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WO2019189071A1 - Substrat doté d'un film antireflet, stratifié et procédé de production de stratifié - Google Patents

Substrat doté d'un film antireflet, stratifié et procédé de production de stratifié Download PDF

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Publication number
WO2019189071A1
WO2019189071A1 PCT/JP2019/012678 JP2019012678W WO2019189071A1 WO 2019189071 A1 WO2019189071 A1 WO 2019189071A1 JP 2019012678 W JP2019012678 W JP 2019012678W WO 2019189071 A1 WO2019189071 A1 WO 2019189071A1
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WO
WIPO (PCT)
Prior art keywords
antiglare film
film
substrate
antiglare
antifouling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/012678
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English (en)
Japanese (ja)
Inventor
耕司 池上
宏之 熊谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP2020510852A priority Critical patent/JP7188439B2/ja
Publication of WO2019189071A1 publication Critical patent/WO2019189071A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments

Definitions

  • the present invention relates to a substrate with an antiglare film, a laminate, and a method for producing the laminate.
  • the glass substrate when a glass substrate is used as the cover member, the glass substrate may be provided with an antifouling film that suppresses the adhesion of dirt.
  • a compound having a fluorine group is known as a material for the antifouling film (see Patent Document 1).
  • an antiglare film may be provided on the glass substrate.
  • a silica film formed from a silica precursor is known (see Patent Document 2).
  • the antifouling performance can be further exhibited in the laminate in which the antiglare film is further provided with respect to the antiglare film provided on a substrate such as a glass substrate. It is preferable that the antifouling film provided in this way has durability that allows the antifouling performance to be easily maintained even under relatively severe conditions.
  • the present invention has been made by finding a configuration in which the durability of the antifouling film can be easily maintained.
  • An object of the present invention is to provide a substrate with an antiglare film, a laminate, and a method for producing the laminate, which can enhance the durability of the antifouling membrane.
  • the substrate with an antiglare film that solves the above problem is a substrate with an antiglare film comprising a substrate and an antiglare film provided on the substrate, wherein the antiglare film has a hydroxyl group and is a time-of-flight type It has a surface with a hydroxide ion count of 127,000 or more when standardized with a total anion count of 1,000,000 detected by secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS secondary ion mass spectrometry
  • the substrate with an antiglare film that solves the above problem is a substrate with an antiglare film provided with a substrate and an antiglare film provided on the substrate, wherein the antiglare film has a hydroxyl group, and the antiglare film
  • the contact angle of water on the surface of is 10 ° or less.
  • the antiglare film preferably contains SiO 2 .
  • the substrate is preferably a glass substrate.
  • a manufacturing method of a laminate according to one aspect for solving the above-described problem includes a laminate comprising: a substrate; a substrate with an antiglare film provided with an antiglare film provided on the substrate; and an antifouling film provided on the antiglare film.
  • the antiglare film has a hydroxyl group, and in the cleaning process, the surface of the antiglare film is detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • the film forming process is a step of performing cleaning until the hydroxide ion count reaches 127,000 or more when standardized with a total anion count of 1,000,000. It is deposited a hydroxyl group and chemically bonded by the antifouling film of the anti-glare film.
  • a laminate manufacturing method comprising: a substrate, a substrate with an antiglare film provided with an antiglare film provided on the substrate; and a antifouling film provided on the antiglare film.
  • a method of manufacturing a laminate for manufacturing a body, the cleaning step of cleaning the surface of the antiglare film in the substrate with the antiglare film, and the antifouling film on the surface of the antiglare film cleaned in the cleaning step A film forming step of forming a film, wherein the antiglare film has a hydroxyl group, and the cleaning step is a step of cleaning until a contact angle of water on the surface of the antiglare film is 10 ° or less.
  • the film forming step forms an antifouling film that is chemically bonded to the hydroxyl group of the antiglare film.
  • the cleaning step preferably uses a cleaning liquid containing water.
  • the durability of the antifouling film can be increased.
  • the substrate 11 with an antiglare film has a substrate 12 and an antiglare film 13 provided on the substrate 12.
  • the substrate 12 is made of glass or a resin material.
  • glass publicly known glass, such as alkali free glass, aluminosilicate glass, soda lime glass, can be used, for example.
  • tempered glass such as chemically tempered glass and crystallized glass such as LAS-based crystallized glass can also be used.
  • the thickness of the substrate 12 may be set in consideration of mechanical properties and the like, and is preferably in the range of 0.05 mm or more and 10 mm or less, for example.
  • the antiglare film 13 in the substrate 11 with the antiglare film is a film that scatters light by the uneven surface.
  • the anti-glare film 13 has a hydroxyl group, and the number of hydroxide ions counted when the total number of anions detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) is normalized to 1 million.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the antiglare film 13 is preferably composed of at least one oxide selected from, for example, SiO 2 , Al 2 O 3 , ZrO 2 , and TiO 2 , and more preferably includes SiO 2 .
  • the surface of an oxide such as SiO 2 has a hydroxyl group, and this hydroxyl group can be detected as a hydroxide ion by analysis by TOF-SIMS.
  • the thickness of the antiglare film 13 is, for example, in the range of not less than 40 nm and not more than 500 nm.
  • the laminate 14 includes a substrate 11 with an antiglare film and an antifouling film 15 chemically bonded to the hydroxyl groups of the antiglare film 13.
  • the antifouling film 15 is formed on the antiglare film 13 and imparts functions such as water repellency, oil repellency, antifouling property, and slipperiness to the substrate 11 with the antiglare film.
  • the antifouling film 15 can be chemically bonded to the hydroxyl groups of the antiglare film 13 by silanol groups that undergo a dehydration reaction (dehydration condensation) with the hydroxyl groups of the antiglare film 13.
  • the antifouling film 15 preferably has a fluorine group, and more preferably has a perfluoropolyether group.
  • the thickness of the antifouling film 15 is, for example, in the range of 1 nm or more and 30 nm or less.
  • the manufacturing method of the laminated body 14 includes a cleaning step S11 for cleaning the surface of the antiglare film 13 in the substrate 11 with the antiglare film, and an antifouling on the surface of the antiglare film 13 cleaned in the cleaning step S11.
  • the substrate 11 with an antiglare film used in the cleaning step S11 is obtained by applying a coating agent for forming an antiglare film on the substrate 12 and then drying (heating).
  • This coating agent contains a precursor of the antiglare film 13.
  • the method of applying the coating agent is preferably a spray application method.
  • a known nozzle such as a two-fluid nozzle or a one-fluid nozzle can be used.
  • the surface properties (surface roughness, etc.) of the antiglare film 13 can be controlled by, for example, the particle size of the coating agent droplets ejected from the nozzle.
  • the particle diameter of the droplets of the coating agent sprayed from the nozzle is preferably, for example, 0.1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
  • the particle size of the droplet is 0.1 ⁇ m or more, the coating film can be formed in a shorter time.
  • the particle size of the droplet is 100 ⁇ m or less, the performance of the antiglare film 13 is easily improved.
  • the particle size of the droplet can be adjusted by the type of nozzle, spray pressure, liquid amount, and the like. For example, when a two-fluid nozzle is used, the droplet becomes smaller as the spray pressure becomes higher, and the droplet becomes larger as the liquid amount increases.
  • the droplet diameter is the Sauter average particle diameter measured by a laser measuring instrument.
  • the antiglare film 13 is formed by baking in a temperature range of 100 ° C. or more and 400 ° C. or less.
  • the precursor contained in the coating agent for forming an antiglare film include inorganic precursors such as a silica precursor, an alumina precursor, a zirconia precursor, and a titania precursor.
  • the precursor of the antiglare film 13 preferably contains a silica precursor because the refractive index of the antiglare film 13 is low and the reactivity is easily controlled.
  • the silica precursor examples include a silane compound having a hydrocarbon group and a hydrolyzable group bonded to a silicon atom, a hydrolysis condensate of a silane compound, and a silazane compound. From the viewpoint of suppressing the occurrence of cracks in the antiglare film 13, the silica precursor preferably contains at least one of a silane compound and a hydrolysis condensate of the silane compound.
  • the silane compound has a hydrocarbon group bonded to a silicon atom and a hydrolyzable group.
  • the hydrocarbon group is one or two selected from —O—, —S—, —CO—, and —NR′— (R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms. You may have the group which combined two or more.
  • the hydrocarbon group may be a monovalent hydrocarbon group bonded to one silicon atom or a divalent hydrocarbon group bonded to two silicon atoms.
  • Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
  • Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group.
  • hydrolyzable group examples include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, a halogen atom and the like, and the stability of the silane compound and the ease of hydrolysis.
  • an alkoxy group, an isocyanate group, and a halogen atom are preferable.
  • the alkoxy group an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
  • silane compounds include alkoxysilanes (tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, etc.), alkoxysilanes having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), alkoxysilanes having a vinyl group (vinyl) Trimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilane having an epoxy group (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl) Diethoxysilane, 3-glycidoxypropyltriethoxysilane and the like), alkoxysilanes having an acryloyloxy group (such as 3-acryloyloxypropyltrimethoxysilane) and the
  • a silazane compound is a compound having a bond of silicon and nitrogen (—SiN—) in its structure.
  • the silazane compound may be a low molecular compound or a high molecular compound (a polymer having a predetermined repeating unit).
  • Examples of low molecular weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, and the like. It is done.
  • Examples of the alumina precursor include aluminum alkoxide, hydrolysis condensate of aluminum alkoxide, water-soluble aluminum salt, aluminum chelate and the like.
  • Examples of the zirconia precursor include zirconium alkoxide, a hydrolysis condensate of zirconium alkoxide, and the like.
  • Examples of the titania precursor include titanium alkoxide, hydrolysis condensate of titanium alkoxide, and the like.
  • the coating agent further contains a liquid medium that dissolves the precursor.
  • the liquid medium include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds.
  • Examples of alcohols include methanol, ethanol, isopropanol, butanol, diacetone alcohol and the like.
  • Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • Examples of ethers include tetrahydrofuran and 1,4-dioxane.
  • Examples of cellosolves include methyl cellosolve and ethyl cellosolve.
  • Examples of esters include methyl acetate and ethyl acetate.
  • Examples of glycol ethers include ethylene glycol monoalkyl ether.
  • nitrogen-containing compound examples include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and the like.
  • sulfur-containing compound examples include dimethyl sulfoxide.
  • a liquid medium may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the liquid medium is preferably a liquid medium containing water, that is, water or a mixed liquid of water and another liquid medium.
  • a liquid medium containing water
  • water that is, water or a mixed liquid of water and another liquid medium.
  • alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and butanol are particularly preferable.
  • the coating agent for forming the antiglare film may contain an acid catalyst that promotes hydrolysis and condensation of the precursor.
  • the acid catalyst include inorganic acids (such as nitric acid, sulfuric acid, and hydrochloric acid) and organic acids (such as formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid).
  • the cleaning step S11 in the method of manufacturing the laminate 14 is performed when the surface of the antiglare film 13 is standardized with the total anion count detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) as 1 million. In this step, washing is performed until the hydroxide ion count reaches 127,000 or more, preferably 130,000 or more.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the conditions of the cleaning step S11 can be set according to the surface state of the antiglare film 13. Specifically, it can be determined by cleaning the sample of the substrate 11 with the antiglare film under a predetermined condition and then performing the analysis by the TOF-SIMS. For example, by setting the cleaning conditions in the cleaning step S11 so as to further enhance the cleanliness of the surface of the antiglare film 13, the count number of the hydroxide ions detected by TOF-SIMS on the surface of the antiglare film 13 is increased. Tend to. Specifically, for example, by increasing the cleaning time in the cleaning step S11 or increasing the temperature of the cleaning liquid, the hydroxide ion count tends to increase.
  • the temperature of the cleaning liquid is preferably 35 ° C. or higher, more preferably 40 ° C. or higher.
  • the time for which the cleaning liquid is brought into contact with the surface of the antiglare film 13 is preferably 1 second or longer.
  • the cleaning liquid used in the cleaning step S11 for example, a hydrophilic solvent such as alcohol, water, or the like can be used.
  • the cleaning liquid may contain cleaning components such as an alkali component and a surfactant.
  • the cleaning component remaining on the surface of the antiglare film 13 is included in the cleaning liquid, the cleaning component remaining on the surface of the antiglare film 13 is performed by performing a cleaning process in which the surface of the antiglare film 13 is washed only with water or alcohol. Can be removed.
  • an antifouling film 15 that is chemically bonded to the hydroxyl groups of the antiglare film 13 is formed.
  • the antifouling film 15 is obtained by applying a coating agent for forming an antifouling film on the antiglare film 13 and then drying (heating).
  • the method of applying the coating agent is preferably a spray coating method.
  • dip coating, spin coating, flow coating, roll coating, or gravure coating can be used in addition to spray coating.
  • a silane compound having a fluorine group As the precursor contained in the coating agent for forming the antifouling film, a silane compound having a fluorine group can be used.
  • the silane compound having a fluorine group further has a hydrocarbon group and a hydrolyzable group bonded to a silicon atom.
  • the precursor preferably includes a perfluoropolyether group-containing silane compound.
  • Examples of the perfluoropolyether group-containing silane compound include a compound represented by the following general formula (1a) and a compound represented by the following general formula (1b).
  • Rf 1 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • a, b, c and s are each independently an integer of 0 to 200, and the sum of a, b, c and s is at least 1.
  • the order of presence of each repeating unit in parentheses with a, b, c or s is arbitrary in the formula, d and f are 0 or 1, and e and g are integers of 0 or more and 2 or less.
  • M and l are integers of 1 or more and 10 or less.
  • X represents a hydrogen atom or a halogen atom
  • Y represents a hydrogen atom or a lower alkyl group
  • Z represents a fluorine atom or a lower fluoroalkyl group
  • T represents a hydrolyzable group.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms
  • n is an integer of 1 or more and 3 or less.
  • Rf 1 is preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with one or two or more fluorine atoms, and more preferably a perfluoroalkyl group.
  • the sum of a, b, c and s is preferably 1 to 100.
  • the repeating unit — (OC 4 F 8 ) — may be linear or branched, and — (OCF 2 CF 2 CF 2 CF 2 ) — is preferred.
  • the repeating unit — (OC 3 F 6 ) — may be linear or branched, and is preferably — (OCF 2 CF 2 CF 2 ) —.
  • the repeating unit — (OC 2 F 4 ) — may be linear or branched, and is preferably — (OCF 2 CF 2 ) —.
  • X is a halogen atom, it is preferably an iodine atom, a chlorine atom, or a fluorine atom.
  • Y is a lower alkyl group, it is preferably an alkyl group having 1 to 20 carbon atoms.
  • examples of the lower fluoroalkyl group include a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro A methyl group or a pentafluoroethyl group, more preferably a trifluoromethyl group.
  • d and f are 1 and Z is preferably a fluorine atom.
  • Examples of the hydrolyzable group represented by T include —OA, —OCOA, —O—N ⁇ C (A) 2 , —N (A) 2 , —NHA, and halogen.
  • A represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms.
  • R 1 is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
  • R 1 is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
  • a perfluoropolyether group containing silane compound the compound shown to the following general formula (2a) and the compound shown to the following general formula (2b) is mentioned, for example.
  • Rf 2 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • a, b, c and s are each independently an integer of 0 or more and 200 or less, and the sum of a, b and c is at least 1.
  • the order of presence of each repeating unit in parentheses with a, b, c or s is arbitrary in the formula, d and f are 0 or 1, h and j are 1 or 2, and i And k is an integer of 2 or more and 20 or less.
  • Z represents a fluorine atom or a lower fluoroalkyl group, and T represents a hydrolyzable group.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 or more and 3 or less.
  • Rf 2 is preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with one or more fluorine atoms, and more preferably a perfluoroalkyl group.
  • the sum of a, b, c and s is preferably 1 to 100.
  • — (OC 4 F 8 ) — may be linear or branched, and — (OCF 2 CF 2 CF 2 CF 2 )-Is preferred.
  • the repeating unit — (OC 3 F 6 ) — may be linear or branched, and is preferably — (OCF 2 CF 2 CF 2 ) —.
  • the repeating unit — (OC 2 F 4 ) — may be linear or branched, and is preferably — (OCF 2 CF 2 ) —.
  • examples of the lower fluoroalkyl group include a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro A methyl group or a pentafluoroethyl group, more preferably a trifluoromethyl group.
  • d and f are 1 and Z is preferably a fluorine atom.
  • Examples of the hydrolyzable group represented by T include —OA, —OCOA, —O—N ⁇ C (A) 2 , —N (A) 2 , —NHA, and halogen.
  • A represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms.
  • R 2 is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
  • R 2 is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
  • the compound represented by following General formula (3) is mentioned, for example.
  • Rf 3 [—L 3 pXR 31 —Si (OR 32 ) 3 ] q (3)
  • Rf 3 represents a perfluoropolyether group, and is preferably a perfluoropolyether group having 1 to 300 carbon atoms. However, at least a part of the fluorine atoms bonded to the terminal carbon atom in Rf 3 may be a hydrogen atom.
  • p represents 0 or 1.
  • q represents 1 or 2.
  • R 31 represents an alkylene group, and is preferably an alkylene group having 1 to 3 carbon atoms.
  • R 32 represents an alkyl group and is preferably an alkyl group having 1 to 3 carbon atoms.
  • L 3 represents —CO—.
  • X is, -O -, - NR 33 - , - S -, - SO 2 -, - SO 2 NR 33 -, and represents a group selected from -NR 33 CO-, is preferably -O-.
  • R 33 represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.
  • the perfluoropolyether group-containing silane compound may be used alone or in combination of two or more. Moreover, you may use what is disclosed by patent document 1 as a perfluoro polyether group containing silane compound.
  • the coating agent for forming the antifouling film contains a solvent capable of dissolving the perfluoropolyether group-containing silane compound and the like.
  • a solvent capable of dissolving the perfluoropolyether group-containing silane compound and the like.
  • hydrofluoroether HFE
  • hydrofluoroether examples include perfluoropropyl methyl ether (C 3 F 7 OCH 3 ), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5).
  • C 2 F 5 CF (OCH 3 ) C 3 F 7 perfluorohexyl methyl ether
  • a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
  • a catalyst, fluorine-containing oil, silicone oil, and the like disclosed in Patent Document 1 can be contained in the coating agent for forming the antifouling film.
  • the coating agent can further contain a function-imparting agent such as a hard coat agent.
  • Examples of the use of the laminate 14 include a display application, a touch panel application, and an electronic device application. Moreover, as an application location of the laminated body 14, an electric equipment, a vehicle, etc. are mentioned, for example.
  • the antiglare film 13 in the substrate 11 with the antiglare film has a hydroxyl group, and the number of hydroxide ions counted when the total number of anions detected by TOF-SIMS is standardized to 1 million. Has a surface of 127,000 or more.
  • the antifouling film 15 is further provided on the surface of the antiglare film 13, it is considered that the chemical bond of the antifouling film 15 to the hydroxyl group on the surface of the antiglare film 13 can be increased.
  • the antifouling film 15 provided on the antiglare film 13 is difficult to peel off. Thereby, it becomes possible to improve the durability of the antifouling film 15.
  • the antiglare film 13 in the substrate 11 with the antiglare film preferably contains SiO 2 . In this case, for example, occurrence of cracks in the antiglare film 13 can be suppressed.
  • the substrate 12 in the substrate 11 with an antiglare film is preferably a glass substrate.
  • the heat resistance and strength of the substrate 11 with an antiglare film can be increased.
  • the laminated body 14 includes a substrate 11 with an antiglare film and an antifouling film 15 chemically bonded to a hydroxyl group of the antiglare film 13. According to this configuration, as described above, the antifouling film 15 provided on the antiglare film 13 is difficult to peel off, so that the durability of the antifouling film 15 can be increased.
  • the method of manufacturing the laminate 14 includes a cleaning step S11 for cleaning the surface of the antiglare film 13 in the substrate 11 with the antiglare film, and an antifouling film 15 on the surface of the antiglare film 13 cleaned in the cleaning step S11. And a film forming step S12 for forming a film.
  • the antiglare film 13 has a hydroxyl group
  • the cleaning step S11 is a process in which the surface of the antiglare film 13 is cleaned until the hydroxide ion count number detected by TOF-SIMS becomes 127,000 or more. is there.
  • the film forming step S12 is a step of forming the antifouling film 15 that is chemically bonded to the hydroxyl groups of the antiglare film 13.
  • the laminate 14 from which the antifouling film 15 is difficult to peel can be easily obtained.
  • (1-6) In the method for manufacturing the laminate 14, it is preferable to use a cleaning liquid containing water in the cleaning step S11. In this case, since the handleability of the cleaning liquid is improved, the cleaning equipment can be simplified.
  • the antiglare film 13 in the substrate 11 with the antiglare film of the second embodiment has a hydroxyl group, and the contact angle of water on the surface of the antiglare film 13 is 10 ° or less.
  • the contact angle of water can be measured according to JIS R3257 (1999).
  • the cleaning step S11 in the method for manufacturing the laminated body 14 is a step of cleaning until the contact angle of water on the surface of the antiglare film 13 becomes 10 ° or less.
  • the antiglare film 13 in the substrate 11 with the antiglare film has a hydroxyl group, and the contact angle of water on the surface of the antiglare film 13 is 10 ° or less.
  • the antifouling film 15 When the antifouling film 15 is further provided on the surface of the antiglare film 13, the components for forming the antifouling film 15 bonded to the hydroxyl group are easily brought into contact with the hydroxyl groups on the surface of the antiglare film 13. It is considered that the chemical bond of the antifouling film 15 to the hydroxyl groups on the surface of the film 13 can be increased.
  • the antifouling film 15 provided on the antiglare film 13 is difficult to peel off. Thereby, it becomes possible to improve the durability of the antifouling film 15. (2-2) The effect similar to that described in the columns (1-2) to (1-4) of the first embodiment can be obtained for the substrate 11 with the antiglare film of the second embodiment.
  • the method of manufacturing the laminate 14 includes a cleaning step S11 for cleaning the surface of the antiglare film 13 in the substrate 11 with the antiglare film, and an antifouling film 15 on the surface of the antiglare film 13 cleaned in the cleaning step S11. And a film forming step S12 for forming a film.
  • the antiglare film 13 has a hydroxyl group
  • the cleaning step S11 is a step of cleaning until the contact angle of water on the surface of the antiglare film 13 is 10 ° or less.
  • the film forming step S12 is a step of forming the antifouling film 15 that is chemically bonded to the hydroxyl groups of the antiglare film 13.
  • the laminate 14 from which the antifouling film 15 is difficult to peel can be easily obtained.
  • the same effects as those described in the section (1-6) of the first embodiment can be obtained.
  • Test Example 1-1 A coating agent for forming an antiglare film was spray-coated on one main surface of a glass substrate (soda lime glass, thickness 2.5 mm) and dried to form a coating layer on the substrate.
  • a coating agent for forming an antiglare film a solution (precursor concentration: 3% by mass) in which a precursor (tetraethyl orthosilicate) of an antiglare film was dissolved in a liquid medium containing water was used.
  • a sample 11A of a glass substrate with an antiglare film was obtained.
  • sample 11B was obtained by washing the surface of the antiglare film of sample 11A.
  • an aqueous alkaline cleaning liquid adjusted to a concentration of 6.5% and a temperature of 45 ° C. was used to remove the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.
  • the surface of the antiglare film of Sample 11B was analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) under the following conditions.
  • Analytical instrument name manufactured by IONTOF, TOF-SIMS IV
  • Primary beam conditions Ga, +2.5 keV, 0.1 pA
  • Secondary mass spectrometry Time-of-flight mass spectrometer
  • a coating agent for forming an antifouling film was spray-coated on the antiglare film of Sample 11B and dried to form a coating layer on the antiglare film.
  • a coating agent for forming an antifouling film is prepared by mixing 0.1 part by mass of a commercial product containing a perfluoropolyether group-containing silane compound and 99.9 parts by mass of a solvent (perfluorobutyl ethyl ether). did. By heating the coating layer on the antiglare film at 180 ° C. for 30 minutes, a sample 11C of a laminate having an antifouling film was obtained.
  • Test Example 1-2 Sample 12A was obtained in the same manner as Sample 11A in Test Example 1-1.
  • sample 12B was obtained by washing the surface of the antiglare film of sample 12A.
  • an aqueous alkaline cleaning liquid adjusted to a concentration of 6.5% and a temperature of 45 ° C. was used to remove the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.
  • the surface of the antiglare film of sample 12B was analyzed in the same manner as in Test Example 1-1 using TOF-SIMS. As a result, the number of hydroxide ions counted when standardizing the total number of detected anions as 1 million was used. Was 132,000.
  • a sample 12C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of Sample 12B in the same manner as in Test Example 1-1.
  • Sample 13A was obtained in the same manner as Sample 11A in Test Example 1-1.
  • sample 13B the surface of the antiglare film of sample 13A was washed to obtain sample 13B.
  • an aqueous alkaline cleaning liquid adjusted to a concentration of 6.5% and a temperature of 45 ° C. was used to remove the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.
  • the surface of the antiglare film of Sample 13B was analyzed in the same manner as in Test Example 1-1 using TOF-SIMS. As a result, the number of hydroxide ions counted when standardized with the total number of detected anions being 1 million. Was 125,000.
  • a sample 13C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of Sample 13B in the same manner as in Test Example 1-1.
  • Sample 14A was obtained in the same manner as Sample 11A in Test Example 1-1.
  • sample 14B was obtained by washing the surface of the antiglare film of sample 14A.
  • an aqueous alkaline cleaning liquid adjusted to a concentration of 5.0% and a temperature of 37 ° C. was used to remove the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.
  • the surface of the antiglare film of Sample 14B was analyzed in the same manner as in Test Example 1-1 using TOF-SIMS. As a result, the number of hydroxide ions counted when standardized with the total number of detected anions being 1 million. Was 123,000.
  • a sample 14C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of Sample 14B in the same manner as in Test Example 1-1.
  • Sample 15A was obtained in the same manner as Sample 11A in Test Example 1-1.
  • sample 15B was obtained by washing the surface of the antiglare film of sample 15A.
  • an aqueous alkaline cleaning solution adjusted to a concentration of 3.0% and a temperature of 37 ° C. was used to remove the surface of the antiglare film using a shower nozzle. After spraying, it was washed with water and dried.
  • the surface of the antiglare film of Sample 15B was analyzed in the same manner as in Test Example 1-1 using TOF-SIMS, and as a result, the number of hydroxide ions counted when standardized with the total number of detected anions being 1,000,000. was 90000.
  • a sample 15C of a laminate having an antifouling film was obtained by providing an antifouling film on the antiglare film of Sample 15B in the same manner as in Test Example 1-1.
  • Test Example 2-1 In Test Example 2-1, first, a sample 21A was obtained in the same manner as the sample 11A in Test Example 1-1, and then, as shown in Table 2, the sample 21A was washed in the same manner as the sample 11A. Got.
  • a sample 21C of a laminate having an antifouling film was obtained by providing an antifouling film on the sample 21B in the same manner as the sample 11B of Test Example 1-1.
  • Test Example 2-2 In Test Example 2-2, first, a sample 22A was obtained in the same manner as the sample 12A in Test Example 1-2, and then, as shown in Table 2, the sample 22A was washed in the same manner as the sample 12A. Got.
  • Test Example 2-3 In Test Example 2-3, first, a sample 23A was obtained in the same manner as the sample 13A in Test Example 1-3, and then, as shown in Table 2, the sample 23A was washed in the same manner as the sample 13A, whereby a sample 23B was obtained. Got.
  • Test Example 2-4 In Test Example 2-4, first, a sample 24A was obtained in the same manner as the sample 14 in Test Example 1-4, and then, as shown in Table 2, the sample 24A was washed in the same manner as the sample 14A. Got.
  • Test Example 2-5 In Test Example 2-5, first, a sample 25A was obtained in the same manner as Sample 15A in Test Example 1-5, and then, as shown in Table 2, the sample 25A was washed in the same manner as Sample 15A, whereby Sample 25B Got.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

L'invention concerne un substrat (11) pourvu d'un film antireflet comprenant un substrat (12) et un film antireflet (13) formé sur le substrat (12). Le film antireflet (13) du substrat (11) comporte un groupe hydroxyle et une surface qui possède un nombre d'ions hydroxyde égal ou supérieur à 127 000 par nombre total d'anions de 1 000 000 tel que détecté par spectrométrie de masse d'ions secondaires à temps de vol (TOF-SIMS).
PCT/JP2019/012678 2018-03-26 2019-03-26 Substrat doté d'un film antireflet, stratifié et procédé de production de stratifié Ceased WO2019189071A1 (fr)

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Cited By (1)

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JPH08143332A (ja) * 1994-11-16 1996-06-04 Oputoron:Kk 強固な撥水性薄膜の形成方法
JP2002292776A (ja) * 2001-03-28 2002-10-09 Tdk Corp 物体表面の防汚処理方法及び防汚処理された物体
JP2005208290A (ja) * 2004-01-22 2005-08-04 Konica Minolta Opto Inc 防汚性光学薄膜、防汚性反射防止フィルム及びそれを用いた偏光板、表示装置
WO2014199991A1 (fr) * 2013-06-11 2014-12-18 日本電気硝子株式会社 Élément de recouvrement, dispositif d'affichage et procédé de production d'un élément de recouvrement
JP2015511174A (ja) * 2012-02-28 2015-04-16 ダイキン工業株式会社 含フッ素シラン系膜を有する物品の製造方法
WO2016190047A1 (fr) * 2015-05-22 2016-12-01 ダイキン工業株式会社 Procédé de fabrication d'article comprenant une couche de traitement de surface

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Publication number Priority date Publication date Assignee Title
JPS62169102A (ja) * 1986-01-21 1987-07-25 Seiko Epson Corp 無機コ−ト膜の表面改質法
JPH08143332A (ja) * 1994-11-16 1996-06-04 Oputoron:Kk 強固な撥水性薄膜の形成方法
JP2002292776A (ja) * 2001-03-28 2002-10-09 Tdk Corp 物体表面の防汚処理方法及び防汚処理された物体
JP2005208290A (ja) * 2004-01-22 2005-08-04 Konica Minolta Opto Inc 防汚性光学薄膜、防汚性反射防止フィルム及びそれを用いた偏光板、表示装置
JP2015511174A (ja) * 2012-02-28 2015-04-16 ダイキン工業株式会社 含フッ素シラン系膜を有する物品の製造方法
WO2014199991A1 (fr) * 2013-06-11 2014-12-18 日本電気硝子株式会社 Élément de recouvrement, dispositif d'affichage et procédé de production d'un élément de recouvrement
WO2016190047A1 (fr) * 2015-05-22 2016-12-01 ダイキン工業株式会社 Procédé de fabrication d'article comprenant une couche de traitement de surface

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112684521A (zh) * 2020-12-25 2021-04-20 安徽鸿程光电有限公司 抗菌防眩光膜及其制备方法
CN112684521B (zh) * 2020-12-25 2022-07-26 安徽鸿程光电有限公司 抗菌防眩光膜及其制备方法

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