof.
  • the said chain aliphatic epoxy monomer is 1, 4- butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl Ethers, polyethylene glycol diglycidyl ethers, glycerin triglycidyl ethers, polypropylene glycol diglycidyl ethers, polyglycidyl ethers of polyether polyols, and diglycidyl esters of aliphatic dibasic acids; Monoglycidyl ethers of aliphatic alcohols and glycidyl ethers of fatty acids; Epoxidized soybean oil. Butyl epoxy stearate, octyl epoxy stearate, epoxidized amine oil, epoxidized polybutadiene, and combinations thereof.
  • the cyclic aliphatic epoxy monomers are 4-vinylcyclohexene dioxide, cyclohexene vinyl monooxide, (3,4-epoxycyclohexyl) methyl, 3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexyl Methylmethacrylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -1,3-dioxolane and It can be selected from the group consisting of a combination of these.
  • the monomer which has the said oxetane group is 3-methyl oxetane, 2-methyl oxetane, 3-oxetanol, 2-methylene oxetane, 3, 3- oxetane dimethane thiol, 4- (3-methyl Oxetan-3-yl) benzonitrile,-(2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3-jade Cetanemethaneamine, (3-ethyloxetan-3-yl) methylmethacrylate, and 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl-3- Hydroxymethyloxetane, 2-ethylhexyl oxetane, xylylene bis oxetane, 3-ethyl
  • the hard coating composition may include a solvent, a polymerization initiator, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, It may further comprise at least one component selected from the group consisting of a silane coupling agent, an inorganic filler, an antifoaming agent, and an antifouling agent.
  • the present invention is a substrate; It is formed on the substrate, and provides a hard coating film comprising a hard coating layer made of a cured product of the above-described hard coating composition.
  • the base material may be polyester resin, cellulose resin, polycarbonate resin, acrylic resin, styrene resin, polyolefin resin, polyimide resin, polyether sulfone resin, sulfone resin, and air thereof It may be made of a material selected from the group consisting of coalescence.
  • the present invention is a display panel; And a hard coating film positioned on one surface of the display panel.
  • the present invention proposes a siloxane oligomer produced by reacting three different siloxane monomers with an organic metal, a hard coating composition comprising the siloxane oligomer, a hard coat film and a display device which are cured products of the composition.
  • the organometallic compound chemically bonds with the silane of the siloxane, and contains metal atoms in the molecular structure, thereby further securing the intermolecular space. Accordingly, the curling phenomenon can be dramatically reduced by minimizing the curing shrinkage.
  • the hard coat film to which the siloxane oligomer according to the present invention is applied may have improved physical properties such as flexibility and scratch resistance, and thus may be utilized as an optical film of a display device.
  • FIG. 1 is a schematic cross-sectional view of a hard coat film according to an exemplary embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of a display device to which a hard coat film is applied to a cover window according to an exemplary embodiment of the present invention.
  • the shrinkage is increased, the flexibility is reduced, and the curl phenomenon and hard to stretch in one direction back and forth, which does not maintain a flat state A crack phenomenon occurs in which a part of the coating layer is broken.
  • increasing the flexibility of the hard coating layer can solve the curl phenomenon and crack phenomenon, but the problem is that the surface hardness is lowered. Therefore, the development of a high hardness coating material having excellent flexibility, no curling phenomenon and ease of processing is urgently needed for wider application of the polymer film.
  • One of the coating agents generally used for hard coating is a light or thermosetting coating agent.
  • Photocurable coatings can be cured in a short time, as well as room temperature can be used as a surface protective coating of various plastic products.
  • the hardness and adhesion to the film should be excellent, and there should be no curling or rainbow phenomenon.
  • the present invention provides a siloxane oligomer obtained by reacting three different siloxane monomers with an organic metal.
  • Another siloxane oligomer in one aspect of the invention may be represented by the formula (1).
  • R 1 is directly connected to a silicon atom or silicon via a C 1 to C 10 aliphatic linking group, C 3 to C 10 cycloaliphatic linking group, C 6 to C 20 aromatic linking group or C 6 to C 20 heteroaromatic linking group Silicon directly connected to a glycidoxy group or silicon atom linked to an atom, or via a C 1 to C 10 aliphatic linking group, a C 3 to C 10 cycloaliphatic linking group, a C 6 to C 20 aromatic linking group or a C 6 to C 20 heteroaromatic linking group
  • R 2 is an unsubstituted or substituted C 1 to C 10 alkylene group or an unsubstituted or substituted C 5 to C 30 arylene group, which may be substituted with the alkylene group and the arylene group
  • Substituents include C 1 to C 30 straight or branched chain alkyl groups, C 1 to C 20 alkoxy groups, amino groups,
  • the (R 1 SiO 3/2 ) moiety is derived from the first siloxane monomer described below, and in Formula 1, R 1 is directly connected to a silicon atom or a C 1 to C 10 aliphatic linking group, C 3 to C 10 cycloaliphatic linking group, C 6 ⁇ C 20 aromatic linking group or a C 6 ⁇ C 20 heteroaromatic through a bonding group directly to the glycidyl sidok group or a silicon atom connected to a silicon atom or C 1 ⁇ C 10 aliphatic linking group, C 3 ⁇ It has a functional group R 1 which may be an alicyclic epoxy group connected to a silicon atom through a C 10 cycloaliphatic linking group, a C 6 to C 20 aromatic linking group or a C 6 to C 20 heteroaromatic linking group. Since it has an epoxy group like a group epoxy group, excellent surface hardness and low hardening shrinkage rate can be achieved and a curling phenomenon can be prevented.
  • R 1 may be a glycidoxy group or an alicyclic epoxy group which is unsubstituted or has a C 1 to C 10 straight or branched alkyl group. More specifically, R 1 may be selected from the group consisting of glycidoxypropyl group, epoxycyclohexylethyl group, and epoxycyclohexylmethyl group, but the present invention is not limited thereto.
  • x which is a mole fraction of the (R 1 SiO 3/2 ) moiety derived from the first siloxane monomer, is 0.25 ⁇ x ⁇ 0.979, preferably 0.32 ⁇ x ⁇ 0.919, more preferably Is 0.43 ⁇ x ⁇ 0.839.
  • the mole fraction x of the (R 1 SiO 3/2 ) moiety having an epoxy group satisfies the above-mentioned range, a siloxane oligomer having excellent surface hardness and low cure shrinkage can be obtained.
  • the (SiO 4/2 ) moiety is derived from the second siloxane monomer described later, and the (SiO 3/2 -R 2 -SiO 3/2 ) moiety is derived from the third siloxane monomer described later. Including these components, the flexibility of the siloxane oligomer represented by the formula (1) can be improved.
  • the mole fraction y of the (SiO 4/2 ) moiety in the siloxane oligomer represented by Formula 1 is 0.01 ⁇ y ⁇ 0.35, preferably 0.04 ⁇ y ⁇ 0.32, more preferably 0.08 ⁇ y ⁇ 0.27
  • the mole fraction z of the (SiO 3/2 -R 2 -SiO 3/2 ) moiety is 0.01 ⁇ z ⁇ 0.35, preferably 0.04 ⁇ z ⁇ 0.32, more preferably 0.08 ⁇ z ⁇ 0.27.
  • Substituents include C 1 to C 30 straight or branched chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; C 1 -C 20 alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group; Amino group; Acrylic group; Methacryl group; Halogen such as fluoro, bromine and chlorine; Mercapto group; Allyl group; Ether group; Ester group; Carbonyl group; Carboxyl groups; Vinyl group; Nitro group; Sulfun groups; Hydroxyl group; C 3 -C 8 cycloal
  • the siloxane oligomer according to the present invention includes an organometallic moiety defined as (M (acac) o .
  • the organometallic inclusions can ensure a space between the molecular structure, and thus the siloxane represented by the formula (1)
  • the flexibility and processing properties of the oligomers can be improved
  • the mole fraction m of the organometallic (M (acac) moiety) is 0.001 ⁇ m ⁇ 0.05, preferably 0.001 ⁇ m ⁇ 0.04, more preferably 0.001 ⁇ m ⁇ 0.03.
  • the organometallic component (M (acac) o in Formula 1 is aluminum acetylacetone, titanium acetylacetone, titanium ethyl acetylacetone, zirconium monoacetylacetone, zirconium tetraacetylacetone, zinc acetylacetone and these
  • these organic metals may be selected from the group consisting of metal alkylenes (eg, C 1 -C 10 alkylenes such as ethylene / octylene) glycolate, ammonium metal lactate salt, metal
  • metal alkylenes eg, C 1 -C 10 alkylenes such as ethylene / octylene
  • ammonium metal lactate salt metal
  • the weight average molecular weight of the siloxane oligomer represented by Formula 1 may range from 1,000 to 100,000, preferably 1,000 to 50,000, more preferably 1,500 to 20,000.
  • the weight average molecular weight of the siloxane oligomer satisfies the above-mentioned range, high flexibility, low cure shrinkage rate, high surface hardness, and excellent processing characteristics can be ensured.
  • the present invention is a method for producing a siloxane oligomer represented by the following formula (1), the first siloxane monomer represented by the formula (2), the second siloxane monomer represented by the formula (3), It provides a method comprising the step of reacting the third siloxane monomer represented by and the organic metal represented by the formula (5).
  • R 1 is directly connected to a silicon atom or is C 1 ⁇ C 10 aliphatic linking group, C 3 ⁇ C 10 cycloaliphatic linking group, C 6 ⁇ C 20 aromatic linking group or C 6 ⁇ C 20 heteroaromatic linking group Glycidoxy or C 1 to C 10 aliphatic linking group, C 3 to C 10 cycloaliphatic linking group, C 6 to C 20 aromatic linking group or C 6 to C 20 heteroaromatic linking group directly connected to silicon atom or silicon atom via an alicyclic that is connected to a silicon atom through an epoxy group being;
  • formula (I) and the formula from 4 R 2 is unsubstituted or substituted C 1 ⁇ C 10 alkyl group or unsubstituted or substituted C 5 ⁇ C as 30 aryl group, said alkyl Substituents which may be substituted with the ethylene group and the arylene group may be C 1 to C 30 straight or branched alkyl group, C 1 to C 20 alkoxy
  • the first siloxane monomer of the formula (2) which is a siloxane monomer having an epoxy group
  • the flexibility of the siloxane oligomer represented by the formula (1) can be improved by using the second siloxane monomer of the formula (3) and the third siloxane monomer of the formula (4).
  • the organometallic compound of Formula 5 the intermolecular space of the siloxane oligomer represented by Formula 1 may be further secured to improve flexibility and processing characteristics.
  • the first siloxane monomer represented by Formula 2 is gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane , Gamma-glycidoxypropyl methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltripropoxysilane and combinations thereof, but the present invention is not limited thereto.
  • the second siloxane monomer represented by the formula (3) includes a straight or branched C 1 ⁇ C 4 tetraalkyl orthosilicate.
  • tetraalkylorthosilicates consist of tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate, tetraisopropylorthosilicate, tetrabutylorthosilicate and combinations thereof although it may be selected from the group, the present invention is not limited thereto.
  • the third siloxane monomer represented by the formula (4) is 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,2-bis (trimethoxysilyl) ethane (1 , 2-bis (trimethoxysilyl) ethane), 1,6-bis (triethoxysilyl) hexane (1,6-bis (triethoxysilyl) hexane), 1,6-bis (trimethoxysilyl) hexane (1,6 -bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane (1,8-bis (triethoxysilyl) octane), 1,8-bis (trimethoxysilyl) octane (1,8-bis (trimethoxysilyl) octane), 1,4-bis (triethoxysilyl)
  • an acidic catalyst or a basic catalyst capable of promoting the hydrolysis and condensation reaction of three different siloxane monomers represented by Formulas 2 to 4 and the organic metal represented by Formula 5 Suitable catalysts, such as these, can be used.
  • a basic catalyst capable of promoting the hydrolysis and condensation reaction of three different siloxane monomers represented by Formulas 2 to 4 and the organic metal represented by Formula 5 Suitable catalysts, such as these, can be used.
  • it may be stirred for 1 hour to 120 hours at 50 °C to 120 °C.
  • Specific catalysts that can promote the hydrolysis and condensation reactions of three different siloxane monomers and organic metals include acid catalysts such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, and iodide sulfate, ammonia, potassium hydroxide, sodium hydroxide and barium hydroxide. , Base catalysts such as imidazole, and ion exchange resins such as Amberite may be used. These catalysts may be used alone, but may be used in combination. The amount of the catalyst is not particularly limited, but may be added in an amount of about 0.0001 to about 10 parts by weight based on 100 parts by weight of the total components of the siloxane monomer and the organic metal represented by Formula 2 to Formula 5 described above.
  • the present invention also provides a hard coating composition
  • a hard coating composition comprising a siloxane oligomer represented by Formula 1, a hard coating film including a cured product of the hard coating composition, and a display device to which the hard coating film is applied as a kind of optical film.
  • the hard coat film includes a siloxane oligomer represented by Formula 1 as an essential component, and includes a crosslinking agent, a polymerization initiator, a solvent, a surfactant, a leveling agent, an antioxidant, and the like, as necessary.
  • Cross-linkers for promoting crosslinking of siloxane oligomers include, but are not particularly limited to, at least one of chained aliphatic epoxy monomers, cyclic aliphatic epoxy monomers, hydrogenated aromatic hydrocarbon epoxy monomers, and oxetane monomers. These may be included alone or in combination.
  • Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol Diglycidyl ether (neopentylglycoldiglycidyl ether), trimethylolpropane triglycidyl ether, polyethyleneglycol diglycidylether, glycerin triglycidyl ether, glycerintriglycidyl ether Polypropyleneglycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long chain (C 5 ⁇ C 20 ) dibasic acids; Monoglycidyl ethers of aliphatic higher
  • the cyclic aliphatic epoxy monomer is a compound having one or more epoxy groups in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like.
  • the cyclic aliphatic epoxy monomer is (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate (3,4-epoxycyclohexyl) methyl-3', 4'-epoxycyclohexanecarboxylate) , Diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Meta-dioxane (2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metha-dioxane), bis (3,4-epoxycyclohexylmethyl) adipate (bis (3 , 4-epoxycyclohexylmethyl) adipate), bis (3,4-epoxy-6-methylcycl
  • Aromatic epoxy monomers include, for example, bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, and the like; Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac epoxy resins; One or more compounds selected from glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and polyfunctional epoxy resin such as epoxidized polyvinyl phenol, and the like, but the present invention is limited thereto. It doesn't work.
  • the monomer which has an oxetane group is 3-methyl oxetane, 2-methyl oxetane, 3-oxetanol, 2-methylene oxetane, 3, 3- oxetane dimethane thiol, 4- (3-methyl jade Cetane-3-yl) benzonitrile,-(2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3-oxetane Methanamine, (3-ethyloxetan-3-yl) methylmethacrylate, and 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl-3-hydro Consisting of oxymethyloxetane, 2-ethylhexyl oxetane, xylylene bis oxetane
  • the crosslinking agent may be included in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the siloxane oligomer represented by Formula 1 being cured with a siloxane resin.
  • content of the crosslinking agent satisfies the aforementioned range, physical properties such as hardness, flexibility, scratch resistance, and the like of the hard coat film to be manufactured may be improved.
  • the hard coating composition may further include at least one component selected from the group consisting of a solvent, a polymerization initiator, and a functional additive.
  • the hard coating composition includes a suitable solvent capable of dispersing solid components such as the siloxane oligomers described above.
  • the solvent may be an organic solvent.
  • the organic solvent is preferably a polar, nonpolar and / or aprotic solvent.
  • the organic solvent may be C 1 to C 6 aliphatic alcohols, in particular methanol, ethanol and lower alcohols such as n- and I-propanol and butanol; Polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol; Ketones such as acetone, methyl ethyl ketone and butanone; Esters such as ethyl acetate; Ethers such as diethyl ether, detrahydrofuran and tetrahydropyran; Amides such as dimethylacetamide and dimethylformamide; Sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; Aliphatic (optionally halogenated) hydrocarbons such as pentane, hexane and cyclohexane; And mixtures thereof.
  • Polyhydric alcohols such as ethylene glycol, propylene glycol, butane
  • the solvent has a boiling point that can be easily removed by distillation, and for example, the boiling point is preferably 200 ° C. or lower, particularly 150 ° C. or lower.
  • the solvents exemplified above may be included in the ratio of 50 to 95 parts by weight in the hard coating composition. If the content of the solvent is less than 50 parts by weight, it is difficult to coat the thin film due to the high viscosity, and if it exceeds 95 parts by weight, it takes a long time in the curing process and there is a problem of low economic efficiency.
  • the hard coating composition may include a polymerization initiator.
  • An optical radical polymerization initiator, a photoion polymerization initiator, a thermal polymerization initiator, etc. can be used as a polymerization initiator, These can be used individually or in mixture of 2 or more types. Preferably it is a photoion polymerization initiator.
  • radical photopolymerization initiator 1-hydroxycyclohexylphenyl ketone, 2,2'-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, mihiraketone, benzoylpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethyl thioxanthone , 2-isopropyl thioxanthone, 2-chlorothioxanth
  • Irgacure 184 Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F.
  • a photocationic polymerization initiator can be used as a photoion polymerization initiator.
  • the photocationic polymerization initiator may include, but are not limited to, onium salts and / or organometallic salts.
  • a diaryl iodonium salt, a triarylsulfonium salt, an aryldiazonium salt, an iron-arene complex, etc. can be used as a photoion polymerization initiator.
  • the photocationic polymerization initiator is an aryl sulfonium hexafluoro antimony salt, an aryl sulfonium hexafluoro phosphate salt, diphenyl iodonium hexafluoro antimony salt, diphenyl iodonidon Um hexafluorophosphate salts, ditoryl iodonium hexafluorophosphate salts, 9- (4-hydroxyethoxyphenyl) cyanrenium hexafluorophosphate salts, and the like, and the antimony salts are environmental Since there is a contamination problem, hexafluorophosphate salt-based initiators are more preferred. These can be used individually or in mixture of 2 or more types.
  • thermal polymerization initiator for example, 3-methyl-2 butenyl tetramethylenesulfonium hexafluorolomonate salt, ytterbium trilomethenesulfonate salt, samarium trifluoromethenesulfonate salt, erbium trifluoro Lomethenesulfonate salt, dysprosium trifluoromethenesulfonate salt, lanthanum trifluoromethenesulfonate salt, tetrabutylphosphonium methenesulfonate salt, ethyltriphenylphosphonium bromide salt, benzyldimethylamine, Dimethylaminomethylphenol, triethanolamine, Nn-butylimidazole, 2-ethyl-4-methylimidazole, etc. can be used. These can be used individually or in mixture of 2 or more types.
  • the cationic polymerization initiator is 3-methyl-2butenyltetramethylenesulfonium hexafluoroantimonate salt, ytterbium (III) trifluoromethenesulfonate salt, samarium (III) trifluoromethenesulfo Nate salt, erbium trifluoromethenesulfonate salt, triaryl sulfonium hexafluoroantimonate salt, triaryl sulfonium hexafluorophosphate salt, lanthanum (III) trifluoromethenesulfonate salt, tetrabutyl Phosphonium methenesulfonate salt, ethyltriphenylphosphonium bromide salt,
  • the anionic polymerization initiator may be, but not limited to, tertiary amine or imidazole.
  • the anionic polymerization initiators include ⁇ - (dimethylaminomethyl) phenol, tris- (dimethylaminomethyl) phenol, benzyldimethylamine, ⁇ -methylbenzyldimethylamine, and 2-ethyl-4methyl. It may include one or more selected from the group consisting of midazoles, but is not limited thereto.
  • the content of the polymerization initiator in the hard coating composition according to the present invention is not particularly limited, for example, 0.1 to 20 parts by weight, preferably 0.5 to 10, based on 100 parts by weight of the siloxane oligomer represented by Formula 1 cured with a silicone resin. It may be included in parts by weight.
  • the content of the polymerization initiator is in the above range, it is possible to maintain the curing efficiency of the hard coating composition excellent, and to prevent the reduction of physical properties of the hard coating film due to the remaining components after curing.
  • the hard coating composition according to the present invention is a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, a UV absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, an antifoaming agent. And at least one functional additive from the group consisting of antifouling agents.
  • the leveling agent may be an acrylic leveling agent, a silicone leveling agent, a fluorine leveling agent, a silicone-acrylate copolymer leveling agent, a fluorine-modified acrylic leveling agent, a fluorine-modified silicone leveling agent, and a functional group (eg, alkoxy).
  • a functional group eg, alkoxy.
  • Groups such as methoxy or ethoxy groups, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, or isocyanate groups), and in the group consisting of combinations thereof Can be selected.
  • the content of these functional additives can be variously adjusted within the range of not lowering the physical properties of the hard coat film of the present invention, it is not particularly limited, for example, 100 parts by weight of the siloxane oligomer represented by the formula (1) cured with a siloxane resin 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight.
  • FIG. 1 is a cross-sectional view schematically showing a hard coating film prepared from a composition for hard coating according to an exemplary embodiment of the present invention.
  • the hard coating film 100 includes a substrate 110 and a hard coating layer 120 stacked on the substrate 110.
  • Substrate 110 is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy.
  • the base material 100 may include polyester resins such as polyethylene terephthalate, polyethylene isophthalate, and polybutylene terephthalate; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resins; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, cycloolefin or polyolefin resin having a norbornene structure, and ethylene propylene copolymer; Polyimide resin; Polyether sulfone resin; Sulfone resins; And it may be a substrate made of a copolymer thereof.
  • the thickness of the substrate 110 is not particularly limited
  • the hard coating layer 120 may include a siloxane oligomer represented by Formula 1, and may be obtained from the above-described hard coating composition including a crosslinking agent, a solvent, a polymerization initiator, a functional additive, and the like, as necessary.
  • the hard coating composition including the siloxane oligomer represented by Chemical Formula 1 may be coated on an appropriate substrate 110, and may be dried, polymerized, or the like to form a hard coating layer 120.
  • the coating method is not particularly limited.
  • a coating process may be performed in a suitable manner such as a die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, or spin coating to coat the composition for hard coating.
  • the hard coating layer 120 may be formed on the substrate 110.
  • the thickness of the hard coating layer 120 is not particularly limited, and may be, for example, 0.05 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m. Since the hard coating layer 120 has a siloxane resin which is a cured product of the siloxane oligomer represented by Chemical Formula 1, the hard coating film 100 may improve the flexibility, surface hardness and scratch resistance of the hard coating film 100, and may cause curling due to a decrease in curing shrinkage. Etc. can be prevented.
  • the hard coat film 100 according to the present invention is excellent in hardness, scratch resistance, wear resistance, chemical resistance, and the like. Therefore, the hard coat film 100 of the present invention may be applied to an optical film, for example, a window film such as a cover window, for which hardness characteristics are required in the display device.
  • a window film such as a cover window
  • 2 is a schematic cross-sectional view of a display apparatus 200 to which a cover window 100 made of a hard coat film according to the present invention is applied.
  • the cover window 100 made of a hard coating film covers one surface of the display panel 210 displaying an image and protects the display panel 210.
  • the cover window 100 made of a hard coating film according to the present invention is a display device 200 having a flexible or foldable characteristics by preventing damage caused by external impact and damage caused by scratch Applicable to
  • the display apparatus 200 includes a display panel 210, a back cover 230 in which the display panel 210 is accommodated, and a cover window coupled to the back cover 230 at the front of the display panel 210. 100).
  • the display panel 210 may be a liquid crystal display panel, an organic light emitting diode (OLED) device, and a quantum dot light emitting diode (QLED) device.
  • OLED organic light emitting diode
  • QLED quantum dot light emitting diode
  • the display panel 210 when the display panel 210 is a liquid crystal display panel, the display panel 210 includes a liquid crystal panel for displaying an image, a backlight unit (not shown) disposed under the liquid crystal panel, a liquid crystal panel and a backlight. It may include a main frame surrounding the side of the unit, a bottom frame connected to the main frame from the back of the backlight unit, and a top frame covering the front edge of the liquid crystal panel.
  • the back cover 230 covers a rear surface of the display panel 210 and includes a space in which the display panel 210 is accommodated.
  • the cover window 100 covers the front surface of the display panel 210 to protect the display panel 210 and is a surface on which a user or external contact is made.
  • an adhesive layer 220 such as an optically clear adhesive (OCA) may be interposed between the cover window 100 and the display panel 210.
  • OCA optically clear adhesive
  • Cover window 100 is composed of a hard coating film according to the present invention, excellent physical properties such as flexibility, impact resistance, surface hardness, scratch resistance. Therefore, damage or breakage of the cover window 100 may be minimized due to user contact or external pressure.
  • siloxane oligomers prepared in Examples 1 to 27 and Comparative Examples 1 to 21, 20 parts by weight of a crosslinking agent (3-ethyl-3-hydroxymethyloxetane, OXT 101, Toagosei), and a photopolymerization initiator (4- Methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (Irgacure-250, BASF Co.) 3 parts by weight, solvent methyl ethyl ketone by mixing the composition for forming a window coating layer (all components except solvent: 50 Weight percent)).
  • a crosslinking agent (3-ethyl-3-hydroxymethyloxetane, OXT 101, Toagosei)
  • a photopolymerization initiator (4- Methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (Ir
  • the prepared composition for forming a window coating layer was coated on one surface of a transparent polyimide film (CPI (Colorless POlymidie, thickness: 100 ⁇ m)) as a base layer with Mey bar # 34, and dried at 100 ° C. for 5 minutes. , 1000 mJ / cm 2 was irradiated with UV, Aging at 50 °C for 24 hours to prepare a window film having a window coating layer (thickness: 20 ⁇ m) formed on one surface of the transparent polyimide film.
  • CPI Colorless POlymidie, thickness: 100 ⁇ m
  • the coating layer of the film was measured by the JIS K5400 method using a pencil hardness tester (Heidon).
  • Heidon pencil hardness tester
  • the pencil used the pencil of 6B-9H by Mitsubishi.
  • the load of the pencil on the coating layer was 0.75 kg
  • the angle at which the pencil was drawn was 45 °
  • the speed at which the pencil was drawn was 60 mm / min.
  • the pencil hardness was measured using the pencil of the step below, and the maximum pencil hardness value when there is no scratch in all five evaluations are shown in Table 3 and Table 4.
  • CPI Colorless Polyimide
  • JIG CFT-200R, COVOTECH Co., Ltd.
  • the radius of curvature is measured by making the window coating layer contact JIG.
  • the radius of curvature was measured by gradually decreasing the diameter of the JIG starting from the maximum radius of the JIG, and the minimum radius of the JIG without cracking is shown in Table 3 and Table 4 as the radius of curvature.
  • ⁇ Y.I. measured the yellow index (Y1) using a color difference meter (CM3600D, Konica Minolta) at a D65 light source 2 ° (angle of the window film and the light source) for the window film. Then, the window film was irradiated with light having a peak wavelength of 306 nm for 72 hours using an optical device (CT-UVT, Core Tech), and the yellow index (Y2) was evaluated in the same manner. Light reliability was shown in Table 3 and Table 4 using the difference between the yellow index before light irradiation and after light irradiation (Y2-Y1, ⁇ Y.I.).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un oligomère de siloxane formé par réaction de trois types différents de monomères de siloxane avec un métal organique, son procédé de préparation, une composition de revêtement dur contenant l'oligomère de siloxane, un film de revêtement dur résultant du durcissement de la composition de revêtement dur, et un dispositif d'affichage. Le film de revêtement dur composé de l'oligomère de siloxane durci selon la présente invention présente d'excellentes propriétés telles qu'une résistance aux rayures, etc. Le film de revêtement dur dérivé de l'oligomère de siloxane selon la présente invention peut être appliqué à un film optique, par exemple, un film de fenêtre tel qu'une fenêtre de couverture, pour obtenir un dispositif d'affichage ayant d'excellentes propriétés.
PCT/KR2019/006505 2018-06-12 2019-05-30 Oligomère de siloxane ayant un métal organique, procédé de préparation d'oligomère de siloxane, composition de revêtement dur contenant un oligomère de siloxane, film de revêtement dur et dispositif d'affichage WO2019240408A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020180067658A KR101965682B1 (ko) 2018-06-12 2018-06-12 유기 금속을 가지는 실록산 올리고머, 실록산 올리고머의 제조 방법, 실록산 올리고머를 포함하는 하드 코팅 조성물, 하드 코팅 필름 및 디스플레이 장치
KR10-2018-0067658 2018-06-12

Publications (1)

Publication Number Publication Date
WO2019240408A1 true WO2019240408A1 (fr) 2019-12-19

Family

ID=66165273

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/006505 WO2019240408A1 (fr) 2018-06-12 2019-05-30 Oligomère de siloxane ayant un métal organique, procédé de préparation d'oligomère de siloxane, composition de revêtement dur contenant un oligomère de siloxane, film de revêtement dur et dispositif d'affichage

Country Status (2)

Country Link
KR (1) KR101965682B1 (fr)
WO (1) WO2019240408A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112310304A (zh) * 2019-07-26 2021-02-02 乐金显示有限公司 柔性显示装置

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101965682B1 (ko) * 2018-06-12 2019-04-03 (주)켐텍인터내셔날 유기 금속을 가지는 실록산 올리고머, 실록산 올리고머의 제조 방법, 실록산 올리고머를 포함하는 하드 코팅 조성물, 하드 코팅 필름 및 디스플레이 장치
KR102702298B1 (ko) * 2019-12-16 2024-09-19 삼성디스플레이 주식회사 커버 윈도우 및 이를 포함하는 표시 장치
KR102259822B1 (ko) * 2020-07-30 2021-06-02 (주)애드파인테크놀러지 커버 유리 코팅 조성물, 공정 및 이를 이용한 초박형 디스플레이 및 전자 소자
CN112116878B (zh) * 2020-09-24 2022-08-23 Tcl华星光电技术有限公司 显示面板及其制作方法、显示装置
WO2023054559A1 (fr) * 2021-09-30 2023-04-06 積水化学工業株式会社 Composition de résine durcissable, couche de revêtement et film

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06347605A (ja) * 1993-06-04 1994-12-22 Asahi Optical Co Ltd コーティング組成物の製造方法
US20050020758A1 (en) * 2003-07-24 2005-01-27 Terry Karl W. Abrasion resistant coating composition
KR20060016298A (ko) * 2004-08-17 2006-02-22 삼성전자주식회사 유무기 금속 하이브리드 물질 및 이를 포함하는 유기절연체 조성물
KR20070057655A (ko) * 2005-12-01 2007-06-07 주식회사 엘지화학 중굴절 및 고굴절 실록산계 피복 조성물, 이의 제조방법,및 이로부터 제조되는 광학 렌즈
WO2016088901A1 (fr) * 2014-12-04 2016-06-09 株式会社トクヤマ Composition de revêtement et produit optique présentant une couche de revêtement réalisée à partir de ladite composition de revêtement
KR101965682B1 (ko) * 2018-06-12 2019-04-03 (주)켐텍인터내셔날 유기 금속을 가지는 실록산 올리고머, 실록산 올리고머의 제조 방법, 실록산 올리고머를 포함하는 하드 코팅 조성물, 하드 코팅 필름 및 디스플레이 장치

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06347605A (ja) * 1993-06-04 1994-12-22 Asahi Optical Co Ltd コーティング組成物の製造方法
US20050020758A1 (en) * 2003-07-24 2005-01-27 Terry Karl W. Abrasion resistant coating composition
KR20060016298A (ko) * 2004-08-17 2006-02-22 삼성전자주식회사 유무기 금속 하이브리드 물질 및 이를 포함하는 유기절연체 조성물
KR20070057655A (ko) * 2005-12-01 2007-06-07 주식회사 엘지화학 중굴절 및 고굴절 실록산계 피복 조성물, 이의 제조방법,및 이로부터 제조되는 광학 렌즈
WO2016088901A1 (fr) * 2014-12-04 2016-06-09 株式会社トクヤマ Composition de revêtement et produit optique présentant une couche de revêtement réalisée à partir de ladite composition de revêtement
KR101965682B1 (ko) * 2018-06-12 2019-04-03 (주)켐텍인터내셔날 유기 금속을 가지는 실록산 올리고머, 실록산 올리고머의 제조 방법, 실록산 올리고머를 포함하는 하드 코팅 조성물, 하드 코팅 필름 및 디스플레이 장치

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112310304A (zh) * 2019-07-26 2021-02-02 乐金显示有限公司 柔性显示装置
CN112310304B (zh) * 2019-07-26 2024-03-15 乐金显示有限公司 柔性显示装置

Also Published As

Publication number Publication date
KR101965682B1 (ko) 2019-04-03

Similar Documents

Publication Publication Date Title
WO2019240408A1 (fr) Oligomère de siloxane ayant un métal organique, procédé de préparation d'oligomère de siloxane, composition de revêtement dur contenant un oligomère de siloxane, film de revêtement dur et dispositif d'affichage
WO2013187699A1 (fr) Composition de résine de revêtement dur de siloxane
KR101758438B1 (ko) 윈도우 필름용 조성물, 이로부터 형성된 플렉시블 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치
WO2016089021A1 (fr) Composition destinée à un film pour fenêtre, film souple pour fenêtre formé à partir de celle-ci, et dispositif d'affichage souple comprenant celui-ci
WO2020013461A1 (fr) Oligomère de siloxane comprenant un métal organique, procédé de production d'oligomère de siloxane, composition de revêtement dur comprenant l'oligomère de siloxane, film de revêtement dur et dispositif d'affichage
WO2010058988A2 (fr) Substrat en plastique stratifié et son procédé de production
WO2018208049A1 (fr) Stratifié optique et dispositif d'affichage souple l'utilisant
WO2017126773A1 (fr) Composition pour film de fenêtre, film de fenêtre formé à partir de celle-ci, et dispositif d'affichage flexible le comprenant
US20150218319A1 (en) Polyhedral polysiloxane modified product and composition using the modified product
WO2020149597A1 (fr) Stratifié optique
WO2018110830A2 (fr) Film de fenêtre, son procédé de fabrication et dispositif d'affichage l'intégrant
WO2017022987A1 (fr) Composition pour film de fenêtre, film de fenêtre flexible formé à partir de celle-ci, et dispositif d'affichage flexible le comprenant
WO2017039159A1 (fr) Composition durcissant à basse température, film durci formé dessus, et dispositif électronique présentant le film durci
WO2016105088A1 (fr) Composition pour film de fenêtre, film de fenêtre souple formé à partir de celle-ci, et dispositif d'affichage souple le comprenant
KR101908164B1 (ko) 윈도우 필름용 조성물, 이로부터 형성된 플렉시블 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치
WO2020013462A1 (fr) Oligomère de siloxane comprenant un composé organométallique, procédé de préparation d'oligomère de siloxane, composition de revêtement dur comprenant l'oligomère de siloxane, film de revêtement dur et appareil d'affichage
WO2017217609A1 (fr) Composition pour film de fenêtre, film de fenêtre formé à partir de celle-ci, et dispositif d'affichage souple comprenant la composition
WO2018004072A1 (fr) Composition pour film de fenêtre et film de fenêtre flexible formé à partir de celle-ci
WO2016108676A1 (fr) Composition de résine pour revêtement dur, et film de revêtement dur comprenant une forme durcie de cette dernière en tant que couche de revêtement
WO2016175509A1 (fr) Composition pour un film de fenêtre, film de fenêtre flexible formé à partir de cette dernière et dispositif d'affichage flexible comprenant ce dernier
WO2017195927A1 (fr) Nouveau composé de type uréthane-acrylate à base de 2,4,6-triaminotriazine et procédé pour sa préparation
WO2021060961A1 (fr) Stratifié optique et dispositif d'affichage souple le comprenant
JP2015066778A (ja) 成形体の製造方法
WO2015141899A1 (fr) Composition liquide de revêtement dur et vitrage en polycarbonate l'utilisant
WO2016175510A1 (fr) Composition pour film de fenêtre, film de fenêtre flexible formé à partir de celle-ci, et dispositif d'affichage flexible comprenant celui-ci

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: 19819656

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: 19819656

Country of ref document: EP

Kind code of ref document: A1