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WO2025041708A1 - Procédé de fabrication de substrat à film antireflet, et substrat à film antireflet - Google Patents

Procédé de fabrication de substrat à film antireflet, et substrat à film antireflet Download PDF

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Publication number
WO2025041708A1
WO2025041708A1 PCT/JP2024/029102 JP2024029102W WO2025041708A1 WO 2025041708 A1 WO2025041708 A1 WO 2025041708A1 JP 2024029102 W JP2024029102 W JP 2024029102W WO 2025041708 A1 WO2025041708 A1 WO 2025041708A1
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group
polysiloxane
formula
mol
carbon atoms
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Japanese (ja)
Inventor
和輝 江口
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials

Definitions

  • the present invention relates to a plastic substrate on which an anti-reflective film with excellent glass cleaner resistance is formed.
  • Such a refractive index reducing coating that exhibits reduced light reflectance is used as an anti-reflection coating and is applied to the surfaces of various substrates.
  • methods for forming such an antireflection film include gas phase methods such as CVD (Chemical Vapor Deposition), PVD (Physical Vapor Deposition) and sputtering, and liquid phase methods using an alkoxide compound or the like.
  • gas phase methods require expensive, large-scale equipment such as a vacuum deposition apparatus.
  • sol-gel method is known as a liquid phase method using an alkoxide compound or the like. This method has advantages such as being applicable to coating on a large area and being able to accommodate patterning when a film is formed by a flexographic printing method or the like. For this reason, antireflection films formed by liquid phase methods have been actively studied (see, for example, Patent Document 1).
  • the object of the present invention is to provide an anti-reflective film-forming material capable of obtaining an anti-reflective film that is suppressed from peeling off when wiped with a glass cleaner and has excellent resistance to glass cleaners, an anti-reflective film obtained from the anti-reflective film-forming material, and a plastic substrate with an anti-reflective film.
  • One embodiment of the present invention includes the following aspects.
  • Anti-reflection film forming material An anti-reflective coating material comprising the following component (A): Component (A): A polysiloxane (A) having a styryl group, and a ureido group and/or a urea bond, wherein the molar amount of the styryl group contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less relative to 100 mol % of Si atoms.
  • * represents a bond in each case.
  • the present invention provides an anti-reflective film-forming material capable of producing an anti-reflective film that is highly resistant to glass cleaners and suppresses peeling when wiped with a glass cleaner, as well as an anti-reflective film obtained from the anti-reflective film-forming material and a plastic substrate with an anti-reflective film.
  • the anti-reflective coating material (P) of the present invention is a material for forming an anti-reflective coating containing the following component (A):
  • Polysiloxane (A) may be composed of one kind or two or more kinds of polysiloxanes.
  • the polysiloxane (A) is a polysiloxane containing a styryl group, and the molar amount of the styryl group contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less, and more preferably 1 mol % or more and 30 mol % or less, relative to 100 mol % of Si atoms.
  • the polysiloxane (A) can be obtained, for example, by polycondensing an alkoxysilane compound component containing an alkoxysilane having at least one styryl group in the molecule, which optionally has one or more substituents, or a hydrolyzate thereof (hereinafter, these are also collectively referred to as compound (St)).
  • compound (St) A preferred specific example of compound (St) is a compound represented by the following formula (0).
  • R 1 is a hydrogen atom or an alkyl group, and multiple R 1 may be the same or different.
  • L is a divalent linking group, and when multiple Ls are present, the Ls may be the same or different.
  • n is an integer of 1 to 5.
  • n is preferably an integer of 1 to 4, more preferably 1 or 2, and most preferably 1.
  • m is an integer from 1 to 3.
  • R2 represents a hydrogen atom or an arbitrary substituent, and when a plurality of R2 are present, R2 's may be the same or different and may be bonded to each other to form a ring structure together with the carbon atoms of the benzene ring.
  • R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and any hydrogen atom possessed by R may be substituted with a halogen atom, an aromatic ring, or an aliphatic ring. When a plurality of R are present, the R may be the same or different from each other.
  • the alkyl group represented by R 1 in formula (0) is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group.
  • the divalent linking group represented by L in formula (0) includes a single bond or a group represented by *-L 1 -L 2 -L 3 -*, where L 1 , L 2 and L 3 independently represent a group selected from the group consisting of a single bond, -(CH 2 ) n - (n is an integer of 1 to 5), -NH-, -S-, -O-, -C( ⁇ O)-, and a phenylene group which may be substituted with any substituent.
  • L is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, or an arylene group having 5 to 12 carbon atoms, and is most preferably a single bond.
  • R2 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an acyl group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an arylcarbonyl group having 6 to 12 carbon atoms, or an arylcarbonyloxy group having 6 to 12 carbon atoms.
  • Examples of the ring structure formed by combining a plurality of R2s together with the carbon atoms of the benzene ring include cycloalkyl rings such as a cyclopentane ring and a cyclohexane ring, and aromatic rings such as a benzene ring.
  • R2 is more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and most preferably a hydrogen atom.
  • Preferred examples of the compound represented by formula (0) include the following compounds (a0-1) to (a0-23).
  • the proportion of the alkoxysilane compound represented by formula (0) or its hydrolysate in the total alkoxysilane used to obtain the polysiloxane (A) is preferably 0.5 mol% or more, more preferably 1 mol% or more, from the viewpoint of obtaining the effects of the present invention, and is preferably 65 mol% or less, more preferably 30 mol% or less, from the viewpoint of obtaining the effects of the present invention.
  • the polysiloxane (A) is a polysiloxane having a ureido group and/or a urea bond.
  • Polysiloxane having a ureido group and/or a urea bond can be obtained, for example, by polycondensation of an alkoxysilane compound component including an alkoxysilane compound represented by the following formula (1) (hereinafter also referred to as compound (U)).
  • R 1 ⁇ Si(OR 1' ) 3 ⁇ p (1)
  • p represents an integer of 1 or 2.
  • R 1 is a p-valent organic group having 2 to 13 carbon atoms and containing a ureido group and/or a urea bond, more preferably a p-valent organic group having 2 to 7 carbon atoms.
  • R 1 is preferably a monovalent organic group in which any hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms is substituted with a ureido group, more preferably a monovalent organic group in which any hydrogen atom of a hydrocarbon group having 1 to 6 carbon atoms is substituted with a ureido group.
  • R 1 is preferably a divalent organic group in which a urea bond is inserted between any carbon-carbon bond of a hydrocarbon group having 2 to 12 carbon atoms, more preferably a divalent organic group in which a urea bond is inserted between any carbon-carbon bond of a hydrocarbon group having 2 to 6 carbon atoms.
  • R 1' is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. Multiple R 1's may be the same or different.
  • R 1 and R 1′ may have a linear or branched structure.
  • alkoxysilane compound represented by formula (1) when p is 1, it is an alkoxysilane compound represented by formula (1-1).
  • alkoxysilane compound represented by formula (1-1) include, but are not limited to, ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, ⁇ -ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, and the like.
  • ⁇ -ureidopropyltriethoxysilane and ⁇ -ureidopropyltrimethoxysilane are particularly preferred because they are readily available as commercial products.
  • alkoxysilane compound represented by formula (1-2) include, but are not limited to, the following.
  • 1,3-bis[3-(triethoxysilyl)propyl]urea 1,3-bis[2-(triethoxysilyl)ethyl]urea, 1,3-bis[3-(trimethoxysilyl)propyl]urea, 1,3-bis[3-(tripropoxysilyl)propyl]urea, etc.
  • 1,3-bis[3-(triethoxysilyl)propyl]urea is particularly preferred because it is readily available as a commercial product.
  • the ratio of the alkoxysilane compound represented by formula (1) in the total alkoxysilane used to obtain polysiloxane (A) is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, and even more preferably 2.0 mol% or more, from the viewpoint of obtaining the effects of the present invention, and is preferably 99.9 mol% or less, more preferably 99.8 mol% or less, and even more preferably 99.5 mol% or less, from the viewpoint of obtaining the effects of the present invention.
  • the polysiloxane (A) may be a polysiloxane having a fluorine-containing organic group.
  • Such a fluorine-containing organic group is an organic group in which some or all of the hydrogen atoms of an aliphatic group or aromatic group are substituted with fluorine atoms, specific examples of which include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, a pentafluorophenyl group, and a perfluoroalkyl group.
  • perfluoroalkyl groups are preferred because they are easy to use to obtain a highly transparent coating film, and the fluorine-containing organic group is more preferably a perfluoroalkyl group having 3 to 15 carbon atoms. Specific examples include a perfluoropropyl group, a perfluorooctyl group, and a perfluorodecyl group.
  • a plurality of polysiloxanes having a fluorine-containing organic group on the side chain may be used in combination.
  • the method for obtaining the polysiloxane having the above-mentioned fluorine-containing organic group on the side chain but it is generally obtained by polycondensation of an alkoxysilane having the above-mentioned organic group on the side chain.
  • polysiloxanes obtained by polycondensation of an alkoxysilane component containing an alkoxysilane compound represented by formula (2a) are preferred.
  • R2Si (OR2 ' ) 3 The alkoxysilane compound represented by formula (2a) is an alkoxysilane having the above-mentioned fluorine-containing organic group on the side chain.
  • R2 in formula (2a) represents the above-mentioned fluorine-containing organic group, but the number of fluorine atoms contained in this organic group is not particularly limited. Multiple R2 ' may be the same or different.
  • R 2' in formula (2a) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group, where n- means normal, i- means iso, s- means secondary, and t- means tertiary, respectively.
  • alkoxysilane compounds represented by formula (2a) an alkoxysilane compound in which R 2 is a perfluoroalkyl group, or an alkoxysilane compound in which R 2 is an organic group represented by the following formula (2F) is more preferred.
  • k represents an integer of 0 to 12
  • k is preferably an integer of 2 to 12.
  • alkoxysilane compound represented by formula (2a) include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, (1H,1H,2H,2H-tridecafluorooctyl)trimethoxysilane, (1H,1H,2H,2H-tridecafluorooctyl)triethoxysilane, (1H,1H,2H,2H-heptadecafluorodecyl)trimethoxysilane, and (1H,1H,2H,2H-heptadecafluorodecyl)triethoxysilane.
  • the alkoxysilane compounds represented by formula (2a) may be used, but multiple kinds may be used as necessary.
  • the total molar amount of the alkoxysilane represented by formula (2a) is preferably 1 mol% or more, more preferably 2 mol% or more, based on the total molar amount of silicon atoms contained in the alkoxysilane compound used in the synthesis of polysiloxane (A). From the viewpoint of obtaining a homogeneous coating solution, it is preferably 20 mol% or less, more preferably 15 mol% or less.
  • Polysiloxane (A) may be a polysiloxane having a fluorine-containing organic group in the main chain direction of polysiloxane.
  • an alkoxysilane compound having two trialkoxysilyl groups bonded to a divalent organic group having a fluorine atom may be used as a monomer component for synthesizing such polysiloxane.
  • Specific examples of the alkoxysilane compound include the alkoxysilane compound represented by the following formula (2b).
  • R 2b in formula (2b) represents the above-mentioned fluorine-containing organic group, but the number of fluorine atoms contained in this organic group is not particularly limited.
  • R 2b in formula (2b) is preferably a divalent perfluoroalkyl chain or a divalent organic group represented by *-CH 2 -CH 2 -(CF 2 ) p -CH 2 -CH 2 -* (p is an integer of 1 to 12).
  • R 2b' each independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, or s-butyl group. Multiple R 2b' may be the same or different. Specific examples of the compound of formula (2b) include 1,6-bis(2-trimethoxysilylethyl)dodecafluorohexane and 1,6-bis(2-triethoxysilylethyl)dodecafluorohexane.
  • alkoxysilane compounds may be used in addition to the alkoxysilane compounds represented by the above formula (0), the above formula (1), and the above formula (2a) or (2b) used as required.
  • One or more kinds of the other alkoxysilane compounds may be used.
  • Other preferred specific examples of the alkoxysilane compound include an alkoxysilane compound represented by the following formula (3), an alkoxysilane compound represented by the following formula (4), and an alkoxysilane compound represented by the following formula (5), but are not limited thereto.
  • R 3 n Si(OR 3' ) 4-n (3) (In formula (3), R3 represents a monovalent organic group having no styryl group, no ureido group, no urea bond, and no fluorine atom, R3 ' represents a hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 3.) Si( OR4 ) 4 (4) ( R4 in formula (4) represents a hydrocarbon group.) (R 5' O) 3 Si-R 5 -Si(OR 5' ) 3 (5) (In formula (5), R5 represents a divalent organic group having 1 to 20 carbon atoms that does not have any of a styryl group, a ureido group, a urea bond, and a fluorine atom, and R5 ' represents a hydrocarbon group having 1 to 5 carbon atoms.)
  • the number of carbon atoms in R 3 in formula (3) is preferably 1 to 20, more preferably 1 to 15. When n is 2 or 3, R 3 may be the same or different. In R 3 ' in formula (3), when n is 1 or 2, R 3 ' may be the same or different. Specific examples of the alkoxysilane represented by formula (3) are shown below, but the invention is not limited thereto.
  • the proportion of the alkoxysilane compound represented by formula (3) in the total alkoxysilane compounds used to obtain polysiloxane (A) is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more, from the viewpoint of favorably obtaining the effects of the present invention. Also, from the viewpoint of favorably obtaining the effects of the present invention, it is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less.
  • R 4 in formula (4) represents a hydrocarbon group, and from the viewpoint of increasing reactivity, it is preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group.
  • R 4 may be the same or different.
  • tetraalkoxysilane compound of formula (4) examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which are readily available as commercial products.
  • at least one of the alkoxysilane compounds represented by formula (4) may be used, but multiple types may be used as necessary.
  • the amount of the alkoxysilane compound of formula (4) used is preferably 40 mol % or more, more preferably 50 mol % or more, based on the total amount of all alkoxysilane compounds used in the synthesis of polysiloxane (A), and is preferably 99 mol % or less, more preferably 96 mol % or less.
  • R 5' is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.
  • R 5' may be the same or different.
  • R5 is a divalent organic group having 1 to 20 carbon atoms that does not have any of a styryl group, a ureido group, a urea bond, or a fluorine atom, and the divalent organic group may contain a double bond, a triple bond, or a ring structure or a branched structure such as a phenyl group.
  • the divalent organic group may contain a heteroatom such as a nitrogen atom, an oxygen atom, or a fluorine atom.
  • a plurality of types of alkoxysilane compounds represented by formula (5) can be used as necessary.
  • Preferred examples of the alkoxysilane compound represented by formula (5) include dimethyldimethoxysilane and dimethyldiethoxysilane.
  • the proportion of the alkoxysilane compound represented by formula (5) in the total amount of the alkoxysilane compounds used in the synthesis of polysiloxane (A) is preferably 1 mol % or more, more preferably 2 mol % or more, and is preferably 20 mol % or less, more preferably 15 mol % or less.
  • the anti-reflective coating material (P) of the present invention may be an anti-reflective coating material containing the following component (B): polysiloxane (B) different from polysiloxane (A).
  • the polysiloxane (B) is a polysiloxane different from the polysiloxane (A). More preferred embodiments include, for example, a polysiloxane that does not contain a styryl group and a polysiloxane that does not contain either a ureido group or a urea bond.
  • Examples of monomer components for obtaining polysiloxane (B) include the alkoxysilane compounds exemplified for polysiloxane (A) or derivatives thereof, provided that the monomer components for obtaining polysiloxane (B) do not simultaneously include an alkoxysilane compound or derivative thereof containing a styryl group and an alkoxysilane compound or derivative thereof having at least one group of a ureido group and a urea bond. From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the monomer component for obtaining the polysiloxane (B) contains at least one compound selected from the group consisting of the alkoxysilane compounds represented by the above formulas (1) to (5).
  • the polysiloxane (B) may be a polysiloxane containing at least one functional group selected from the group consisting of a ureido group and a urea bond.
  • the polysiloxane (B) may be a polysiloxane having a fluorine-containing organic group.
  • the polysiloxane (B) may be a polysiloxane obtained by using the above-mentioned other alkoxysilane compounds.
  • alkoxysilane compound used in the synthesis of polysiloxane (B) from the viewpoint of suitably obtaining the effects of the present invention, at least one compound selected from the group consisting of the alkoxysilane compound represented by the above formula (3) and the alkoxysilane compound represented by the above formula (4) may be used.
  • the polysiloxane (B) may be composed of one kind or two or more kinds of polysiloxanes.
  • the mass ratio of the content of the polysiloxane (A) to the content of the polysiloxane (B) is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and even more preferably 10/90 to 90/10.
  • the method for polycondensing the polysiloxane used in the present invention is not particularly limited, but may be, for example, a method of hydrolyzing and condensing an alkoxysilane compound in an organic solvent such as alcohols or glycols.
  • the hydrolysis and condensation reaction may be either partial hydrolysis or complete hydrolysis.
  • water may be added in an amount of 0.5 times or more by mole of the total alkoxy groups in the alkoxysilane compound.
  • the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.1 to 2.5 times, and preferably 0.1 to 2.0 times the molar amount of all alkoxy groups in the alkoxysilane compound.
  • an acid or an alkali may be added as a catalyst.
  • the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as acetic acid, oxalic acid, and formic acid.
  • the alkali catalyst include inorganic salts such as sodium and potassium; and various amines (e.g., methylamine, ethylamine, ethanolamine, triethylamine, ammonia, etc.).
  • the amount of the catalyst used in the reaction is preferably 0.001 to 0.05 times by mole, more preferably 0.01 to 0.03 times by mole, based on the total alkoxy groups in the alkoxysilane compound.
  • the hydrolysis and condensation reaction may be accelerated by heating the solution in which the alkoxysilane compound is dissolved.
  • the heating temperature can be appropriately selected as desired, and the reaction system is preferably at 50° C. or higher, and preferably at 180° C. or lower.
  • the heating time can be appropriately selected as desired, and is preferably at least 10 minutes, and more preferably within 24 hours. More preferred reaction conditions include, for example, a method in which the mixture is stirred while being heated at 50° C. for 24 hours, and a method in which the mixture is stirred while being heated under reflux for 2 to 10 hours.
  • a method of heating a mixture of an alkoxysilane compound, a solvent, and an acid can be mentioned.
  • an acid is added to an alcoholic solvent in advance to prepare an alcoholic solution of the acid, and then the solution is mixed with an alkoxysilane and heated.
  • the amount of the acid is preferably 0.2 to 2 mol, and more preferably 0.5 to 2 mol, per mol of the total alkoxy groups in the alkoxysilane compound.
  • the heating temperature is preferably a liquid temperature of 50° C. or higher and 180° C. or lower.
  • the reaction time is preferably 10 minutes or longer and 24 hours or shorter.
  • the plurality of alkoxysilane compounds may be mixed in advance, or the plurality of alkoxysilane compounds may be added sequentially.
  • the total amount of silicon atoms in the alkoxysilane compound used in the reaction is preferably 20% by mass or less, more preferably 15% by mass or less, as a concentration calculated as SiO2 (hereinafter referred to as SiO2 equivalent concentration).
  • SiO2 equivalent concentration a concentration calculated as SiO2
  • the solvent used in polycondensing the alkoxysilane compound is not particularly limited as long as it dissolves the alkoxysilane compound represented by formula (1) and, if necessary, the alkoxysilane compound represented by formula (2a), the alkoxysilane compound represented by formula (2b), and the alkoxysilane compounds represented by formulas (3) to (5).
  • alcohols or organic solvents having good compatibility with alcohols are used.
  • organic solvent used in polycondensing the alkoxysilane compound examples include alcohols such as methanol, ethanol, propanol, and butanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • alcohols such as methanol, ethanol, propanol, and butanol
  • glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether
  • ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • a mixture of two or more of the above organic solvents may be used.
  • the polysiloxane used in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of preferably 500 to 500,000, more preferably 1,000 to 300,000.
  • Mw weight average molecular weight
  • the polysiloxane used in the present invention also has a molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC of preferably 15 or less, more preferably 10 or less. From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the molecular weight is within this range.
  • the anti-reflection film forming material (P) of the present invention is preferably a coating liquid containing a polymer component and a solvent, and contains polysiloxane (A) and, if necessary, polysiloxane (B) as the polymer component.
  • Specific examples of the solvent that can be used in the anti-reflective film-forming material (P) include the following solvents.
  • Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and diacetone alcohol; cyclic alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, and cyclodecanol; glycols such as ethylene glycol, propanediol, diethylene glycol, dipropylene glycol, butanediol (1,3-butanediol, 2,3-butanediol, etc.), 2-methyl-2,4
  • the solvent that can be used in the anti-reflection film-forming material (P) preferably contains one or more solvents selected from the group consisting of cyclic alcohols having 3 to 10 carbon atoms and glycols having 3 to 10 carbon atoms (e.g., ethylene glycol, propanediol, 2-methyl-2,4-pentanediol, etc.).
  • the solvents that can be used in the anti-reflection film-forming material (P) it is preferable to include one or more glycol ethers having 4 to 8 carbon atoms (for example, the above-mentioned glycol ethers having 4 to 8 carbon atoms are preferable, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether).
  • the method of preparing the anti-reflective coating material (P) is not particularly limited.
  • a method of using the polymerization solution containing the polysiloxane (A) and/or the polysiloxane (B) as it is and mixing and diluting with a solvent is simple.
  • the polymerization solution may be concentrated and diluted by adding a solvent, or may be replaced with another solvent and then diluted by mixing with a solvent.
  • the content of polysiloxane (A) in the anti-reflection film forming material (P) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, expressed as the concentration ( SiO2 equivalent concentration) of the total amount of silicon atoms contained in polysiloxane (A) converted into SiO2 . From the viewpoint of improving the storage stability of the solution, the content is preferably 15% by mass or less, more preferably 8% by mass or less.
  • the total content of polysiloxane (A) and polysiloxane (B) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, as a concentration ( SiO2 equivalent concentration) obtained by converting the total amount of silicon atoms contained in polysiloxane (A) and polysiloxane (B) into SiO2 .
  • it is preferably 15 mass% or less, more preferably 8 mass% or less.
  • the content of polysiloxane (A) in the anti-reflective film-forming material (P) is preferably 10 mass % or more, and more preferably 20 mass % or more, based on the total mass of the solids contained in the anti-reflective film-forming material (P).
  • the content of polysiloxane (A) is preferably 99.9 mass% or less, and more preferably 99 mass% or less, based on the total mass of the solid contents contained in the anti-reflective coating-forming material (P).
  • the anti-reflective film-forming material (P) contains polysiloxane (B)
  • the total content of polysiloxane (A) and polysiloxane (B) in the anti-reflective film-forming material (P) is, from the viewpoint of suitably obtaining the effects of the present disclosure, preferably 10 mass % or more, and more preferably 20 mass % or more, based on the total mass of the solids contained in the anti-reflective film-forming material (P).
  • the total amount of polysiloxane (A) and polysiloxane (B) is preferably 99.9 mass% or less, and more preferably 99 mass% or less, based on the total mass of the solid contents contained in the anti-reflective coating-forming material (P).
  • total mass of the solid content of the anti-reflective coating-forming material (P) means the total mass of the anti-reflective coating-forming material (P) when the anti-reflective coating-forming material (P) does not contain a solvent, and means the mass obtained by subtracting the mass of the solvent from the total mass of the anti-reflective coating-forming material (P) when the anti-reflective coating-forming material (P) contains a solvent.
  • other components may be contained in addition to the polysiloxane (A), the polysiloxane (B) and the solvent.
  • the other components include inorganic fine particles, a filler, a leveling agent, a surface modifier, a surfactant, and the like.
  • inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles.
  • metal oxide fine particles include fine particles of silica, alumina, titanium oxide, zirconium oxide, tin oxide, zinc oxide, etc. These may be in the form of beads.
  • the metal double oxide fine particles include fine particles of ITO (indium tin oxide), ATO (antimony trioxide), AZO (aluminum zinc oxide), zinc antimonate, and the like.
  • Other examples include hollow silica fine particles and porous silica fine particles.
  • the hollow silica fine particles may be in the form of beads.
  • the inorganic fine particles may be either a powder or a colloidal solution, but a colloidal solution is preferred because it is easy to handle.
  • the colloidal solution may be one in which inorganic fine particle powder is dispersed in a dispersion medium, or a commercially available colloidal solution.
  • inorganic fine particles include organosilica sol (methanol silica sol, MA-ST-S, MA-ST-M, MA-ST-L, MEK-ST-40, TOL-ST, MA-ST-UP, IPA-ST, IPA-ST-UP, MEK-ST-UP, EG-ST, NPC-ST-30, etc.) manufactured by Nissan Chemical Industries, Ltd.
  • organosilica sol methanol silica sol, MA-ST-S, MA-ST-M, MA-ST-L, MEK-ST-40, TOL-ST, MA-ST-UP, IPA-ST, IPA-ST-UP, MEK-ST-UP, EG-ST, NPC-ST-30, etc.
  • the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. If the average particle size of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured coating film formed from the prepared anti-reflective coating material may decrease.
  • the "average particle size” refers to the average primary particle size of inorganic fine particles, and may be determined by a method using a converted particle size from a specific surface area by a nitrogen gas adsorption method (BET method) or a value measured by observation with a transmission electron microscope.
  • the average particle size is indicated by the method using a converted particle size from a specific surface area by a nitrogen gas adsorption method (BET method).
  • BET method nitrogen gas adsorption method
  • the dispersion medium for the inorganic fine particles include water and organic solvents.
  • the pH or pKa of the colloidal solution is preferably adjusted to 2 to 10, more preferably 3 to 7.
  • organic solvents used as the dispersion medium for the colloidal solution include alcohols such as methanol, ethanol, propanol, and butanol; glycols such as ethylene glycol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide and dimethylacetamide; lactams such as N-methylpyrrolidone; esters such as ethyl acetate and butyl acetate; lactones such as ⁇ -butyrolactone; glycol ethers such as ethylene glycol monopropyl ether; and ethers such as tetrahydrofuran and 1,4-dioxane.
  • alcohols such as methanol, ethanol, propanol, and butanol
  • glycols such as ethylene glycol
  • ketones such as methyl ethyl ketone and methyl iso
  • alcohols and ketones are preferred.
  • These organic solvents can be used as the dispersion medium either alone or in combination of two or more.
  • the filler, leveling agent, surface modifier, surfactant, and the like may be any known material, and commercial products are particularly preferred because they are easily available.
  • the anti-reflection film-coated substrate of the present invention includes an anti-reflection film.
  • the anti-reflection film of the present invention is obtained by using the anti-reflection film-forming material (P) described above.
  • One embodiment of the antireflective film of the present invention is A step (1) of coating an anti-reflective coating material (P) on a substrate (also referred to as substrate (A)) having a heat-resistant temperature of 150° C. or less to form a coating film; A step (2) of drying the coating film; and (3) exposing the coating film dried in (2) above to light.
  • the substrate (A) has a heat-resistant temperature of 150° C. or less.
  • the heat resistance temperature refers to a temperature at which problems such as deformation do not occur even if the substrate is exposed to the heat during processing such as the formation of a resin film on the substrate.
  • the temperature varies depending on the degree of stretching treatment, but it is necessary that the temperature does not exceed at least the glass transition temperature (Tg).
  • Examples of the material of the substrate (A) include polycarbonate (PC), poly(meth)acrylate, polyurethane, polyolefin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polystyrene, polyethylene naphthalate, nylon 6, tetrafluoroethylene, (meth)acrylonitrile, diacetyl cellulose, triacetyl cellulose (TAC), acetate butyrate cellulose, etc.
  • the heat resistance temperature is disclosed in, for example, JP-A-09-100363.
  • the anti-reflection film-forming material (P) can be applied to form a coating film by a commonly used coating method, such as dip coating, spin coating, spray coating, slit coating, brush coating, roll transfer, screen printing, inkjet printing, or flexographic printing.
  • the viscosity of the anti-reflective film-forming material (P) is preferably 8 mPa ⁇ s or more, more preferably 9 mPa ⁇ s or more, and preferably 80 mPa ⁇ s or less, more preferably 70 mPa ⁇ s or less, and even more preferably 60 mPa ⁇ s or less.
  • the viscosity of the anti-reflective film forming material (P) is more preferably 0.5 mPa ⁇ s or more, and even more preferably 0.8 mPa ⁇ s or more.
  • the viscosity of the anti-reflective film forming material (P) is more preferably 80 mPa ⁇ s or less, and even more preferably 50 mPa ⁇ s or less.
  • the thickness of the coating formed on the substrate can be adjusted by the above-mentioned parameters during coating, but can also be easily adjusted by the SiO2 equivalent concentration of the anti-reflection coating material.
  • the above step (2) is a drying step for drying the solvent, and is suitable for cases where the time from coating to baking or exposure is not constant for each substrate, or where baking or exposure is not performed immediately after coating.
  • This drying is sufficient as long as the solvent is removed to an extent that the coating film shape is not deformed by transportation of the substrate, and the drying method is not particularly limited.
  • a method of drying on a hot plate at a drying temperature of 30 to 150° C. (set so as not to exceed the heat resistance temperature of the substrate), preferably 40 to 100° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes, can be mentioned.
  • the method for producing a substrate with an anti-reflection film of the present invention may include the following step (2') after the above step (2). Note that step (2') may be performed after the above step (3).
  • Step (2'): Step of curing the dried coating film by baking
  • the baking temperature can be any temperature between 70 and 150° C., but is preferably between 80 and 120° C. Heating can be performed by a conventional method, for example, using a hot plate, a hot air circulation oven, a far-infrared heating furnace (IR oven), a belt furnace, etc.
  • the coating thus obtained is characterized by good film-forming properties and high transmittance.
  • the light to be irradiated may be, for example, ultraviolet light having a wavelength of 150 to 800 nm or visible light, with ultraviolet light having a wavelength of 300 to 400 nm being preferred.
  • Examples of light sources for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), and microwave-excited electrodeless lamps.
  • the amount of light irradiation is preferably 1,000 to 200,000 J/ m2 , and more preferably 1,000 to 100,000 J/ m2 .
  • the coating can be formed according to the method of the present invention on a substrate having a higher refractive index than that of the coating, such as a surface of ordinary glass or film, to convert the substrate into one having anti-reflection properties.
  • the coating can be effectively used as a single coating on the substrate surface, but can also be effectively used as an anti-reflection laminate in which the coating is formed on an underlayer coating having a high refractive index.
  • the antireflection film of the present invention preferably has an average luminous reflectance for visible light having a wavelength of 380 nm to 800 nm of 3.0% or less, and more preferably 2.0% or less.
  • the average luminous reflectance is obtained from the spectral reflectance curve.
  • the spectral reflectance curve is obtained after the surface of the anti-reflection substrate opposite to the low refractive index layer is matte-treated with black paint or a black film is attached, and the incident angle from the perpendicular direction to the surface of the low refractive index layer is set to 5 degrees, a C light source is used as the light source, and the average luminous reflectance is the reflectance value obtained by calibrating the reflectance of each wavelength of visible light by the relative luminous efficiency and averaging it.
  • the relative luminous efficiency is the standard relative luminous efficiency for photopic vision.
  • the anti-reflection film-coated substrate of the present invention may further have an anti-soiling film laminated on the anti-reflection film.
  • the anti-soiling film is a film that suppresses adhesion of organic or inorganic substances to the surface, or a film that has the effect of allowing the adhesion of organic or inorganic substances to be easily removed by cleaning such as wiping even if the organic or inorganic substances adhere to the surface.
  • the thickness of the anti-soiling film is not particularly limited, but when the anti-soiling film is a fluorine-containing organosilicon compound coating, the film thickness is preferably 2 to 20 nm, more preferably 2 to 15 nm, and even more preferably 2 to 10 nm. If the film thickness is 2 nm or more, the anti-soiling layer will cover the entire surface uniformly, and will be practical from the viewpoint of abrasion resistance.
  • the anti-reflection film forming material (P) of the present invention can be suitably used in fields where anti-reflection of light is desired, such as displays of televisions, computers, car navigation systems, and mobile phones; mirrors with glass surfaces; and solar cells.
  • it is useful for anti-reflection films used in cover lenses and front panels of liquid crystal displays, plasma displays, projection displays, EL (Electro Luminescence) displays, SEDs (Surface-conduction Electron-emitter Displays), FEDs (Field Emission Displays), CRTs (Cathode Ray Tubes), and solar cells.
  • STMS p-styryltrimethoxysilane (contained in compound (St)) UPS: ⁇ -ureidopropyltriethoxysilane (contained in compound (U))
  • TEOS Tetraethoxysilane F13: (1H,1H,2H,2H-tridecafluorooctyl)trimethoxysilane GPS: ⁇ -glycidoxypropyltrimethoxysilane
  • MPMS ⁇ -methacryloxypropyltrimethoxysilane MeOH: Methanol EtOH: Ethanol HG: 2-methyl-2,4-pentanediol
  • PB Propylene glycol monobutyl ether
  • TEOS (18.7 g, 90.0 mmol), STMS (1.12 g, 5.0 mmol), and MeOH (18.6 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C., after which MeOH (9.4 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred for 30 minutes in an ice bath at 10 ° C. Then, the mixture was stirred at 65 ° C.
  • TEOS (17.7 g, 85.0 mmol), STMS (2.24 g, 10.0 mmol), and MeOH (18.6 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C., after which MeOH (9.2 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred for 30 minutes in an ice bath at 10 ° C. Then, the mixture was stirred at 65 ° C.
  • TEOS (19.8 g, 95.0 mmol) and MeOH (19.7 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C., after which MeOH (8.4 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred for 30 minutes in an ice bath at 10 ° C. Then, the mixture was stirred at 60 ° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the mixture was further reacted at 60 ° C. for 1 hour. Then, the mixture was allowed to cool to room temperature, EtOH (40.0 g) was added thereto, and the mixture was stirred at room temperature for 30 minutes to obtain solution K4.
  • TEOS (13.5 g, 65.0 mmol), GPS (7.09 g, 30.0 mmol), and MeOH (18.1 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C., after which MeOH (9.1 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred for 30 minutes in an ice bath at 10 ° C. Then, the mixture was stirred at 65 ° C. for 2 hours, and then UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the mixture was reacted at 65 ° C. for another 2 hours. Then, the mixture was allowed to cool to room temperature, EtOH (40.0 g) was added thereto, and the mixture was stirred at room temperature for 30 minutes to obtain solution K5.
  • TEOS (18.7 g, 90.0 mmol), F13 (2.34 g, 5.0 mmol), and MeOH (17.9 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C., after which MeOH (8.9 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred for 30 minutes in an ice bath at 10 ° C. Then, the mixture was stirred at 65 ° C.
  • Example 1 K8 (36.2 g) was added to a 200 mL eggplant-shaped flask and stirred at room temperature, K1 (13.8 g) was added thereto and stirred for an additional 30 minutes at room temperature, and then HG (5.0 g) and PB (45.0 g) were added thereto and stirred for an additional 30 minutes at room temperature to obtain anti-reflective coating material KL1.
  • Examples 2 to 7 and Comparative Examples 1 to 4 As shown in Table 2, anti-reflective coating materials KL2 to 7 and KM1 to 4 were obtained in the same manner as in Example 1, except that the type and amount of the polysiloxane solution used was changed.
  • the numbers in parentheses indicate the blending ratio of each component when the total of the polysiloxane and silica particles contained in the anti-reflective coating material is taken as 100 mass %.
  • the anti-reflective coating material KL7 of Example 7 was prepared so that the blending ratio of the total of the polysiloxanes contained in K3 and K6 to the silica particles contained in K8 was 27.5% and 72.5%, respectively, and the blending ratio of the polysiloxane (A) contained in K3 to the polysiloxane (B) contained in K6 was 1:1.
  • Example 8 HG (1.0 g) and PB (9.0 g) were added to the KL1 solution (10.0 g) and stirred to obtain a solution KL1'.
  • the substrate was irradiated with ultraviolet light at 50 mW/cm 2 (wavelength 365 nm equivalent) for 20 seconds (accumulated 1000 mJ/cm 2 ) using an ultraviolet irradiation device (manufactured by Eye Graphics, UB 011-3A type) and a high-pressure mercury lamp (input power supply 1000 W) to obtain a substrate with an anti-reflection coating.
  • an ultraviolet irradiation device manufactured by Eye Graphics, UB 011-3A type
  • a high-pressure mercury lamp input power supply 1000 W
  • Table 3 shows that by using polysiloxanes having styryl and ureido groups as substituents, it is possible to obtain anti-reflective coatings and coated substrates with excellent chemical resistance.
  • the present invention has excellent anti-reflection properties and chemical resistance, making it anticipated to be used in a variety of displays, particularly in vehicle cover lenses for automobiles, motorcycles, and other vehicles that are cleaned with various chemicals during maintenance.

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  • General Physics & Mathematics (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

Selon la présente invention, il est possible d'obtenir un film antireflet présentqnt une excellente résistance au nettoyage du verre qui empêche le film antireflet d'être retiré lorsqu'il est essuyé avec un dispositif de nettoyage de verre.　Un matériau de formation de film antireflet (P) contient un composant (A). Composant (A) : Un polysiloxane (A) qui a un groupe styryle et un groupe uréido et/ou une liaison urée, et dans lequel la quantité molaire du groupe styryle inclus dans le polysiloxane est de 0,1 à 70 % en moles par rapport à 100 % en moles d'atomes de Si.
PCT/JP2024/029102 2023-08-21 2024-08-15 Procédé de fabrication de substrat à film antireflet, et substrat à film antireflet Pending WO2025041708A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570546A (ja) * 1990-04-26 1993-03-23 Ciba Geigy Ag ポリシロキサン−尿素スチレン系マクロマー及びその架橋重合体
JP2000010090A (ja) * 1998-06-18 2000-01-14 Casio Comput Co Ltd 液晶表示装置
WO2011125984A1 (fr) * 2010-04-06 2011-10-13 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2019102655A1 (fr) * 2017-11-21 2019-05-31 東レ株式会社 Composition de résine de siloxane, film durci et dispositif d'affichage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570546A (ja) * 1990-04-26 1993-03-23 Ciba Geigy Ag ポリシロキサン−尿素スチレン系マクロマー及びその架橋重合体
JP2000010090A (ja) * 1998-06-18 2000-01-14 Casio Comput Co Ltd 液晶表示装置
WO2011125984A1 (fr) * 2010-04-06 2011-10-13 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2019102655A1 (fr) * 2017-11-21 2019-05-31 東レ株式会社 Composition de résine de siloxane, film durci et dispositif d'affichage

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