Classifications

• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • 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
• • 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
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
  • G02B1/115—Multilayers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

• the present invention relates to a light-transmitting article having an optical surface with excellent alkali resistance and a method for improving the alkali resistance of a light-transmitting article.
• the present invention relates to a light-transmitting article and a method for improving the alkali resistance of a light-transmitting article, which are characterized in that the outermost surface has a protective layer made of a material that does not contain fluorine atoms, and the lower surface has an anti-reflection layer made of a laminate structure of two or more materials with different refractive indices, and the protective layer does not affect the optical properties of the anti-reflection layer.
• image display devices such as monitors and optical components such as camera lenses
• light reflection on the surface reduces light transmission, causes external light to be reflected, and leads to deterioration in image quality such as ghosts and flares. Therefore, an anti-reflection layer to prevent light reflection on the surface has traditionally been placed on the surface of image display devices and optical components.
• a typical anti-reflection layer has a laminate structure in which high refractive index layers and low refractive index layers are alternately repeated, and the low refractive index layer is disposed on the outermost surface (outermost surface) on the side opposite the substrate (air side).
• metal oxides or metal nitrides such as titanium oxide ( TiO2 ), niobium oxide ( Nb2O5 ), zirconium oxide ( ZrO2 ), and silicon nitride ( Si3N4 ) are used, while for low refractive index layers, silicon dioxide ( SiO2 ), magnesium fluoride ( MgF2 ), etc. are generally used.
• each high and low refractive index layer is generally smaller than the wavelength of the light to be anti-reflection, and precise control of the refractive index and film thickness is required during film formation to achieve high anti-reflection performance.
• the anti-reflective film is placed on the outermost surface, it is required to be durable against friction, chemicals, etc. (Patent Document 1: JP 2021-092768 A). If part of the anti-reflective film falls off due to friction or chemicals, or if the thickness of the anti-reflective layer changes, the reflectance will change. In some cases, the reflectance may become higher than that of the substrate itself.
• Patent Documents 2, 3, and 4 JP 2011-069995 A, JP 2011-100111 A, and JP 2020-060657 A.
• a thin film of a fluorine-containing organosilicon compound with a thickness of about 10 nm is used as a protective layer that is thin enough not to affect the optical properties of the anti-reflection film and is durable.
• Some organofluorine compounds are known to accumulate in the environment and living organisms, including the human body, and are harmful, and the harmful properties of other organofluorine compounds are not fully understood, so there is a need for substitutes for organofluorine compounds in general.
• films that are thin enough not to affect the optical properties of the anti-reflection film do not provide sufficient durability.
• the present invention has been made in consideration of the above circumstances, and aims to provide a light-transmitting article having an optical surface with excellent durability (particularly alkali resistance) using a protective layer on the outermost surface made of a material that does not contain fluorine atoms, and a method for improving the alkali resistance of a light-transmitting article.
• a protective layer made of a material that does not contain fluorine atoms preferably a cured layer of a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms and/or a metal oxide layer
• the change in visual reflectance of the article surface with or without the protective layer is less than 0.5%, and that the change in visual reflectance of the article surface before and after the alkali resistance test described below is less than 1.0%
• the optical properties of the anti-reflective layer do not change before and after the formation of the protective layer, and that the article with the anti-reflective layer (light-transmitting article) has excellent alkali resistance, which led to the present invention.
• a light-transmitting article comprising an antireflection layer formed on an outer surface of a substrate and having a laminate structure of two or more materials having different refractive indices, and a protective layer formed on the outer surface of the antireflection layer and made of a material that does not contain fluorine atoms, wherein the change in visual reflectance of the article surface due to the presence or absence of the protective layer is less than 0.5%, and the change in visual reflectance of the article surface before and after the following alkali resistance test is less than 1.0%.
• test liquid aqueous sodium hydroxide solution
• pure water is poured over it for 1 minute to remove the test liquid, and moisture on the surface of the test article is removed by blowing dry air over it.
• the protective layer is a layer of a cured product of a hydrolyzable group-containing water-repellent organosilicon compound not containing a fluorine atom and/or a metal oxide layer.
• the protective layer is composed of two or more layers, namely a metal oxide layer and a cured layer of a hydrolyzable group-containing, water-repellent organosilicon compound that does not contain fluorine atoms, the outermost layer being the cured layer of the hydrolyzable group-containing, water-repellent organosilicon compound that does not contain fluorine atoms, and the water contact angle of the protective layer surface is 90 degrees or more.
• a method for improving the alkali resistance of a light-transmitting article in which changes in anti-reflection performance are suppressed the method being characterized in that in the light-transmitting article having a substrate, an anti-reflection layer formed on the substrate and consisting of a laminate structure of two or more materials having different refractive indices, and a protective layer formed on the anti-reflection layer, the protective layer being made of a cured layer of a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms and/or a metal oxide layer, and the thickness of the protective layer is 1 nm or more and 10 nm or less.
• a light-transmitting article with an anti-reflective layer in which a protective layer made of a material containing no fluorine atoms according to the present invention is disposed on the surface, the change in visual reflectance of the article surface with or without the protective layer is less than 0.5%, and the change in visual reflectance of the article surface before and after the alkali resistance test described below is less than 1.0%, has excellent alkali resistance without the protective layer affecting the optical properties of the anti-reflective layer.
• the light-transmitting article of the present invention is a light-transmitting article comprising an antireflection layer made of a laminate structure of two or more materials having different refractive indices on the outer surface of a substrate, and a protective layer made of a material not containing fluorine atoms on the outer surface of the antireflection layer, characterized in that the change in visual reflectance of the article surface due to the presence or absence of the protective layer is less than 0.5%, and the change in visual reflectance of the article surface before and after the alkali resistance test described below is less than 1.0%.
• the light-transmitting article of the present invention is composed of a substrate, an antireflection layer, and a protective layer.
• the substrate that can be used in the present invention is not particularly limited as long as it is light-transmitting, and may be made of various materials such as glass, plastic, ceramic, and quartz. In addition, the substrate may be made of these materials as a base material on which a functional layer is formed. Examples of the functional layer include an antistatic layer and a hard coat layer.
• the substrate may be in the form of a plate, a film, or other shapes. In particular, a transparent glass plate, a plastic plate with a hard coat, or a plastic film with a hard coat can be suitably used as the substrate.
• the substrate surface may be pretreated before forming the anti-reflective layer. Pretreatment ensures good adhesion between the substrate and the anti-reflective layer, resulting in high durability.
• the method of pretreating the substrate is not particularly limited as long as it can remove contaminants from the substrate surface and make the substrate surface hydrophilic.
• Examples include treatment with an alcohol such as ethanol or 2-propanol, treatment with an alkaline cleaner, treatment with oxygen or argon plasma, and treatment with OH radicals. These methods may be used in combination. Treatment with an alkaline cleaner is preferred, and treatment with plasma or OH radicals is more preferred. It is even more preferred to perform treatment with an alkaline cleaner followed by treatment with plasma or OH radicals.
• Hydrophilicity can be evaluated by the contact angle of water on the substrate, which is preferably 40 degrees or less, more preferably 20 degrees or less, and even more preferably 10 degrees or less.
• the contact angle of water is measured in accordance with JIS R 3257:1999.
• the anti-reflection layer is made of a laminated structure of two or more materials with different refractive indices, and has a laminated structure in which high refractive index layers and low refractive index layers are alternately repeated.
• Metal oxides and metal nitrides such as titanium oxide ( TiO2 ), niobium oxide ( Nb2O5 ), zirconium oxide ( ZrO2 ), and silicon nitride ( Si3N4 ) are used as the high refractive index layers, and niobium oxide ( Nb2O5 ) is preferred among them.
• Silicon dioxide ( SiO2 ) and magnesium fluoride ( MgF2 ) are used as the low refractive index layers, and silicon dioxide ( SiO2 ) is preferred among them.
• the anti-reflection layer can be formed by a dry film-forming method or a wet film-forming method.
• the dry film-forming method include a vacuum deposition method, a sputtering method, and a chemical vapor deposition (CVD) method.
• the wet film-forming method include a spray method using metal oxide nanoparticles or a metal alkoxide as a precursor, a spin coating method, a dip method, a brush coating method, a gravure coating method, and a bar coating method.
• the vacuum deposition method can use a heating method for the material to be deposited, such as a resistance heating method or an electron beam heating method.
• a heating method for the material to be deposited such as a resistance heating method or an electron beam heating method.
• heating of the deposition substrate or plasma/ion beam irradiation (ion assist) can be used.
• an anti-reflection layer can be formed by electron beam deposition or ion-assisted deposition using a method such as that shown in Patent Document 3.
• a sputtering method of a target material such as a high-frequency plasma method, a direct current plasma method, or an ion beam method
• a sputtering method of a target material such as a high-frequency plasma method, a direct current plasma method, or an ion beam method
• reactive sputtering by heating the deposition substrate, irradiating plasma or an ion beam (ion-assisted, radical-assisted), or introducing a reactive gas such as oxygen gas or nitrogen gas can be used.
• an anti-reflection layer by the sputtering method can be deposited by the method shown in Patent Document 4.
• the CVD method may be thermal CVD, plasma-assisted CVD, photo-CVD, or other methods.
• the film may be formed by the method shown in JP 2007-284791 A (Patent Document 5).
• the film thickness (total) of the antireflective layer is preferably 100 to 1,000 nm, and more preferably 200 to 500 nm. If the total film thickness of the antireflective layer is too thin, it may not be possible to obtain a low light reflectance over the entire wavelength range of visible light, while if it is too thick, cracks and peeling from the substrate may occur easily, and uniform light reflection characteristics may not be obtained within the antireflective layer.
• the film thickness of the antireflective layer can be measured by cross-sectional observation using a scanning electron microscope or transmission electron microscope.
• the surface of the antireflection layer may be pretreated before the formation of the protective layer, which provides good adhesion between the antireflection layer and the protective layer and high durability.
• the method for pretreating the antireflection layer is not particularly limited as long as it can remove contaminants from the surface of the antireflection layer.
• treatment with oxygen plasma, argon plasma, or OH radicals can be suitably used.
• substrates such as those shown in JP 2011-069995 A (Patent Document 2), JP 2011-100111 A (Patent Document 3), JP 2020-060657 A (Patent Document 4), Japanese Patent No. 4834939 A (Patent Document 6), Japanese Patent No. 7121070 A (Patent Document 7), Japanese Patent No. 7217118 A (Patent Document 8), and Japanese Patent No. 7389259 A (Patent Document 9) can be used.
• the protective layer is made of a material that does not contain fluorine atoms, and is preferably composed of a cured layer of a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms, or a metal oxide layer, or two or more of these layers.
• Cured layer of hydrolyzable group-containing, water-repellent organosilicon compound that does not contain fluorine atoms The cured layer of the hydrolyzable group-containing, water-repellent organosilicon compound that does not contain fluorine atoms is formed using a protective layer-forming agent that contains a hydrolyzable group-containing, water-repellent organosilicon compound that does not contain fluorine atoms.
• the hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms is one that has a hydrolyzable silyl group at one or both ends of a hydrocarbon group, or one that has a hydrolyzable group bonded to a hydrocarbon group-containing silicon atom, and the hydrocarbon group may be linear or branched, and the total number of carbon atoms contained in the hydrocarbon group portion is preferably 12 or more.
• the hydrolyzable group-containing water-repellent organosilicon compound not containing a fluorine atom is preferably a compound represented by the following formula (1), formula (2) or formula (3) (wherein formula (2) represents the molecular formula of a monomer or the composition formula of a polymer).
• A is a monovalent hydrocarbon group having 1 to 50 carbon atoms
• B is a hydrogen atom or a hydroxyl group
• E is a hydrogen atom or a monovalent hydrocarbon group having 1 to 50 carbon atoms, the total number of carbon atoms contained in A and E is 12 or more
• Y is a single bond, or a divalent hydrocarbon group which may have one or more types selected from silicon atoms and siloxane bonds
• R is an alkyl group or phenyl group having 1 to 4 carbon atoms
• X is independently a hydrolyzable group
• c is 2 or 3.
• each G is independently a monovalent hydrocarbon group having 8
• A is a monovalent hydrocarbon group having 1 to 50 carbon atoms, preferably 10 to 50 carbon atoms
• B is a hydrogen atom or a hydroxyl group
• E is a hydrogen atom or a monovalent hydrocarbon group having 1 to 50 carbon atoms, preferably 10 to 50 carbon atoms.
• Examples of the monovalent hydrocarbon group having 1 to 50 carbon atoms for A and E include the following.
• A is preferably a linear, saturated monovalent hydrocarbon group having 10 to 50 carbon atoms
• B is preferably a hydroxyl group
• E is preferably a linear, saturated monovalent hydrocarbon group having 10 to 50 carbon atoms.
• the total number of carbon atoms contained in A and E is 12 or more, and preferably 20 to 60.
• Y may have one or more bonds selected from a single bond, a silicon atom, and a siloxane bond, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.
• the divalent hydrocarbon group include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, or a silarylene structure, and divalent groups in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or
• the groups bonded to silicon atoms in the diorganosilylene group, silalkylene structure, silarylene structure, and organopolysiloxane residue are preferably alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl, or phenyl groups.
• the alkylene groups in the silalkylene structure are preferably ethylene groups having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), and the like.
• the organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are bonded by an alkylene group such as an ethylene group or a propylene group.
• Y examples include the following groups: In the following structure, it is preferable that the left bond is bonded to a carbon atom, and the right bond is bonded to a silicon atom.
• f is independently an integer of 1 to 10
• g and h are each an integer of 1 to 8, and the sum of g and h is an integer of 2 to 10.
• j is an integer of 1 to 9, and k is an integer of 2 to 4.
• X is independently a hydrolyzable group.
• hydrolyzable groups include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy and propionoxy groups; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy groups; and halogen groups, such as chlorine, bromo, and iodine groups. Among these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred.
• R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and among these, a methyl group and an ethyl group are preferable.
• c is 2 or 3, and preferably 3.
• e is a number between 0 and 3 (0 or a positive number less than 3), preferably a number between 0 and 2, and more preferably 0.
• d is (3-e)/2, preferably 1.5.
• G is independently a monovalent hydrocarbon group having 8 to 50 carbon atoms, preferably 10 to 36 carbon atoms, and more preferably 12 to 28 carbon atoms.
• Examples of such a monovalent hydrocarbon group include those shown below.
• m is an integer of 7 to 49, preferably an integer having 9 to 35 carbon atoms, more preferably an integer having 11 to 27 carbon atoms, and each n is an integer of 1 or more such that the total number of carbon atoms in each structure is 8 to 50, preferably 10 to 36, more preferably 12 to 28.
• J is independently a hydrogen atom, a hydroxyl group or a methyl group, and among these, a methyl group is preferred.
• Specific examples of the compound represented by the above formula (1) include octadecyltrimethoxysilane, octadecyltrichlorosilane, octadecyltriethoxysilane, dodecyltrimethoxysilane, triacontyltrichlorosilane, and the compounds shown below.
• compounds represented by the above formula (3) include 1,3-dioctadecyl-1,1,3,3-tetramethyldisilazane, 1,3-didodecyl-1,1,3,3-tetramethyldisilazane, 1,3-didecyl-1,1,3,3-tetramethyldisilazane, and 1,3-dioctyl-1,1,3,3-tetramethyldisilazane.
• the polysiloxane can be produced by mixing a hydrocarbon terminal group-containing compound having a terminal SiH group with a compound having an alkenyl group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst (Preparation Method 2).
• an example of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal is a compound represented by the following formula (1a):
• a and B are the same as above.
• E1 is a monovalent hydrocarbon group having 1 to 50 carbon atoms, the total number of carbon atoms contained in A and E1 is 12 or more, and Y1 may have one or more types selected from a silicon atom and a siloxane bond, and is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms.
• E 1 is a monovalent hydrocarbon group having 1 to 50 carbon atoms, and examples thereof include the same monovalent hydrocarbon groups having 1 to 50 carbon atoms as those for E described above.
• Y1 may have one or more bonds selected from silicon atoms and siloxane bonds, and is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, examples of which include those shown below.
• it is preferable that the bond on the left side is bonded to the carbon atom bonded to A, B, or E1 , and the bond on the right side is bonded to a vinyl group.
• f' is an integer of 0 to 8
• h' is an integer of 0 to 6
• the sum of g and h' is an integer of 2 to 8.
• the amount of the compound having a SiH group and a hydrolyzable silyl group used is preferably 1 to 6 moles, and more preferably 1.5 to 4 moles, per mole of alkenyl group in the hydrocarbon end group-containing compound having an alkenyl group at the end.
• hydrocarbon terminal group-containing compound having a SiH group at the terminal is a compound represented by the following formula (1b): (In the formula, A, B, and E1 are the same as above, and Y2 is a divalent hydrocarbon group having a silicon atom or a siloxane bond.)
• Y2 is a divalent hydrocarbon group having a silicon atom or a siloxane bond, and examples thereof include those shown below.
• the bond on the left side is bonded to a carbon atom, and the bond on the right side is bonded to a hydrogen atom.
• f and k are the same as above.
• Examples of compounds having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane.
• the amount of the compound having an alkenyl group and a hydrolyzable silyl group used is preferably 1 to 5 moles, and more preferably 1 to 3 moles, per mole of SiH group in the hydrocarbon end group-containing compound having an SiH group at the end.
• examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium.
• platinum compounds such as vinylsiloxane coordination compounds. It is preferable to use the platinum compounds by dissolving them in solvents such as toluene, lower alcohols, higher alcohols, and silicones.
• the amount of the hydrosilylation catalyst used is preferably 0.001 to 1,000 ppm, and more preferably 0.01 to 100 ppm, calculated as transition metal (by mass), based on the mass of the hydrocarbon terminal group-containing compound having an alkenyl group or SiH group at the terminal.
• a solvent can be used when carrying out the reaction in Preparation Methods 1 and 2.
• the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having an alkenyl group or a SiH group at the terminal.
• the reaction conditions for the hydrocarbon end group-containing compound having an alkenyl group at the end with the compound having a SiH group and a hydrolyzable silyl group, and the reaction conditions for the hydrocarbon end group-containing compound having a SiH group at the end with the compound having an alkenyl group and a hydrolyzable silyl group are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, and a reaction time of 0.5 to 72 hours, particularly 1 to 36 hours.
• the amount of ammonia gas used is preferably 1 to 300 cc/min, and more preferably 30 to 200 cc/min.
• the reaction conditions for the reaction between the hydrocarbon end group-containing compound having an alkenyl group at the end and trichlorosilane reactant and ammonia gas are preferably room temperature (23 ⁇ 15°C, the same applies below), particularly 20 to 30°C, and 2 to 36 hours, particularly 4 to 12 hours.
• a hydrolysis condensation catalyst such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added to the protective layer forming agent containing the hydrolyzable group-containing water-repellent organosilicon compound not containing fluorine atoms.
• organotin compound dibutyltin dimethoxide, dibutyltin dilaurate, etc.
• an organotitanium compound tetra n-butyl titanate, etc.
• an organic acid acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.
• acetic acid tetra n-butyl titanate, dibutyltin dilaurate, etc. are particularly desirable.
• the amount added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the hydrolyzable group-containing water-repellent organosilicon compound not containing fluorine atoms.
• the protective layer forming agent containing the hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms may contain a solvent.
• the solvent is desirably a non-fluorine-based solvent, and is preferably a hydrocarbon-based solvent (petroleum benzine, mineral spirits, toluene, xylene, etc.), a ketone-based solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an alcohol-based solvent (ethanol, 1-propanol, 2-propanol, butanol, etc.), or an ether-based solvent (tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, etc.).
• THF tetrahydrofuran
• the above solvents may be used in combination of two or more kinds, and it is preferable to dissolve the hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms uniformly.
• the optimum concentration of the hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms to be dissolved in the solvent may be appropriately selected depending on the method of use of the protective layer forming agent, and is not limited. It is usually dissolved to a concentration of 0.01 to 30% by mass, preferably 0.02 to 25% by mass, and more preferably 0.05 to 20% by mass.
• Metal Oxide Layer examples of metals constituting the metal oxide layer include zirconium, niobium, hafnium, and tantalum.
• the metal oxide layer is formed using a protective layer forming agent containing metal oxide nanoparticles, or a precursor material that can be converted into a metal oxide salt or a metal oxide. Note that in the present invention, the metal oxide does not include silicon oxide.
• Metal oxide nanoparticles include nanoparticles of zirconium oxide (ZrO x ), niobium oxide (Nb x O y ), hafnium oxide (HfO x ), tantalum oxide (Ta x O y ), and the like.
• the average particle diameter is preferably 1 nm to 10 nm, more preferably 2 to 8 nm, and is measured by a dynamic light scattering method in accordance with JIS Z 8828:2019.
• the metal oxide nanoparticles can be commercially available. Examples include Zirconeo (manufactured by ITEC) and Baylar Nb-G6000 (manufactured by Taki Chemical).
• Precursor materials that can be converted to metal oxide salts or metal oxides include ammonium zirconium carbonate, zirconium acetate, zirconium oxynitrate, zirconium nitrate, zirconium oxychloride, zirconium hydroxide chloride, ammonium niobium oxalate, niobium oxalate, tantalum oxalate, and the like.
• the protective layer forming agent containing metal oxide nanoparticles, or a precursor material that can be converted to a metal oxide salt or metal oxide may contain a diluent.
• the diluent is preferably water (distilled water, ion-exchanged water, purified water, ultrapure water, etc.), a ketone-based solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), or an alcohol-based solvent (ethanol, 1-propanol, 2-propanol, butanol, etc.). Water is particularly preferred.
• the diluent may be a mixture of two or more of these, and it is preferable that the metal oxide nanoparticles are uniformly dispersed, or that the precursor substance that can be converted to a metal oxide salt or a metal oxide is uniformly dissolved.
• the optimum concentration of the metal oxide nanoparticles or the precursor substance that can be converted to a metal oxide salt or a metal oxide to be dissolved or dispersed in the diluent may be appropriately selected depending on the method of using the protective layer forming agent, and is not limited.
• the metal oxide is dissolved or dispersed to a concentration of 0.01 to 0.9 mass%, preferably 0.02 to 0.9 mass%, and more preferably 0.05 to 0.5 mass%.
• the protective layer is formed on the antireflection layer using a protective layer forming agent containing the above-mentioned hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms, or a protective layer forming agent containing metal oxide nanoparticles, or a precursor substance that can be converted into a metal oxide salt or a metal oxide.
• a protective layer using a protective layer forming agent containing a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms can be achieved by known methods such as brush coating, dipping, spraying, bar coating, and vapor deposition.
• the heating method used during the vapor deposition process can be either a resistance heating method or an electron beam heating method, and is not particularly limited.
• the protective layer in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferable to apply the protective layer at 60 to 150°C and a relative humidity of 85% or less for 30 minutes to 4 hours, and in the case of vapor deposition coating, it is preferable to apply the protective layer at 25 to 150°C and a relative humidity of 85% or less for 30 minutes to 4 hours.
• a protective layer using a protective layer forming agent containing metal oxide nanoparticles, or a precursor substance that can be converted into a metal oxide salt or metal oxide can be performed by known methods such as brushing, dipping, spraying, bar coating, and vapor deposition.
• the heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited.
• the protective layer is dried after formation.
• the drying conditions are exposure to an environment of 20-200°C temperature and 95% or less relative humidity for at least 1 minute.
• the conditions are set appropriately depending on the method of forming the protective layer. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferable to dry for 30 minutes to 4 hours at 60-150°C and 85% or less relative humidity, and in the case of vapor deposition coating, it is preferable to dry for 30 minutes to 4 hours at 25-150°C and 85% or less relative humidity.
• a reaction process is carried out after the formation of the protective layer.
• the reaction process conditions are exposure to an environment with a temperature of 20 to 200°C and a relative humidity of 95% or less for 1 minute or more.
• the conditions are set appropriately depending on the method of forming the protective layer. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferable to apply the coating at 60 to 150°C and a relative humidity of 85% or less for 30 minutes to 4 hours, and in the case of vapor deposition coating, it is preferable to apply the coating at 25 to 150°C and a relative humidity of 85% or less for 30 minutes to 4 hours.
• the protective layer can also be composed of two or more layers, the above-mentioned hardened layer of the water-repellent organosilicon compound containing hydrolyzable groups that does not contain fluorine atoms, and a metal oxide layer.
• the outermost layer is a hardened layer of the water-repellent organosilicon compound containing hydrolyzable groups that does not contain fluorine atoms.
• the thickness of the protective layer is preferably 1 to 10 nm, and more preferably 1.5 to 5 nm. If the thickness of the protective layer is less than 1 nm, the surface coverage of the protective layer is low, and the antireflection layer is exposed, so that durability may not be obtained. If the thickness exceeds 10 nm, the change in luminous reflectance becomes large, and the antireflection film properties may deteriorate.
• the thickness of the protective layer is preferably 1 nm to 10 nm, more preferably 1.5 to 5 nm.
• the thickness of the protective layer is less than 1 nm, the surface coverage of the protective layer is low and the antireflection layer is exposed, which may result in poor durability, whereas if the thickness exceeds 10 nm, the change in luminous reflectance becomes large and the antireflection film properties may deteriorate.
• the thickness of the protective layer is preferably 1 nm or more and less than 10 nm, and more preferably 2 to 5 nm. If the thickness of the protective layer is less than 1 nm, the surface coverage of the protective layer is low, and the antireflection layer is exposed, so that durability may not be obtained.
• the thickness is 10 nm or more, the change in luminous reflectance becomes large, and the antireflection film properties may deteriorate.
• the protective layer is composed of two or more layers, that is, a metal oxide layer and a cured layer of a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms
• the thickness of the protective layer is preferably 2 to 10 nm, and more preferably 3 to 6 nm.
• the change in visual reflectance of the article surface before and after the alkali resistance test described below is less than 1.0% (0% or more and less than 1.0%). If the change in visual reflectance of the article surface before and after the alkali resistance test is 1.0% or more, in addition to deterioration of the protective layer, deterioration of the antireflection layer also occurs, and visibility may also decrease. In order to keep the change in visual reflectance of the article surface before and after the alkali resistance test within the above range, it is preferable to keep the film thickness of the protective layer within the above range.
• test liquid aqueous sodium hydroxide solution
• the water contact angle of the protective layer surface is preferably 90 degrees or more, and more preferably 95 to 105 degrees. If the water contact angle of the protective layer surface is less than 90 degrees, the surface coverage of the protective layer is low and the anti-reflection layer is likely to be exposed, and durability may not be obtained. In order to achieve the above water contact angle, it is preferable to keep the film thickness of the protective layer within the above range.
• the water contact angle of the protective layer surface is preferably less than 65 degrees, and more preferably 10 to 50 degrees. If the water contact angle of the protective layer surface is 65 degrees or more, the surface coverage of the protective layer is low and the anti-reflection layer is likely to be exposed, and durability may not be obtained. In order to achieve the above water contact angle, it is preferable to keep the film thickness of the protective layer within the above range.
• the protective layer when the protective layer is composed of two or more layers, a metal oxide layer and a cured layer of a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms, and the outermost surface is the cured layer of a hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms, the water contact angle of the protective layer surface is preferably 90 degrees or more, more preferably 95 to 105 degrees. If the water contact angle of the protective layer surface is less than 90 degrees, the surface coverage of the protective layer is low and the anti-reflection layer is likely to be exposed, and durability may not be obtained. In order to achieve the above water contact angle, it is preferable to keep the film thickness of the protective layer within the above range.
• the water contact angle can be measured in accordance with JIS R 3257:1999.
• optically transparent article of the present invention is suitable for use in applications such as windows, lenses, display covers, and protective films used in mobile electronic devices, household electrical appliances, automobiles, outdoor products, building materials, housing equipment, and eyeglasses.
• the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
• the molar amount of a compound is a value calculated by dividing the measured mass of the target compound by the molecular weight of the polymer identified by 1 H-NMR analysis.
• the test environment conditions are 23° C. and 50% relative humidity.
• An anti-reflection layer having the thickness shown in Table 1 below was formed on the surface of the glass substrate that had been subjected to the alkaline cleaning under the following conditions using a sputtering film formation device.
• SiO2 was formed as the low refractive index layer
• Nb2O5 was formed as the high refractive index layer.
• Oxygen plasma irradiation was performed before the anti-reflection layer was formed.
• the film formation rate of SiO2 was 0.3 nm /sec
• the film formation rate of Nb2O5 was 0.4 nm/sec, and the film thickness of each layer was controlled by the film formation time.
• Method 1 for forming protective layer The above glass substrate with an antireflection layer was set in a resistance heating type vacuum deposition apparatus (VTR-350M, manufactured by ULVAC KIKOU), 12 ⁇ L of the following protective layer forming agent was dropped on the resistance heating section, and the pressure was reduced. When the pressure inside the container was reduced to 6 ⁇ 10 ⁇ 3 Pa or less, resistance heating was started. The power input to the resistance heating was adjusted so that the maximum evaporation rate measured by a quartz crystal oscillator film thickness meter installed at a position about 20 cm away from the resistance heating section was 1.0 nm/sec or more, and resistance heating was continued for 300 seconds.
• VTR-350M resistance heating type vacuum deposition apparatus
• the apparatus After waiting for 5 minutes to cool the apparatus, the apparatus was opened to the atmosphere, and a glass substrate with an antireflection layer coated with a hydrolyzable group-containing water-repellent organosilicon compound not containing a fluorine atom was obtained.
• the above substrate was left for 4 hours in an environment of 80° C. and 80% relative humidity to fix the protective layer, thereby obtaining a glass substrate (light-transmitting article) with an antireflection layer having a protective layer made of a cured product of the hydrolyzable group-containing water-repellent organosilicon compound that does not contain fluorine atoms.
• the water contact angle of the protective layer was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS R 3257:1999 by the sessile drop method with a droplet size of 2 ⁇ l and an analysis method of ⁇ /2.
• Example 1 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that the above-mentioned protective layer forming agent 1 was used and the amount of the protective layer forming agent dropped was 50 ⁇ L, and the same evaluation was performed.
• Example 2 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer forming agent 2 shown below was used, and the same evaluation was carried out.
• the resulting compound was confirmed to have a structure represented by the following formula (A) by 1 H-NMR.
• the compound represented by the above formula (A) was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 20% by mass, to prepare protective layer forming agent 2.
• PGME propylene glycol monomethyl ether
• Example 2 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer forming agent 3 shown below was used, and the same evaluation was carried out.
• Protective Layer Forming Agent 3 Hexyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 20% by mass, to prepare protective layer forming agent 3.
• PGME propylene glycol monomethyl ether
• Example 3 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer forming agent 4 shown below was used, and the same evaluation was carried out.
• the obtained product was mixed with 3.00g of toluene, and aged for 6 hours at room temperature while bubbling ammonia gas (ammonia gas used at 40cc/min). Thereafter, the mixture was filtered, and the solvent and unreacted matter were distilled off under reduced pressure to obtain a product.
• the resulting compound was confirmed to have a structure represented by the following formula (B) by 1 H-NMR.
• the compound represented by the above formula (B) was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 20% by mass to prepare a protective layer forming agent 4 (wherein formula (B) represents the composition formula of a polymer).
• PGME propylene glycol monomethyl ether
• Example 5 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer was formed by the protective layer forming method 2 described below using the protective layer forming agent 6 described below, and the same evaluation was performed.
• Method 2 for forming protective layer Dip coating was carried out under the following conditions to form a protective layer made of a metal oxide. Immersion time: 30 seconds Pulling speed: 0.5 mm/second Heating conditions: 150° C., 30 minutes
• Example 6 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer was formed by the above-mentioned protective layer forming method 2 using protective layer forming agent 7 shown below, and the same evaluation was performed.
• Protective Layer Forming Agent 7 A water-diluted solution (0.1% by mass in terms of zirconium oxide) of ammonium zirconium carbonate (Baycoat 20, manufactured by Nippon Light Metal Co., Ltd.) was used as protective layer forming agent 7.
• Example 3 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer was formed by the above-mentioned protective layer forming method 2 using protective layer forming agent 8 shown below, and the same evaluation was performed.
• Protective Layer Forming Agent 8 An aqueous dispersion of silicon oxide nanoparticles (average particle size: 2 nm, solid content concentration: 0.1% by mass) was used as protective layer forming agent 6.
• Example 4 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer was formed by the above-mentioned protective layer forming method 2 using protective layer forming agent 9 shown below, and the same evaluation was performed.
• Protective Layer Forming Agent 9 A water-diluted solution (solid content concentration: 1.0% by mass) of niobium oxide nanoparticles (Baylal Nb-G6000, manufactured by Taki Chemical Industry Co., Ltd.) was used as protective layer forming agent 9.
• Example 5 A glass substrate with an antireflection layer having a protective layer was obtained in the same manner as in Example 1, except that a protective layer was formed by the above-mentioned protective layer forming method 2 using protective layer forming agent 10 shown below, and the same evaluation was performed.
• Protective Layer Forming Agent 10 A water-diluted solution (1.0% by mass in terms of zirconium oxide) of ammonium zirconium carbonate (Baycoat 20, manufactured by Nippon Light Metal Co., Ltd.) was used as protective layer forming agent 10.
• Example 7 A glass substrate with an antireflection layer having a protective layer was formed in the same manner as in Example 6, and a second protective layer was further formed thereon using protective layer forming agent 1 in the same manner as in Example 1, thereby obtaining a glass substrate with an antireflection layer having two protective layers, and evaluation was performed in the same manner as in Example 1.
• Example 6 A glass substrate with an antireflection layer was obtained in the same manner as in Example 1 except that no protective layer was formed. The luminous reflectance of the glass substrate with an antireflection layer was measured and the alkali resistance test was carried out in the same manner as in Example 1.
• Table 2 shows the results of measurements of the visual reflectance of the glass substrate with an anti-reflection layer (visual reflectance of the anti-reflection layer), the thickness of the protective layer, the water contact angle of the protective layer surface, the visual reflectance of the glass substrate with an anti-reflection layer having a protective layer (visual reflectance of the protective layer surface), and the alkali resistance test (visual reflectance after the alkali resistance test) for the glass substrate with an anti-reflection layer having a protective layer obtained in Examples 1 to 7 and Comparative Examples 1 to 5 and the glass substrate with an anti-reflection layer obtained in Comparative Example 6.
• the obtained silicone hard-coated polycarbonate substrate with an antireflective layer and having a protective layer had a visual reflectance (visual reflectance of the antireflective layer) of 0.38%, a film thickness of the protective layer of 1.9 nm, a water contact angle of the protective layer surface of 96°, a visual reflectance of the silicone hard-coated polycarbonate substrate with an antireflective layer and having a protective layer (visual reflectance of the protective layer surface) of 0.40%, and a visual reflectance after the alkali resistance test of 1.35%.
• Example 9 A silicone hard-coated polycarbonate (HC/PC) plate (100 mm ⁇ 50 mm ⁇ 3 mm (thickness)) (LEXAN MARGARD manufactured by Sabic) was used as a substrate, and a substrate having an anti-reflection layer and a protective layer was obtained in the same manner as in Example 5.
• the obtained silicone hard-coated polycarbonate substrate with an antireflective layer and having a protective layer had a visual reflectance (visual reflectance of the antireflective layer) of 0.38%, a film thickness of the protective layer of 3.0 nm, a water contact angle of the protective layer surface of 44°, a visual reflectance of the silicone hard-coated polycarbonate substrate with an antireflective layer and having a protective layer (visual reflectance of the protective layer surface) of 0.39%, and a visual reflectance after the alkali resistance test of 1.30%.
• a glass substrate with an anti-reflective layer and a protective layer with a visual reflectance change of within 0.5% before and after the formation of the protective layer and a silicone hard-coated polycarbonate substrate with an anti-reflective layer and a protective layer with a visual reflectance change of within 1% after an alkali resistance test were obtained.

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