WO2016108676A1 - Composition de résine pour revêtement dur, et film de revêtement dur comprenant une forme durcie de cette dernière en tant que couche de revêtement - Google Patents

Composition de résine pour revêtement dur, et film de revêtement dur comprenant une forme durcie de cette dernière en tant que couche de revêtement Download PDF

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Publication number
WO2016108676A1
WO2016108676A1 PCT/KR2015/014594 KR2015014594W WO2016108676A1 WO 2016108676 A1 WO2016108676 A1 WO 2016108676A1 KR 2015014594 W KR2015014594 W KR 2015014594W WO 2016108676 A1 WO2016108676 A1 WO 2016108676A1
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Prior art keywords
hard coating
resin composition
resin
film
formula
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PCT/KR2015/014594
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English (en)
Korean (ko)
Inventor
안상현
우학용
정학기
이동희
안병준
김항근
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코오롱인더스트리 주식회사
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Priority claimed from KR1020150190464A external-priority patent/KR101942006B1/ko
Priority claimed from KR1020150190471A external-priority patent/KR101967147B1/ko
Priority claimed from KR1020150190456A external-priority patent/KR101967146B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to EP19193636.8A priority Critical patent/EP3591017B1/fr
Priority to EP15875770.8A priority patent/EP3241875B1/fr
Priority to US15/540,874 priority patent/US20180010012A1/en
Priority to JP2017535370A priority patent/JP2018506617A/ja
Priority to ES15875770T priority patent/ES2791040T3/es
Priority to CN201580075404.XA priority patent/CN107207906B/zh
Publication of WO2016108676A1 publication Critical patent/WO2016108676A1/fr

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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

Definitions

  • the present invention relates to a hard coating film comprising a resin composition for hard coating and a cured product thereof as a coating layer.
  • glass has been uniquely used as a material for important commercial products including optical functional products such as windows of various electronic products, touch screens for computers, lenses, automotive sunroofs, optical screens, light guide plates, and LED front panels.
  • optical functional products such as windows of various electronic products, touch screens for computers, lenses, automotive sunroofs, optical screens, light guide plates, and LED front panels.
  • the glass is heavy, fragile, and at the same time has the disadvantage that the defect rate is very high in the processing of the product, the situation that can overcome the disadvantages of the glass has been made in many ways.
  • the transparent polymer film is widely used as a core material of the optical and transparent display industries, and in particular, due to its light weight and ease of processing, it has emerged as a substitute material for glass in the display industry.
  • the polymer film has a lower surface hardness than glass, and thus has a disadvantage in that the wear resistance is insufficient. Therefore, a high hardness coating, that is, a hard coating technology for improving the surface hardness of the polymer film has been considered as an important issue.
  • Organic materials have the advantages of flexibility and formability due to the characteristics of organic materials, but have the disadvantage of low surface hardness. It has the advantages of hardness and transparency, but has the disadvantage of poor flexibility and formability.
  • organic-inorganic composite materials having both the advantages of both materials are currently in the spotlight, and much research is being conducted, but it is still insufficient to realize the advantages of both materials.
  • one of the coatings 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 the adhesion to the film should be excellent, and there should be no curl and rainbow.
  • the curl phenomenon may act as a big disadvantage in the roll-to-roll process, which is a mass-produced product, and even when provided as a product, it may cause a problem in the future, which is a particularly required physical property.
  • the display industry is moving into the era of flexible displays, which requires a flexible hard coating film.
  • Korean Patent Laid-Open Publication No. 2010-0041992 provides a hard coating film composition including a hardening polyurethane acrylate oligomer.
  • the patent minimizes curling and prevents rainbow phenomenon due to light interference, but does not overcome the limitation of low surface hardness as a hard coating film.
  • the present invention includes an alkoxy silane containing an alicyclic epoxy, which is an organic-inorganic complex, and a siloxane resin in which an alkoxy metal is chemically bonded, thereby securing a space in the molecular structure, thereby suppressing shrinkage while maintaining surface hardness and curling. It is to provide a resin composition for hard coating without.
  • the alkoxy silane and the alkoxy metal is added to the alkoxy silane containing a Q structure of the silane, such as TEOS (Tetraethyl orthosilicate) is further added to provide a resin composition for hard coating comprising a siloxane resin forming a bonding structure, or the siloxane
  • TEOS Tetraethyl orthosilicate
  • the cured product of the resin composition as a coating layer, there is no curl phenomenon, to provide a hard coating film excellent in high surface hardness, adhesion, wear resistance and flex resistance.
  • a first preferred embodiment of the present invention for solving the above problems is a hard coating comprising a siloxane resin chemically bonded by compounds comprising an alkoxy silane represented by the following formula (1) and an alkoxy metal compound represented by the following formula (2) Resin composition.
  • R 1 is an alkyl group of C 1 to C 3 including an alicyclic epoxy group
  • R 2 is an alkyl group of linear or branched C 1 to C 4
  • R 3 is a linear or branched An alkyl group of C 1 to C 4
  • M is at least one metal element selected from the group consisting of aluminum, titanium and zinc
  • n is an integer of 1 to 3
  • m is an integer of 2 to 4.
  • a second preferred embodiment of the present invention for solving the above problems is an alkoxy silane represented by the formula (1) in the first embodiment, the alkoxy silane represented by the following formula (3) to the alkoxy metal compound represented by the formula (2) It is a resin composition for hard coatings containing the siloxane resin chemically bonded by the containing compound.
  • R 3 is a C 1 to C 4 linear or branched alkyl group.
  • the siloxane resin of the first embodiment or the second embodiment is a first component, and at least one of an epoxy resin and an acrylic resin is further used as the second component. It is a resin composition for hard coatings containing.
  • a fourth preferred embodiment of the present invention for solving the above problems is a base film; And a hard coating layer formed on at least one surface of the base film by curing the resin composition for hard coating of the first to third embodiments.
  • the resin composition for hard coating of the present invention is a metal bond by the alkoxy metal in the molecule based on the alicyclic epoxy to ensure the intermolecular space, thereby minimizing shrinkage during curing, thereby excellent surface hardness When it is secured and formed into a coating layer, it is possible to effectively suppress curl generation of the hard coat film.
  • the resin composition for hard coating that can realize surface hardness during curing and minimal curl generation can be provided.
  • the resin composition for hard coating of the present invention using the alkoxy silane having the Q structure of silane includes the Q structure of the silane in the molecular structure, so that the crosslinking becomes dense during the polymerization reaction of the alicyclic organic material, thereby ensuring excellent surface hardness. It can be formed into a cured product on the film surface to provide a hard coating film of excellent performance.
  • the siloxane resin chemically bonded by the alkoxy silane which has an alicyclic epoxy group, the compound containing an alkoxy metal compound, or the alkoxy silane which has an alicyclic epoxy group, the alkoxy silane which has Q structure of a silane, and the compound containing an alkoxy metal compound,
  • the adhesion and the flex resistance can be further improved.
  • 1 is a reaction scheme showing a synthesis mechanism by a sol-gel (Sol-Gel) method of the siloxane resin contained in the resin composition for hard coating according to the first embodiment of the present invention.
  • the alkoxy silane may be represented by the following Chemical Formula 1, and according to a more preferred embodiment of the present invention, the alkoxy silane represented by the following Chemical Formula 1 is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane.
  • R 1 is a linear C 1 to C 3 alkyl group including an alicyclic epoxy group
  • R 2 is a linear or branched C 1 to C 4 alkyl group
  • n is an integer of 1 to 3.
  • the formula (1) is an epoxy monomer is very significant in terms of having a low curing shrinkage rate and can ensure excellent surface hardness while suppressing curl generation. If the formula (1) is an acrylic monomer may exhibit a fast curing rate and high hardness, but the shrinkage rate is high, it may increase the probability of curling. In addition, if the formula (1) is an isocyanate monomer, the elastic modulus is high and excellent in flexibility and accordingly less curl generation probability, but may exhibit a low surface hardness.
  • the formula (1) is an epoxy monomer
  • the surface hardness is higher than that of the isocyanate group, and it has a lower curing shrinkage rate than the acryl group, thereby suppressing curl generation.
  • the formula (1) of the present invention is an alicyclic epoxy monomer, it is advantageous to secure an intermolecular space during curing than a linear epoxy monomer, so that the resin composition for hard coating of the present invention is more effectively prevented from curling due to cured shrinkage.
  • the siloxane resin of the present invention is capable of densely crosslinking siloxane molecules of various molecular weights during photopolymerization or thermal polymerization, thereby providing a hard coating cured product having high hardness.
  • the present invention provides a hard coating composition for a siloxane resin chemically bonded by compounds containing an alkoxy silane and an alkoxy metal compound represented by the following Formula 2 at the same time. It is made into the main ingredient. That is, by including a structure in which the alkoxy silane and the alkoxy metal compound are combined in the molecular structure, the intermolecular space can be further secured by the metal element, and accordingly, the hard coating resin composition of the present invention minimizes hardening shrinkage to prevent curling. It can be drastically reduced.
  • R 3 is a linear or branched C 1 to C 4 alkyl group
  • M is at least one metal element selected from the group consisting of aluminum, titanium and zinc
  • m is an integer of 2 to 4.
  • the alkoxy metal compound may be included in an amount of 0.2 mol% to 5.0 mol% based on the total moles of the alkoxy silane and the alkoxy metal compound, which may be preferable in terms of ensuring ease of processing and effectively suppressing curl generation. Can be.
  • the alkoxy metal compound When the alkoxy metal compound is included in less than 0.2 mol%, the effect of suppressing curl generation may be insignificant, and when the reaction temperature is lowered or the polymerization is stopped within a short time, up to 5.0 mol% metal compound may be added.
  • the alkoxy metal compound may be more preferably contained in 0.2 mol% to 3.0 mol%.
  • Figure 1 is a schematic of the reaction mechanism by the Sol-Gel method of the chemical reaction of the alkoxy silane and alkoxy metal compound of the present invention, the entire siloxane resin can be formed due to the repetition of Route 1 or Route 2 reaction have.
  • the siloxane resin synthesized by the condensation reaction may adjust the viscosity and the curing rate by the monomers added during the reaction, thereby providing an optimum resin composition suitable for the purpose.
  • the siloxane resin obtained through the reaction as described above can secure the intermolecular space during crosslinking, thereby preventing the curl phenomenon caused by curing shrinkage, and enables high surface hardness by crosslinking and metal elements.
  • the siloxane resin of the present invention is not limited thereto, and may further include alkoxy silane represented by Chemical Formula 1 and an alkoxy metal represented by Chemical Formula 2, further comprising an alkoxy silane represented by Chemical Formula 3 to form a chemical bond. .
  • R 3 is a C 1 to C 4 linear or branched alkyl group.
  • the alkoxy silane represented by Chemical Formula 3 includes a silane Q structure in the molecular structure, that is, a chemical bonding structure such as ⁇ Formula 1> having no alkoxy functional group in Si, thereby ensuring excellent hardness. That is, by including the Q structure found in the molecular structure of the glass in the molecular structure, the resin composition of the present invention is able to realize a rigidity similar to glass at the time of curing.
  • the alkoxy silane represented by the formula (1) and the alkoxy silane represented by the formula (3) in the present invention preferably has a molar ratio of 99: 1 to 20:80, more preferably 85:15 to 45:55. It is easy to prevent gelation during polymerization while securing high hardness.
  • the compound of Formula 1 and Formula 3 are used together, it is more advantageous to improve the surface hardness, but when the compound of Formula 3 is present in excess of the above range, it may be difficult to control the polymerization due to the possibility of gelation during polymerization.
  • the alkoxy metal compound represented by the formula (2) is 0.2 mol% based on a total of 100 mol of the alkoxy silane represented by the formula (1) and the alkoxy silane represented by the formula (3) It is more preferable for the synthesis control to contain from 5.0 mol%.
  • the weight average molecular weight is 5,000 to 22,000
  • the polydispersity index (PDI, molecular weight distribution) is preferably 1.5 to 3.1, and includes the formula (3)
  • the weight average molecular weight is 3000 to 50000
  • the polydispersity index (PDI) is preferably 1.5 to 7.0.
  • the molecular weight and the molecular weight distribution (PDI, Mw / Mn) is obtained by gel permeation chromatography (GPC) (Waters, model name e2695) to obtain the polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) This is the value applied. More specifically, 20 ⁇ l of the solution was dissolved in tetrahydrofuran so as to have a concentration of 1% of the polymer to be measured, and then injected into a GPC, and flowed at a flow rate of 1.0 mL / min, and analysis was performed at 30 ° C.
  • GPC gel permeation chromatography
  • the hard coating composition of this invention makes the said siloxane resin a 1st component, and contains at least one of an epoxy resin and an acrylic resin as a 2nd component.
  • the second component may be a monomer or oligomer including at least one functional group among an epoxy group, an oxetane group, an acrylate group, a methacrylate group, a urethane acrylate group, and an ethylene oxide (EO) addition type acrylate group. have.
  • the second component When the second component is included in the present invention, as the bond between the siloxane resin and the monomer or the siloxane resin and the oligomer is generated, the linear structure becomes longer, and thus the siloxane resin is expressed in contrast to when the second component is not added. While maintaining the hardness as it is, the intramolecular spacing by the monomer or oligomer can be enlarged, and the flexibility of the cured film can be further increased.
  • the epoxy resin may be one or more selected from the group consisting of glycidyl-type epoxy resin, alicyclic epoxy resin and oxetane-based resin.
  • the glycidyl epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, naphthalene type epoxy resin or hydrogenated materials thereof; Epoxy resins having a dicyclopentadiene skeleton; Epoxy resins having a triglycidyl isocyanurate skeleton; Epoxy resins having a cardo skeleton; And an epoxy resin having a polysiloxane structure.
  • the alicyclic epoxy resin is provided at both ends of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,2,8,9-diepoxylimonene and ⁇ -caprolactone oligomer.
  • Each of 3,4-epoxycyclohexyl methanol and 3,4-epoxycyclohexanecarboxylic acid may be ester-bonded or an epoxy resin having a hydrogenated bisphenol A skeleton, and the oxetane-based resin may be an oxetane resin having a hydroxy structure. It may be an oxetane resin having an ether oxetane resin or methoxy methyl benzene structure.
  • the acrylic resin is specifically, for example, bisphenol-A ethylene oxide diacrylate, bisphenol-A ethylene oxide dimethacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A ethoxylate Diacrylate, bisphenol-A polyethoxylate diacrylate, bisphenol-A diacrylate, bisphenol-S diacrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris (2-hydride Roxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, bisphenol-A dimethacrylate, bisphenol-S dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacryl Lates, tris (2-hydroxyethyl) isocyanurate trimethacrylate and pentaerythritol At least one selected from tetramethacrylate may be used,
  • the epoxy resin or acrylic resin is preferably used alone or used by mixing two or more kinds.
  • the compatibility between the resins used in a mixture may be lowered and the uniformity of the coating film may be lowered, it may be more preferable to use the mixture alone or in combination of three or less.
  • the first component and the second component described above are preferably included in a mixing ratio of 9: 1 to 6: 4 by weight in the resin composition for hard coating of the present invention.
  • the siloxane resin is used in an excess ratio, the hardness, abrasion resistance, and heat resistance are excellent, but there is a lack of flexibility, so cracking may occur in a process such as cutting after hard coating, and an epoxy resin or an acrylic resin is used in an excess ratio.
  • the hard coating layer may not be able to secure hardness, which is an essential property.
  • the resin composition for hard coating of the present invention may further include an initiator for the polymerization of the siloxane resin in addition to the first component and the second component, for example, a photopolymerization initiator such as an organometallic salt or an amine, imidazole, and the like.
  • a thermal polymerization initiator can be used, and a cationic polymerizer may also be included.
  • the amount of the initiator may be included in about 0.5 to 5 parts by weight based on 100 parts by weight of the total resin composition. If the content is less than 0.5 parts by weight, the curing time of the hard coating layer to increase the hardness is increased, and the efficiency is lowered. If the content is more than 5 parts by weight, the yellowness of the hard coating layer is increased, making it difficult to obtain a transparent coating layer. have.
  • the resin composition for hard coating of the present invention may further include one or more selected from the group consisting of surfactants, antioxidants and leveling agents, according to the special function or need, in particular, the viscosity of the siloxane resin
  • an organic solvent for controlling the controllability and at the same time to further control the thickness of the coating film.
  • the addition amount of the organic solvent is not particularly limited, but examples of the organic solvent that can be used include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone, or cellosolves such as methyl cellosolve and butyl cellosolve, Or ethers such as ethyl ether and dioxane, alcohols such as isobutyl alcohol, isopropyl alcohol, butanol and methanol, or halogenated hydrocarbons such as dichloromethane, chloroform and trichloroethylene, or normal hexane, benzene and toluene It may include one or more selected from a solvent consisting of hydrocarbons and the like.
  • ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone
  • cellosolves such as methyl cellosolve and butyl cellosolv
  • the present invention is a base film; And it is laminated on at least one side of the base film, it can provide a hard coating film comprising a coating layer prepared by curing the resin composition for hard coating, the hard coating film according to the present invention is hardness, adhesion, bending resistance, It is excellent in physical properties such as chemical resistance and abrasion resistance, and it is possible to prevent phenomena such as curling and peeling due to bending during processing and heat treatment during manufacturing and heat treatment.
  • the hard coating film of the present invention is ASTM D3363 measurement standards, 4H to 9H in the direction in which the coating layer is formed, when the alkoxy silane of formula 3 includes 100mm X 100mm area, 25 °C and 50% RH conditions After 24 hours at, the maximum curl value at which the edge of the film is spaced from the horizontal bottom may be 30 mm, which may be particularly suitably applied as a display protective film.
  • the hard coating film may have a very good bendability such that the minimum curvature radius of the film does not cause cracks in the coating layer when the bend is formed in the opposite direction to the coating surface such that 2mm to 6mm is flexible.
  • the heat treatment may be performed for 2 minutes to 60 minutes at a temperature of 40 ° C. or more and about 200 ° C. or less according to the substrate, and in the case of thermal polymerization, 2 minutes at a temperature of 60 ° C. or more and about 300 ° C. or less depending on the substrate. To 60 minutes, but is not limited thereto.
  • the photo-polymerization heat treatment is 50mJ / cm 2 or more 20,000mJ / cm 2 or less, more preferably 200mJ / cm 2 more than 5,000mJ / cm 2 Performing below may be advantageous in terms of ensuring sufficient hardness while more suppressing the occurrence of yellowing.
  • the hard coating resin composition may be applied to a substrate by spraying, dip coating, spin coating, die coating, comma coating, screen coating, inkjet printing, pad printing, knife coating, kiss coating, bar coating, and gravure coating.
  • the coating may be made by any one method, and the thickness of the hard coating layer formed of the hard coating resin composition may be easily adjusted according to the type of the substrate or the use thereof, and in the present invention, 2 to 60 ⁇ m, preferably 10 to 30. Hardness and flexibility of the hard coat film can be secured at the same thickness.
  • the base film in the present invention is a polyethylene sulfonate (PES) film, polyethylene terephthalate (PET) film, polystyrene (PS), methyl methacrylate-styrene (MS), polycarbonate (PC)
  • the organic synthetic resin film including a film, a polymethyl methacrylate (PMMA) film, a sulfin (Surlyn (manufactured by BFGoodrich, USA)), a polyimide (PI) film, and the like may be laminated alone or two or more.
  • the resin composition for hard coating of the present invention may also be applied to inorganic substrates such as glass, quartz, glass wafers, silicon wafers and the like to form a hard coat layer, depending on the purpose.
  • the molecular weight of the resin was measured using GPC, and it was confirmed that it has a number average molecular weight of 7245, a weight average molecular weight of 20146, and a polydispersity index (PDI, M w / M n ) of 2.78.
  • IRGACURE 250 (BASF Co., Ltd.) was added as a photoinitiator to 100 parts by weight of the resin, and then coated on the surface of the colorless polyimide with varying thicknesses of 10, 20, and 30 ⁇ m, and the UV lamp having a wavelength of 315 nm was 30 It was exposed to light for a second time to prepare a hardened coating cured product.
  • siloxane resin was obtained in the same manner as in Example 1-1, 2-ethyl-4-methylimidazole (Sigma-Aldrich) was added 2 parts by weight based on 100 parts by weight of the resin as a thermal initiator instead of the photoinitiator, and the colorless poly On the mid surface was coated with varying thicknesses of 10, 20, 30um. It was heat-treated at a temperature of 120 ° C. for 4 hours to prepare a hard coating coating.
  • 2-ethyl-4-methylimidazole Sigma-Aldrich
  • Example 1-3 Aluminum alkoxide adding
  • Example 1 except that siloxane resin having a number average molecular weight of 7027, a weight average molecular weight of 21325, and a polydispersity index of 3.03 was prepared by adding 1.62 g of aluminum ethoxide (Sigma-Aldrich) instead of 2.96 mL of titanium isopropoxide. Resin was prepared and coated in the same manner as -1 to prepare a coating cured product.
  • Example 1 except that 1.27 g of zinc methoxide (Sigma-Aldrich) was added instead of 2.96 mL of titanium isopropoxide to prepare a siloxane resin having a number average molecular weight of 7312, a weight average molecular weight of 20072, and a polydispersity index of 2.74. Resin was prepared and coated in the same manner as -1 to prepare a coating cured product.
  • Example 1-5 Titanium alkoxide Change in content ( 0.1mol% )
  • Resin was prepared in the same manner as in Example 1-1, except that 0.30 mL of titanium isopropoxide (Sigma-Aldrich) was added to prepare a siloxane resin having a number average molecular weight of 7592, a weight average molecular weight of 20324, and a polydispersity index of 2.67. To prepare a coating cured product was prepared.
  • titanium isopropoxide Sigma-Aldrich
  • Example 1-6 Titanium alkoxide ratio change ( 0.5mol% )
  • Resin was prepared in the same manner as in Example 1-1, except that 1.48 mL of titanium isopropoxide (Sigma-Aldrich) was added to prepare a siloxane resin having a number average molecular weight of 6985, a weight average molecular weight of 19952, and a polydispersity index of 2.85. Was prepared and coated to prepare a coating cured product.
  • titanium isopropoxide Sigma-Aldrich
  • Example 1-7 Titanium alkoxide ratio change ( 1.5mol% )
  • Resin was prepared in the same manner as in Example 1-1, except that 4.44 mL of titanium isopropoxide (Sigma-Aldrich) was added to prepare a siloxane resin having a number average molecular weight of 7428, a weight average molecular weight of 20523, and a polydispersity index of 2.76. To prepare a coating cured product was prepared.
  • titanium isopropoxide Sigma-Aldrich
  • Example 1-8 Titanium alkoxide ratio change ( 1.8mol% )
  • Resin was prepared in the same manner as in Example 1-1, except that 5.33 mL of titanium isopropoxide (Sigma-Aldrich) was added to prepare a siloxane resin having a number average molecular weight of 7790, a weight average molecular weight of 21338, and a polydispersity index of 2.74. To prepare a coating cured product was prepared.
  • Example 1-9 Titanium alkoxide ratio change ( 2.0mol% ) And reaction time control
  • a siloxane resin having a number average molecular weight of 3438 weight average molecular weight of 5151 polydispersity index of 1.5 was obtained in the same manner as in Example 1-1, except that 5.92 mL of titanium isopropoxide (Sigma-Aldrich) was added and the reaction time was progressed for 5 hours. It was obtained and coated to prepare a coating cured product.
  • Example 1-10 Titanium alkoxide ratio change ( 5.0mol% ) And reaction time control
  • a siloxane resin having a number average molecular weight of 5395, a weight average molecular weight of 15116, and a polydispersity index of 2.80 was obtained by the same method as in Example 1 except that no titanium isopropoxide was added. Thereafter, the coating cured product coated with the siloxane resin obtained through Comparative Example 1 was prepared under the same conditions as in Example 1-1.
  • Example 2 Using the same resin as Comparative Example 1-1, using the same thermosetting coating method as in Example 2 to prepare a cured coating.
  • Titanium isopropoxide (Sigma-Aldrich) was added to 16.28mL and the reaction time was controlled to less than 1 hour to prepare a resin in the same manner as in Example 1-1 to coat the film, but difficult to control the gelation of the resin As a result, the solubility in organic solvents was drastically degraded, which was not suitable for coating.
  • Pencil hardness was measured at 750 gf load at a speed of 180 mm / min in accordance with ASTM D3363 using a pencil hardness tester manufactured by IMOTO, Japan.
  • the TEOS is used for the alkoxy silane represented by the general formula (3) of the present invention because TEOS is cheap and easy to obtain, and even if other alkoxy groups are used, the polymer structure has a Q structure. To be the same.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed at a rate of 365.87 g: 2.50 g: 40.66 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. 0.85 g of Sigma-Aldrich Co., Ltd. was added and stirred at 60 ° C. for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 5000, polydispersity index 2.0). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed in a ratio of 332.61 g: 29.69 g: 41.87 mL into a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. (Sigma-Aldrich Co., Ltd.) was added 2.13g and stirred at 60 °C for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 10000, polydispersity index 2.2). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed in a ratio of 295.66 g: 59.37 g: 43.22 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. (Sigma-Aldrich, Inc.) was added 4.26g and stirred at 60 ° C for 10 hours. Thereafter, the resultant was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 15000, polydispersity index 3.0). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed at a ratio of 184.79 g: 146.87 g: 47.28 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. 12.79 g of Sigma-Aldrich Co., Ltd. was added and stirred at 60 ° C. for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 37000, polydispersity index 4.3). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed in a ratio of 73.91 g: 234.37 g: 51.33 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. (Sigma-Aldrich Co., Ltd.) 21.32g was added and stirred for 10 hours at 60 °C gel was difficult to control. Thereafter, the resultant was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 50000, polydispersity index 6.2). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed in a ratio of 73.91 g: 234.37 g: 51.33 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. (Sigma-Aldrich Co., Ltd.) After the addition of 21.32 g of stirring at 60 ° C. for 3 hours to prevent gelation, the siloxane resin (weight average molecular weight 3500, polydispersity index 1.8) was easily obtained without gelation. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin. Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu Co., Ltd.), TEOS (Sigma-Aldrich Co., Ltd.) and H 2 O were mixed at a ratio of 295.66 g: 53.12 g: 43.22 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. 12.79 g of Sigma-Aldrich Co., Ltd. was added and stirred at 60 ° C. for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 28000, polydispersity index 3.2). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu Co., Ltd.), TEOS (Sigma-Aldrich Co., Ltd.) and H 2 O were mixed at a ratio of 295.66 g: 601.87 g: 43.22 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. 0.85 g of Sigma-Aldrich Co., Ltd. was added and stirred at 60 ° C. for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 24000, polydispersity index 2.8). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100
  • KBM-303 (Shinetsu Co., Ltd.), TEOS (Sigma-Aldrich Co., Ltd.) and H 2 O were mixed at a ratio of 184.79 g: 146.87 g: 48.54 mL, placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. (Sigma-Aldrich Co., Ltd.) 21.32g was added, but when stirred for 10 hours at 60 °C Gel is difficult to control the reaction time was shortened to 5 hours.
  • siloxane resin weight average molecular weight 30000, polydispersity index 5.2.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed at a ratio of 258.70 g: 90.62 g: 44.57 mL, and placed in a 500 mL flask, 0.06 g of sodium hydroxide was added as a catalyst, and Titanium isopropoxide. (Sigma-Aldrich, Inc.) was added 4.26g and stirred at 60 ° C for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 18000, polydispersity index 3.9). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-403 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O (Sigma-Aldrich) were mixed in a ratio of 350.96g: 2.50g: 40.66mL and placed in a 500mL flask, and 0.06g sodium hydroxide was catalyzed.
  • Titanium isopropoxide (Sigma-Aldrich) were added 0.85g and stirred at 60 ° C for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 4000, polydispersity index 1.8).
  • 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to the siloxane resin obtained above, to 100 parts by weight of the siloxane resin, thereby obtaining a hard coating resin composition.
  • KBM-303 (Shinetsu), TEOS (Sigma-Aldrich) and H 2 O were mixed at a ratio of 295.66 g: 60.94 g: 43.22 mL, placed in a 500 mL flask, and 0.06 g of sodium hydroxide was added as a catalyst at 60 ° C. Stir for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 21000, polydispersity index 2.3). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu Co., Ltd.) and Titanium isopropoxide (Sigma-Aldrich Co., Ltd.), H 2 O, were mixed in a ratio of 365.87 g: 4.26 g: 40.66 mL, placed in a 500 mL flask, and 0.06 g of sodium hydroxide was added as a catalyst. Stir at 10 ° C. for 10 hours. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 5000, polydispersity index 2.6). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • KBM-303 (Shinetsu Co., Ltd.), TEOS (Sigma-Aldrich Co., Ltd.) and H 2 O were mixed at a ratio of 36.96 g: 281.25 g: 52.68 mL, and placed in a 500 mL flask, followed by reaction by adding 0.06 g of sodium hydroxide as a catalyst. When stirred for 10 hours at 60 °C Gel was difficult to control the reaction time was shortened to 5 hours to react. Thereafter, the mixture was filtered using a 0.45 um Teflon filter to obtain a siloxane resin (weight average molecular weight 48000, polydispersity index 6.8). Next, 3 parts by weight of IRGACURE 250 (BASF, Inc.) as a photoinitiator was added to 100 parts by weight of the siloxane resin to obtain a resin composition for hard coating.
  • IRGACURE 250 BASF, Inc.
  • Pencil hardness was measured at 750 gf load at a speed of 180 mm / min in accordance with ASTM D3363 using a pencil hardness tester manufactured by IMOTO, Japan.
  • Examples 2-3 to 2-10 all showed excellent surface hardness and wear resistance.
  • Comparative Example 2-1 basically did not include an alkoxy silane having an alicyclic epoxy group even though the alkoxy metal was added, the surface hardness as well as the curl characteristics were not significantly improved.
  • Comparative Example 2-2 the TEOS addition amount was increased to improve the surface hardness than Comparative Example 2-1, but it was also confirmed that curling properties were not improved because no alkoxy metal was added.
  • the amount of TEOS added was less than that of Comparative Example 2-2, and thus the hardness was slightly lower, but it was confirmed that the addition of the alkoxy metal greatly improved the curl.
  • the hard coating film prepared using the hard coating resin composition of the present invention is excellent in hardness, wear resistance and curl characteristics, it could be confirmed through experiments that it may be particularly suitable as a film for display protection.
  • the content of TEOS is 17 mol% to 20 mol% based on the total alkoxy silane, and the alkoxy metal is included in the range of 0.2 mol% to 3 mol% based on the total alkoxy silane.
  • KBM-303 (Shinetsu), Titanium isopropoxide (Sigma-Aldrich) and H 2 O were mixed in a 500mL flask at a ratio of 245.2g: 1.4g: 27.2mL and then sodium hydroxide (Sigma-Aldrich) 0.1g was added as a catalyst and the reaction proceeded while removing the alcohol produced by the Dean Stark apparatus while stirring at 60 ° C. for 10 hours to obtain a siloxane resin polymer 1.
  • KBM-303 (Shinetsu), Titanium isopropoxide (Sigma-Aldrich) and H 2 O were mixed in a 500 mL flask at a ratio of 241.5 g: 5.7 g: 27.2 mL, and then 0.1 g sodium hydroxide (Sigma-Aldrich) was added as a catalyst and the reaction proceeded while removing the alcohol produced by the Dean Stark apparatus while stirring at 60 ° C. for 10 hours to obtain a siloxane resin polymer 2.
  • KBM-303 (Shinetsu), Titanium isopropoxide (Sigma-Aldrich) and H 2 O were mixed in a 500 mL flask at a ratio of 234.1 g: 14.2 g: 27.2 mL, and then 0.1 g sodium hydroxide (Sigma-Aldrich) was added as a catalyst and the reaction proceeded while removing the alcohol produced by the Dean Stark apparatus while stirring at 60 ° C. for 10 hours to obtain a siloxane resin polymer 3.
  • KBM-303 (Shinetsu), Aluminum ethoxide (Sigma-Aldrich) and H 2 O were mixed in a ratio of 259.8 mL: 1.62 g: 27.2 mL into a 500 mL flask, and 0.1 g sodium hydroxide was added as a catalyst. The reaction was carried out while removing the alcohol produced by the Dean Stark apparatus while stirring at 10C to obtain a siloxane resin polymer 4.
  • KBM-303 (Shinetsu Co., Ltd.), H 2 O was mixed in a 500 mL flask at a ratio of 246.4 g: 27.2 mL, and then 0.1 g of sodium hydroxide (Sigma-Aldrich) was added as a catalyst and stirred at 60 ° C. for 10 hours. The reaction was carried out while removing the alcohol produced by the Dean Stark apparatus while obtaining the siloxane resin polymer 5.
  • KBM-303 (Shinetsu), Titanium isopropoxide (Sigma-Aldrich) and H 2 O were mixed in a 500 mL flask at a ratio of 231.6 g: 17.1 g: 27.2 mL, and then sodium hydroxide (Sigma-Aldrich) 0.1 g was added as a catalyst and the reaction proceeded while removing the alcohol produced by the Dean Stark apparatus while stirring at 60 ° C. for 10 hours to obtain a siloxane resin polymer 3.
  • methyl ethyl ketone 40% by weight of methyl ethyl ketone as a diluting solvent, 1% by weight of triarylsulfonium hexafluoroantimonate (Sigma-Aldrich) as a photoinitiator, and a silicone-based leveling agent as an additive based on the total weight of the mixed mixture : BYK, product name: BYK-333) 0.4 wt% was added, and stirred for 1 hour using a stirrer to prepare a hard coat resin composition.
  • Ethyl oxetanyl methyl ether (manufacturer: Toagosei Co., Ltd., product name: OXT221) and cyclo aliphatic epoxide (manufactured by Daicel Co., Ltd., product name: Celloxide2021P) were prepared by mixing in a weight ratio of 1: 1.
  • the hard coating resin composition was prepared in the same manner as in Example 3-1.
  • Phenyl epoxy acrylate (manufacturer: Miwon Corporation, product name: PE110) and bisphenol A type EO addition diacrylate (manufacturer: Miwon Corporation, product name: M2100) was prepared by mixing in a weight ratio of 1: 1, in the polymerization example 2
  • Ethyl oxetanyl methyl ether (manufacturer: Toagosei Co., Ltd., product name: OXT221) and cyclo aliphatic epoxide (manufactured by Daicel Co., Ltd., product name: Celloxide2021P) were prepared by mixing in a weight ratio of 1: 1. It was mixed with the prepared siloxane resin in a weight ratio of 1: 1. After the hard coating resin composition was prepared in the same manner as in Example 3-1.
  • Ethyl oxetanyl methyl ether (manufacturer: Toagosei Co., Ltd., OXT221) and cyclo aliphatic epoxide (manufactured by Daicel Co., Ltd., product name: Celloxide2021P) were prepared by mixing in a weight ratio of 1: 1, and Comparative Polymerization Example 1 It was mixed with the siloxane resin prepared in the weight ratio of 3: 1. After the hard coating resin composition was prepared in the same manner as in Example 3-1.
  • Pencil hardness was measured at 750 gf load at a speed of 180 mm / min in accordance with ASTM D3363 using a pencil hardness tester manufactured by IMOTO, Japan.
  • the hard coat film manufactured using the hard coat resin composition of the present invention is excellent in strength, flexibility, and curl characteristics, and thus can be applied as a display protective film.

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Abstract

La présente invention concerne une composition de résine pour revêtement dur, la composition comprenant une résine de siloxane qui est liée chimiquement au moyen de composés comprenant un composé d'un alcoxy métal et d'un alcoxysilane, et l'invention concerne un film de revêtement dur comprenant une couche de revêtement dur formée à partir de la composition de résine pour revêtement dur.
PCT/KR2015/014594 2014-12-31 2015-12-31 Composition de résine pour revêtement dur, et film de revêtement dur comprenant une forme durcie de cette dernière en tant que couche de revêtement WO2016108676A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP19193636.8A EP3591017B1 (fr) 2014-12-31 2015-12-31 Composition de résine pour revêtement dur, et film de revêtement dur comprenant une forme durcie de cette dernière en tant que couche de revêtement
EP15875770.8A EP3241875B1 (fr) 2014-12-31 2015-12-31 Composition de résine pour revêtement dur, et film de revêtement dur comprenant une forme durcie de cette dernière en tant que couche de revêtement
US15/540,874 US20180010012A1 (en) 2014-12-31 2015-12-31 Resin composition for hard coating, and hard-coating film comprising cured form of same as coating layer
JP2017535370A JP2018506617A (ja) 2014-12-31 2015-12-31 ハードコーティング用樹脂組成物、及びその硬化物をコーティング層として含むハードコーティングフィルム
ES15875770T ES2791040T3 (es) 2014-12-31 2015-12-31 Composición de resina para recubrimiento duro y película de recubrimiento duro que comprende una forma curada de la misma como capa de recubrimiento
CN201580075404.XA CN107207906B (zh) 2014-12-31 2015-12-31 用于硬涂层的树脂组合物以及包括其固化形式作为涂层的硬涂膜

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KR20140196056 2014-12-31
KR10-2014-0196056 2014-12-31
KR1020150190464A KR101942006B1 (ko) 2015-12-30 2015-12-30 하드 코팅용 수지 조성물 및 이의 경화물을 코팅층으로 포함하는 하드코팅 필름
KR1020150190471A KR101967147B1 (ko) 2015-12-30 2015-12-30 하드 코팅용 수지 조성물 및 이의 경화물을 코팅층으로 포함하는 하드코팅 필름
KR10-2015-0190464 2015-12-30
KR10-2015-0190456 2015-12-30
KR10-2015-0190471 2015-12-30
KR1020150190456A KR101967146B1 (ko) 2014-12-31 2015-12-30 하드 코팅용 수지 조성물 및 이의 경화물을 코팅층으로 포함하는 하드코팅 필름

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KR20180072265A (ko) * 2016-12-21 2018-06-29 코오롱인더스트리 주식회사 하드 코팅용 수지 조성물 및 이의 경화물을 코팅층으로 포함하는 하드코팅 필름
CN108864937A (zh) * 2017-05-16 2018-11-23 韩国生产技术研究院 硬涂树脂组合物、硬涂片材及显示装置
JP2020519709A (ja) * 2017-05-31 2020-07-02 コーロン インダストリーズ インク コーティング用樹脂組成物及びその硬化物をコーティング層として含むコーティングフィルム

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JP2005213517A (ja) * 2005-04-01 2005-08-11 Shin Etsu Chem Co Ltd コーティング剤組成物及び被覆物品
JP4615641B2 (ja) * 1999-02-15 2011-01-19 品川リフラクトリーズ株式会社 コーティング用組成物の製造方法
KR20120098588A (ko) * 2009-07-02 2012-09-05 다우 코닝 코포레이션 폴리헤테로실록산의 제조 방법
KR20140004568A (ko) * 2012-06-12 2014-01-13 한국과학기술원 실록산 하드코팅 수지 조성물

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EP0051966A2 (fr) * 1980-11-10 1982-05-19 Dow Corning Corporation Compositions à base de résines époxydes et d'alcoolates de silicium catalysées par l'aluminium
JP4615641B2 (ja) * 1999-02-15 2011-01-19 品川リフラクトリーズ株式会社 コーティング用組成物の製造方法
JP2005213517A (ja) * 2005-04-01 2005-08-11 Shin Etsu Chem Co Ltd コーティング剤組成物及び被覆物品
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KR102109345B1 (ko) * 2016-12-21 2020-05-28 코오롱인더스트리 주식회사 하드 코팅용 수지 조성물 및 이의 경화물을 코팅층으로 포함하는 하드코팅 필름
CN108864937A (zh) * 2017-05-16 2018-11-23 韩国生产技术研究院 硬涂树脂组合物、硬涂片材及显示装置
JP2020519709A (ja) * 2017-05-31 2020-07-02 コーロン インダストリーズ インク コーティング用樹脂組成物及びその硬化物をコーティング層として含むコーティングフィルム
US11236251B2 (en) 2017-05-31 2022-02-01 Kolon Industries, Inc. Resin composition for coating, and coating film comprising cured product thereof as coating layer

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