Classifications

• • 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
• • 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
  • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses

Definitions

• the present disclosure relates to a laminate and an eyeglass lens.
• Patent Document 1 discloses a hard coat film in which a hard coat layer (X), a primer layer (Y) and a surface layer (Z) are laminated in this order on at least one surface of a substrate, and the surface layer (Z) has a water contact angle of 110° or more.
• the present disclosure relates to a laminate having a lens substrate, an anti-reflection layer, an intermediate layer, and a water-repellent layer in this order, the intermediate layer being a vapor deposition layer formed using a composition for forming an intermediate layer, the composition for forming an intermediate layer including at least one compound X selected from the group consisting of a compound represented by formula (X1) described below, a hydrolyzate of a compound represented by formula (X1), and a hydrolysis condensate of a compound represented by formula (X1), and a compound Y which is a compound different from compound X, has at least one of an amino group and an amine skeleton, and has a silicon atom.
• the present disclosure will be described in detail below.
• the laminate of the present disclosure has excellent scratch resistance.
• the description of the components described below may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
• a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
• the “content” of the component means the total content of those two or more components.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
• the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
• a combination of two or more preferred aspects is a more preferred aspect.
• the "solid content" of a composition means a component that forms a layer formed using the composition, and when the composition contains a solvent (e.g., an organic solvent, water, etc.), it means all components excluding the solvent.
• a solvent e.g., an organic solvent, water, etc.
• liquid components are also considered to be solid contents if they form a layer formed using the composition.
• the bonding direction of the divalent group described in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
• the laminate has a substrate, an anti-reflection layer, an intermediate layer, and a water-repellent layer in this order.
• the laminate may have an anti-reflection layer, an intermediate layer, a water-repellent layer, etc. on one surface of the substrate, or may have an anti-reflection layer, an intermediate layer, a water-repellent layer, etc. on both surfaces of the substrate.
• the intermediate layer is preferably disposed adjacent to the anti-reflection layer and the water-repellent layer.
• the laminate preferably has, in this order, a substrate, an anti-reflection layer, an intermediate layer disposed adjacent to the anti-reflection layer, and a water-repellent layer disposed adjacent to the intermediate layer.
• the laminate has a substrate.
• the substrate may be, for example, a substrate made of a material selected from organic materials and inorganic materials, and an organic material substrate is preferred.
• organic materials include acrylic acid ester resins, methacrylic acid ester resins, thiourethane resins, allyl resins, episulfide resins, polycarbonates, urethane resins, polyesters, polystyrenes, polyethersulfones, poly-4-methylpentene-1, and diethylene glycol bisallyl carbonate resins (CR-39), of which thiourethane resins, episulfide resins, and diethylene glycol bisallyl carbonate resins are preferred.
• the thiourethane resin is a resin obtained by polymerizing a polyisocyanate compound and a polythiol compound.
• the polyisocyanate compound is preferably m-xylylene diisocyanate, a mixture of 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]heptane and 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]heptane, isophorone diisocyanate, hexamethylene diisocyanate, or tolylene diisocyanate.
• the polythiol compound is preferably pentaerythritol tetrakis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, or a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.
• the episulfide resin is a resin obtained by ring-opening polymerization of a monomer having an episulfide group (epithio group) or a mixed monomer containing such a monomer.
• the monomer having an episulfide group is preferably bis(2,3-epithiopropyl)sulfide or bis(2,3-epithiopropyl)disulfide.
• lens substrates such as organic material lens substrates and inorganic material lens substrates are also preferred.
• lens substrates include finished lenses in which the convex and concave surfaces are optically finished and molded to match a desired dioptric power, semi-finished lenses in which only the convex surface is finished as an optical surface (e.g., a spherical surface, a rotationally symmetric aspheric surface, and a progressive surface), and semi-finished lenses in which the concave surface is processed and polished to match the wearer's prescription.
• the thickness of the substrate is preferably from 0.8 to 30.0 mm, and more preferably from 1.0 to 10.0 mm.
• the refractive index of the substrate is preferably 1.50 or more, more preferably 1.60 to 1.80, and even more preferably 1.60 to 1.74.
• the laminate includes an anti-reflection layer.
• the anti-reflection layer may have a single layer structure or a multi-layer structure.
• the antireflection layer is preferably an inorganic antireflection layer, which means an antireflection layer made of an inorganic compound.
• the multi-layered antireflection layer may have a structure in which low refractive index layers and high refractive index layers are alternately laminated. Examples of materials constituting the high refractive index layer include oxides of metals selected from titanium, zirconium, aluminum, niobium, tantalum, and lanthanum. Examples of materials constituting the low refractive index layer include silicon oxide.
• Methods for forming an anti-reflective layer include, for example, dry methods such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, and CVD.
• the thickness of the anti-reflection layer is preferably 100 to 10,000 nm, and more preferably 300 to 700 nm.
• the laminate has an intermediate layer.
• the intermediate layer is a vapor-deposited layer formed using a composition for forming an intermediate layer, which will be described later.
• the intermediate layer functions as a primer layer for the water-repellent layer, and the intermediate layer provides the laminate with better scratch resistance.
• the intermediate layer preferably contains various components other than the organic solvent contained in the composition for forming the intermediate layer, or cured products thereof.
• the intermediate layer is a vapor-deposited layer, in other words, the intermediate layer is a layer formed by vapor-depositing a composition for forming an intermediate layer.
• the deposition method may be a known method, such as a vacuum deposition method, in which a deposition source is evaporated in a vacuum chamber and attached to the surface of a substrate.
• the degree of vacuum in the vacuum deposition method is preferably 1.0 ⁇ 10 ⁇ 1 Pa or less, more preferably 5.0 ⁇ 10 ⁇ 2 Pa or less, and even more preferably 2.0 ⁇ 10 ⁇ 2 Pa or less, in terms of pressure during deposition. There is no particular lower limit, and it is often 1.0 ⁇ 10 ⁇ 4 Pa or more.
• Methods for evaporating the deposition source in the vacuum deposition method include, for example, the electron beam method, the resistance heating method, the heater heating method, and the induction heating method, with the electron beam method being preferred in terms of energy conversion efficiency.
• the average deposition rate during deposition is preferably 0.1 to 1.5 nm/s, and more preferably 0.2 to 1.4 nm/s.
• the thickness of the intermediate layer is preferably 2 to 40 nm, more preferably 4 to 37 nm, and even more preferably 5 to 35 nm.
• composition for forming intermediate layer is selected from the group consisting of a compound represented by formula (X1), a hydrolyzate of a compound represented by formula (X1), and a hydrolysis condensate of a compound represented by formula (X1).
• the composition includes at least one selected compound X and a compound Y which is different from the compound X and has at least one of an amino group and an amine skeleton and has a silicon atom.
• the composition comprises compound X and compound Y.
• Compound X-- Compound X is at least one compound selected from the group consisting of a compound represented by formula (X1), a hydrolysate of a compound represented by formula (X1), and a hydrolysis condensate of a compound represented by formula (X1).
• the hydrolysate of the compound represented by formula (X1) means a compound obtained by hydrolyzing the hydrolyzable group in the compound represented by formula (X1).
• the hydrolysate may be one in which all of the hydrolyzable groups are hydrolyzed (complete hydrolysate), or one in which only a part of the hydrolyzable groups are hydrolyzed (partial hydrolysate).
• the hydrolysate may be any of a complete hydrolysate, a partial hydrolysate, and a mixture thereof.
• the hydrolysis condensate of the compound represented by formula (X1) means a compound obtained by hydrolyzing the hydrolyzable group in the compound represented by formula (X1) and condensing the obtained hydrolyzate.
• the hydrolysis condensate may be one in which all the hydrolyzable groups are hydrolyzed and all the hydrolyzates are condensed (complete hydrolysis condensate), or one in which some of the hydrolyzable groups are hydrolyzed and some of the hydrolyzates are condensed (partial hydrolysis condensate).
• the hydrolysis condensate may be any of a complete hydrolysis condensate, a partial hydrolysis condensate, and a mixture thereof.
• R n1 represents an alkyl group having an amino group and optionally having —NH—
• R x1 represents a hydroxyl group or a hydrolyzable group
• R x2 represents a hydrocarbon group
• mx represents an integer of 1 to 3.
• the R x1 's may be the same or different.
• the R x2 's may be the same or different.
• R n1 represents an alkyl group which has an amino group and may have --NH--.
• the alkyl group may be linear, branched or cyclic, and is preferably linear.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.
• the alkyl group preferably has 1 to 5 amino groups (—NH 2 ), more preferably 1 to 3 amino groups, and still more preferably 1 amino group.
• the number of --NH-- that the above alkyl group can have is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0 or 1.
• the total number of the amino groups and the --NH-- groups contained in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
• R x1 represents a hydroxyl group or a hydrolyzable group.
• the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group.
• An alkoxy group or a halogen atom is preferred, and an alkoxy group is more preferred.
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom being preferred.
• R x2 represents a hydrocarbon group.
• the hydrocarbon group may be linear, branched or cyclic.
• the hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
• the hydrocarbon group is preferably an alkyl group.
• R x2 is preferably an alkyl group having 1 to 5 carbon atoms.
• mx represents an integer of 1 to 3. mx is preferably 2 or 3, and more preferably 3.
• L x1 and L x3 each independently represent an alkylene group having 1 to 10 carbon atoms.
• L x2 represents a single bond or -NH-.
• R x3 represents a hydroxyl group or a hydrolyzable group.
• R x4 represents a hydrocarbon group.
• nx represents an integer of 1 to 3.
• R x3 , R x4 and nx in formula (X2) have the same meanings as R x1 , R x2 and mx in formula (X1), respectively, and the preferred embodiments are also the same.
• the R x3 may be the same or different.
• the R x4 may be the same or different.
• L x1 and L x3 each independently represent an alkylene group having 1 to 10 carbon atoms.
• the alkylene group may be linear, branched or cyclic, and is preferably linear.
• the alkylene group has 1 to 10 carbon atoms, and preferably 1 to 8 carbon atoms.
• the total number of carbon atoms in L x1 and L x2 is preferably 2 to 15, and more preferably 3 to 10.
• Examples of compound X include N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, and N-2-(aminoethyl)-aminomethyltrimethoxysilane, their hydrolysates, and their hydrolyzed condensates.
• Compound Y- Compound Y is a compound different from compound X, and has at least one of an amino group and an amine skeleton, and also has a silicon atom. In other words, compounds that fall under compound X are not included in compound Y.
• Compound Y preferably has an amine skeleton (-NR N -), and more preferably has no amino group (-NH 2 ) and has an amine skeleton (-NR N -).
• the number of amino groups (—NH 2 ) that the compound Y can have is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0.
• the number of amine skeletons (-NR N -) that the compound Y can have is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
• R N represents a hydrogen atom or a substituent.
• the substituent is preferably an alkyl group.
• the total number of the amino groups (—NH 2 ) and the amine skeletons (—NR N —) that compound Y has is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.
• the number of silicon atoms contained in compound Y is 1 or more, preferably 1 to 5, and more preferably 1 to 3.
• Compound Y preferably has a group represented by formula (S).
• the number of groups represented by formula (S) that compound Y can have is preferably 1 to 5, and more preferably 1 to 3.
• R s1 represents a hydroxyl group or a hydrolyzable group
• R s2 represents a hydrocarbon group
• ns represents an integer of 1 to 3.
• R s1 , R s2 and ns in formula (S) have the same meanings as R x1 , R x2 and mx in formula (X1), respectively, and the preferred embodiments are also the same.
• the R s1 may be the same or different.
• the R s2 may be the same or different.
• Compound Y preferably has at least one selected from the group consisting of a monovalent reactive group, an alkylene group which may have a fluorine atom, -Si(R s ) 2 -, and a sulfide bond (-S-).
• the monovalent reactive group include a vinyl group, an ⁇ -methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an isocyanate group, an isocyanurate group, an epoxy group, and a mercapto group.
• the number of reactive groups that the compound Y may have may be 1 or 2 or more.
• the compound Y When the compound Y has a monovalent reactive group, the compound Y preferably has the monovalent reactive group at the end of the main chain.
• the alkylene group which may have fluorine atoms may be linear, branched or cyclic, and is preferably linear.
• the number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 10.
• the alkylene group having fluorine atoms means an alkylene group in which one or more hydrogen atoms in the alkylene group are substituted with fluorine atoms.
• All hydrogen atoms in the alkylene group may be substituted with fluorine atoms, or some hydrogen atoms may be substituted with fluorine atoms.
• R s in -Si(R s ) 2 - represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom.
• the alkyl group which may have a fluorine atom may be any of linear, branched, and cyclic, and is preferably linear.
• the number of carbon atoms in the alkyl group is preferably 1 to 30, and more preferably 1 to 10.
• the number of fluorine atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. All hydrogen atoms in the alkyl group may be replaced with fluorine atoms, or some hydrogen atoms may be replaced with fluorine atoms. Multiple R s may be the same or different.
• Compound Y preferably includes at least one selected from the group consisting of a compound represented by formula (Y1), a hydrolysate of a compound represented by formula (Y1), and a hydrolysis condensate of a compound represented by formula (Y1), and more preferably includes at least one selected from the group consisting of a compound represented by formula (Y2), a hydrolysate of a compound represented by formula (Y2), and a hydrolysis condensate of a compound represented by formula (Y2).
• the hydrolysate and hydrolysis condensate are as described above for compound X.
• R y1 and R y3 each independently represent a hydroxyl group or a hydrolyzable group.
• R y2 and R y4 each independently represent a hydrocarbon group.
• ny1 and ny2 each independently represent an integer of 1 to 3.
• L y1 represents a divalent linking group having at least -NR L1 -, and the divalent linking group may further have a group selected from the group consisting of -NR L1 -, -C(R L2 )(R L3 )-, and -Si(R L4 )(R L5 )-.
• R L1 represents a hydrogen atom or an alkyl group.
• R L2 to R L5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom.
• R y1 and R y3 in formula (Y1) have the same meaning as R x1 in formula (X1), and the preferred embodiments are also the same.
• R y2 and R y4 in formula (Y1) have the same meaning as R x2 in formula (X1), and the preferred embodiments are also the same.
• ny1 and ny2 in formula (Y1) have the same meaning as mx in formula (X1), and the preferred embodiments are also the same.
• the R y1 may be the same or different.
• the R y2 When there are a plurality of R y2 , the R y2 may be the same or different. When there are a plurality of R y3 , the R y3 may be the same or different. When there are a plurality of R y4 , the R y4 may be the same or different. When there are a plurality of R L1 , the R L1 may be the same or different. When there are a plurality of R L2 , the R L2 may be the same or different. When there are a plurality of R L3 , the R L3 may be the same or different. When there are a plurality of R L4 , the R L4 may be the same or different. When there are a plurality of R L5 , the R L5 may be the same or different.
• L y1 represents a divalent linking group having at least -NR L1 -, and the divalent linking group may further have a group selected from the group consisting of -NR L1 -, -C(R L2 )(R L3 )-, and -Si(R L4 )(R L5 )-.
• R L1 represents a hydrogen atom or an alkyl group.
• R L2 to R L5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom.
• the alkyl group represented by R L1 may be any one of linear, branched, and cyclic, and is preferably linear.
• the number of carbon atoms in the alkyl group is preferably 1 to 5, and more preferably 1 to 3.
• R L1 is preferably a hydrogen atom.
• the alkyl group which may have a fluorine atom and is represented by any one of R L2 to R L5 has the same meaning as the alkyl group which may have a fluorine atom and is represented by R s in --Si(R s ) 2 --, and the preferred embodiments are also the same.
• L y1 is a divalent linking group having —NR L1 —, it may be a divalent linking group formed by combining —NR L1 — with at least one group selected from the group consisting of —C(R L2 )(R L3 )— and —Si(R L4 )(R L5 )—.
• L y1 is preferably a divalent linking group consisting of -NR L1 - and -C(R L2 )(R L3 )-, and more preferably a divalent linking group consisting of at least two (preferably 2 to 3) -NR L1 - and at least two (preferably 2 to 9) -C(R L2 )(R L3 )-.
• R y5 and R y7 each independently represent a hydroxyl group or a hydrolyzable group.
• R y6 and R y8 each independently represent a hydrocarbon group.
• ny3 and ny4 each independently represent an integer of 1 to 3.
• R L6 and R L7 each independently represent a hydrogen atom or an alkyl group.
• L y2 to L y4 each independently represent an alkylene group which may have a fluorine atom.
• R y5 and R y7 in formula (Y2) have the same meaning as R x1 in formula (X1), and the preferred embodiment is also the same.
• R y6 and R y8 in formula (Y2) have the same meaning as R x2 in formula (X1), and the preferred embodiment is also the same.
• ny3 and ny4 in formula (Y2) have the same meaning as mx in formula (X1), and the preferred embodiment is also the same.
• R L6 and R L7 in formula (Y2) have the same meaning as R L1 in formula (Y1), and the preferred embodiment is also the same.
• the R y5 may be the same or different.
• the R y6 may be the same or different.
• the R y7 may be the same or different.
• the R y8 may be the same or different.
• the alkylene group which may have a fluorine atom and is represented by any one of L y2 to L y4 may be linear, branched or cyclic, and is preferably linear.
• the number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 5.
• the alkylene group has a fluorine atom
• the number of fluorine atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 5.
• the alkylene group is also preferably an alkylene group containing no fluorine atoms.
• compound Y is N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine (X12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.).
• the content of compound X is preferably 1.0 to 95.0 mass %, more preferably 10.0 to 90.0 mass %, and even more preferably 33.0 to 71.0 mass %, based on the total content of compound X and compound Y.
• the content of compound X is preferably from 1.0 to 95.0 mass %, more preferably from 10.0 to 90.0 mass %, and even more preferably from 33.0 to 71.0 mass %, based on the total solid content of the intermediate layer forming composition.
• the content of compound Y is preferably from 5.0 to 99.0 mass %, more preferably from 10.0 to 90.0 mass %, and even more preferably from 29.0 to 67.0 mass %, based on the total solid content of the intermediate layer forming composition.
• the total content of compound X and compound Y is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 99% by mass or more, based on the total solid content of the composition for forming an intermediate layer.
• the upper limit is 100% by mass.
• composition for forming an intermediate layer may contain an organic solvent.
• organic solvents examples include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, amide-based solvents, sulfone-based solvents, and sulfoxide-based solvents.
• Organic solvents may be used alone or in combination of two or more.
• the laminate has a water-repellent layer.
• the water-repellent layer reduces the surface energy of the laminate, thereby improving the stain resistance and slipperiness of the laminate, and also improving the abrasion resistance of the laminate.
• the water-repellent layer is preferably a layer formed using a composition for forming a water-repellent layer.
• the water-repellent layer preferably contains various components other than the organic solvent contained in the composition for forming a water-repellent layer, or cured products thereof.
• Methods for forming the water-repellent layer include a method of curing a coating of a composition for forming a water-repellent layer, and a method of depositing the composition for forming a water-repellent layer. That is, the water-repellent layer is preferably a layer obtained by applying the composition for forming a water-repellent layer onto a desired member to form a coating film and curing the coating film, or a vapor-deposited layer obtained by vapor-depositing the composition for forming a water-repellent layer onto a desired member.
• a method for curing a coating film of the composition for forming a water-repellent layer includes a method in which the composition for forming a water-repellent layer is applied onto a desired member to form a coating film, and the coating film is subjected to a curing treatment (e.g., a drying treatment) as necessary to form a water-repellent layer.
• a curing treatment e.g., a drying treatment
• methods for applying the composition for forming a water-repellent layer include a dipping coating method, a spin coating method, a spray coating method, an inkjet coating method, and a flow coating method.
• the method for depositing the composition for forming the water-repellent layer can be the above-mentioned method for depositing the composition for forming the intermediate layer.
• the degree of vacuum during deposition of the water-repellent layer is preferably 1.0 ⁇ 10 ⁇ 1 Pa or less, more preferably 5.0 ⁇ 10 ⁇ 2 Pa or less, and even more preferably 2.0 ⁇ 10 ⁇ 2 Pa or less, in terms of pressure during deposition. There is no particular lower limit, and it is often 1.0 ⁇ 10 ⁇ 4 Pa or more.
• As a method for evaporating the deposition source in the vacuum deposition method for depositing the water-repellent layer an electron beam method or a resistance heating method is preferable.
• the average deposition rate when depositing the water-repellent layer is preferably 0.1 to 1.5 nm/s, and more preferably 0.2 to 1.4 nm/s. The definition of the average deposition rate is as described above.
• the thickness of the water-repellent layer is preferably 2 to 40 nm, and more preferably 4 to 37 nm.
• water-repellent layer-forming composition may contain various components described in detail below.
• the composition for forming a water-repellent layer preferably contains an organosilicon compound having a fluorine atom and a silicon atom, and more preferably contains at least one selected from the group consisting of an organosilicon compound A having at least one selected from the group consisting of a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain and having a silicon atom, and an organosilicon compound B having neither a perfluorooxyalkylene group nor a poly(perfluorooxyalkylene) chain and having a silicon atom.
• organosilicon compound A is a compound having at least one selected from the group consisting of a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain, and having a silicon atom.
• the perfluorooxyalkylene group may be any of linear, branched, and cyclic.
• the perfluorooxyalkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the perfluorooxyalkylene group is preferably -ORf-.
• Rf represents a perfluoroalkylene group.
• the perfluoroalkylene group may be linear, branched, or cyclic.
• the number of carbon atoms in the perfluoroalkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 3.
• the poly(perfluorooxyalkylene) chain may be any of linear, branched and cyclic.
• the number of carbon atoms in the poly(perfluorooxyalkylene) chain is preferably 5 or more, more preferably 30 or more, and even more preferably 50 or more.
• the upper limit is preferably 1,000 or less, and more preferably 500 or less.
• the poly(perfluorooxyalkylene) chain is preferably a group represented by formula (F).
• Rf represents a perfluoroalkylene group.
• mf represents a number of 2 or more.
• Rf has the same meaning as the perfluoroalkylene group constituting the perfluorooxyalkylene group that the organosilicon compound may have, and the preferred embodiments are also the same.
• mf is a number of 2 or more, preferably a number of 10 or more, and more preferably a number of 20 or more.
• the upper limit is preferably a number of 1000 or less, more preferably a number of 500 or less, and even more preferably a number of 100 or less.
• Examples of the poly(perfluorooxyalkylene) chain include -(OCF 2 ) mf -, -(OCF 2 CF 2 ) mf -, -(OCF 2 CF 2 CF 2 ) mf -, -(OCF 2 CF(CF 3 )) mf -, -(OCF 2 CF 2 CF 2 CF 2 ) mf -, -(OCF 2 CF 2 CF 2 CF 2 ) mf - and -(OC(CF 3 ) 2 ) mf -, and -(OCF 2 ) mf -, -(OCF 2 CF 2 ) mf - or -(OCF 2 CF 2 CF 2 ) mf- is preferred.
• the number of silicon atoms contained in the organosilicon compound A is 1 or more, preferably 1 to 20, and more preferably 1 to 10.
• the organosilicon compound A preferably has a group represented by formula (S) which the above-mentioned compound Y may have.
• the number of groups represented by formula (S) which the organosilicon compound A may have is preferably 1 to 20, and more preferably 1 to 10.
• the organosilicon compound A further contains a perfluoroalkyl group.
• the perfluoroalkyl group may be linear, branched or cyclic.
• the perfluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 2 to 8 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
• the perfluoroalkyl group is preferably CF 3 --(CF 2 ) nf --, where nf represents a number of 0 to 10, and preferably a number of 1 to 4.
• the organosilicon compound A preferably contains at least one selected from the group consisting of a compound represented by formula (A1), a hydrolysate of a compound represented by formula (A1), and a hydrolyzed condensate of a compound represented by formula (A1), and more preferably contains at least one selected from the group consisting of a compound represented by formula (A2), a hydrolyzate of a compound represented by formula (A2), a hydrolyzed condensate of a compound represented by formula (A2), a compound represented by formula (A3), a hydrolyzate of a compound represented by formula (A3), and a hydrolyzed condensate of a compound represented by formula (A3).
• the hydrolysate and hydrolysis condensate are as described above for compound X.
• R a1 represents a hydrogen atom or a substituent.
• Lf a1 represents a perfluorooxyalkylene group or a poly(perfluorooxyalkylene) chain.
• L a1 represents a single bond or a divalent linking group other than a poly(perfluorooxyalkylene) chain.
• Z a1 represents a group represented by formula (Z1) or a group having a repeating unit represented by formula (Z2).
• Lf a1 in formula (A1) has the same meaning as the perfluorooxyalkylene group or poly(perfluorooxyalkylene) chain contained in the organosilicon compound A, and the preferred embodiments are also the same.
• R a1 represents a hydrogen atom or a substituent.
• the above-mentioned substituent is preferably a monovalent substituent having at least one selected from the group consisting of -O-, -NR T1 -, -C(R T2 )(R T3 )- and -Si(R T4 )(R T5 )-, more preferably a monovalent substituent having at least one selected from the group consisting of -O-, -C(R T2 )(R T3 )- and -Si(R T4 )(R T5 )-.
• R T1 represents a hydrogen atom or an alkyl group.
• R T2 to R T5 each independently represent a hydrogen atom, a fluorine atom or an alkyl group which may have a fluorine atom.
• R T1 to R T5 each have the same meaning as R L1 to R L5 in formula (Y1), and the preferred embodiments are also the same.
• a substituent having a group represented by formula (Z1) described later or an alkyl group which may have a fluorine atom is preferable, and a substituent having a group represented by formula (Z1) or a perfluoroalkyl group is more preferable.
• the alkyl group which may have a fluorine atom include an alkyl group which may have a fluorine atom and is represented by Rs .
• the perfluoroalkyl group may be linear, branched or cyclic.
• the perfluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 2 to 8 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
• the perfluoroalkyl group is preferably CF 3 --(CF 2 ) nf --, where nf represents a number of 0 to 10, and preferably a number of 1 to 4.
• L a1 represents a single bond or a divalent linking group other than a poly(perfluorooxyalkylene) chain.
• the divalent linking group other than the poly(perfluorooxyalkylene) chain is preferably a divalent linking group other than the poly(perfluorooxyalkylene) chain having at least one selected from the group consisting of -O-, -COO-, -NR T1 -, -C(R T2 )(R T3 )-, and -Si(R T4 )(R T5 )-, where R T1 to R T5 are as described above.
• the divalent linking group other than the poly(perfluorooxyalkylene) chain is preferably a divalent linking group consisting of at least one selected from the group consisting of -O- and -CH2- , or a perfluorooxyalkylene group.
• the perfluorooxyalkylene group is synonymous with the perfluorooxyalkylene group that the organosilicon compound A may have, and the preferred embodiments are also the same.
• Z a1 represents a group represented by formula (Z1) or a group having a repeating unit represented by formula (Z2).
• Z a1 is preferably a group having a repeating unit represented by formula (Z2).
• R a1 -Lf a1 -L a1 - is located at the end of the polymer chain having the repeating unit represented by formula (Z2).
• R z1 represents a hydroxyl group or a hydrolyzable group.
• R z2 represents a hydrocarbon group.
• mz1 represents an integer of 1 to 3.
• R z3 represents a hydrogen atom or a methyl group.
• R z4 represents a hydroxyl group or a hydrolyzable group.
• R z5 represents a hydrocarbon group.
• L z represents a single bond or a divalent linking group.
• mz2 represents an integer of 1 to 3.
• R z1 , R z2 and mz1 in formula (Z1) have the same meanings as R x1 , R x2 and mx in formula (X1), respectively, and the same preferred embodiments as well.
• R z4 , R z5 and mz2 in formula (Z2) have the same meanings as R x1 , R x2 and mx in formula (X1), respectively, and the same preferred embodiments as well.
• the R z1 may be the same or different.
• the R z2 may be the same or different.
• the R z4 When a plurality of R z4 are present, the R z4 may be the same or different.
• the R z5 may be the same or different.
• R z3 is preferably a hydrogen atom.
• Lz represents a single bond or a divalent linking group.
• the divalent linking group represented by Lz include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -, divalent hydrocarbon groups (e.g., alkylene groups, alkenylene groups, and arylene groups), and groups formed by combining these.
• R N represents a hydrogen atom or a substituent. The substituent is preferably an alkyl group.
• Lz is preferably a single bond or a divalent hydrocarbon group, more preferably a single bond or an alkylene group, and further preferably a single bond.
• Rf a2 represents a perfluoroalkyl group.
• Lf a2 represents a perfluoroalkylene group.
• Lf a3 represents an alkylene group which may have a fluorine atom.
• Z a2 represents a group represented by formula (Z1) or a group having a repeating unit represented by formula (Z2).
• ma represents a number of 2 or more.
• Z a2 in formula (A2) has the same meaning as the group represented by formula (Z1) in formula (A1) or the group having a repeating unit represented by formula (Z2), and the preferred embodiments are also the same.
• ma in formula (A2) has the same meaning as mf in formula (F), and the preferred embodiments are also the same.
• the perfluoroalkylene group represented by Lf a2 is preferably a perfluoroalkylene group represented by Rf in formula (F).
• the alkylene group which may have a fluorine atom and is represented by Lf a3 is preferably an alkylene group which may have a fluorine atom and is represented by any of L y2 to L y4 in formula (Y2), more preferably an alkylene group which has a fluorine atom, and even more preferably a perfluoroalkylene group.
• Z a3 and Z a4 each independently represent a group represented by formula (Z1).
• AL 1 and AL 2 each independently represent an alkylene group which may have -O-.
• L fa4 represents a perfluorooxyalkylene group.
• Z a3 and Z a4 in formula (A3) have the same meaning as the group represented by formula (Z1) in formula (A1), and the preferred embodiments are also the same.
• the alkylene group which may have -O- represented by either AL1 or AL2 may be linear, branched or cyclic, and is preferably linear.
• the number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 2 or more.
• the upper limit is preferably 1000 or less, more preferably 500 or less, and even more preferably 10 or less.
• the alkylene group preferably has 0 to 2 --O-- groups, and more preferably has 1.
• the perfluorooxyalkylene group represented by Lfa4 has the same meaning as the perfluorooxyalkylene group that the organosilicon compound A may have, and the preferred embodiments are also the same.
• organosilicon compound A examples include OPTOOL (registered trademark, manufactured by Daikin Industries, Ltd., such as DSX and UF503), SHIN-ETSU SUBELYN KY-130 (manufactured by Shin-Etsu Chemical Co., Ltd.), SHIN-ETSU SUBELYN KY-108 (manufactured by Shin-Etsu Chemical Co., Ltd.), and organosilicon compound A synthesized by the methods described in Synthesis Examples 1 and 2 of JP2014-015609A.
• the number average molecular weight of the organosilicon compound A is preferably 2,000 or more, more preferably 4,000 or more, even more preferably 6,000 or more, and particularly preferably 7,000 or more.
• the upper limit is preferably 40,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
• the organosilicon compound A may be used alone or in combination of two or more.
• the content of the organosilicon compound A is preferably from 1 to 100% by mass, more preferably from 50 to 100% by mass, and even more preferably from 80 to 100% by mass, based on the total solid content of the composition for forming a water-repellent layer.
• the organosilicon compound B is a compound that does not have a poly(perfluorooxyalkylene) chain and has a silicon atom.
• the organosilicon compound B does not have a poly(perfluorooxyalkylene) chain.
• the organosilicon compound B does not have a poly(perfluorooxyalkylene) chain that the organosilicon compound A has.
• the number of silicon atoms contained in the organosilicon compound B is 1 or more, preferably 1 to 100, more preferably 1 to 10, and even more preferably 1 to 3.
• the organosilicon compound B preferably has a group represented by the above formula (S).
• the number of groups represented by the formula (S) that the organosilicon compound B can have is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 3.
• the organosilicon compound B further contains a perfluoroalkyl group.
• the perfluoroalkyl group include the perfluoroalkyl groups that the organosilicon compound A described above can have.
• the organosilicon compound B contains at least one selected from the group consisting of a compound represented by formula (B), a hydrolysate of a compound represented by formula (B), and a hydrolysis condensate of a compound represented by formula (B).
• the hydrolysate and hydrolysis condensate are as described above for compound X.
• R b1 represents an alkyl group having a fluorine atom.
• L b represents a divalent linking group other than a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain.
• R b2 represents a hydroxyl group or a hydrolyzable group.
• R b3 represents a hydrocarbon group.
• mb1 represents an integer of 1 to 3.
• R b2 , R b3 and mb1 in formula (B) have the same meanings as R x1 , R x2 and mx in formula (X1), respectively, and the preferred embodiments are also the same.
• R b1 represents an alkyl group having a fluorine atom.
• the alkyl group having a fluorine atom may be linear, branched or cyclic, and is preferably linear.
• the number of carbon atoms in the alkyl group is preferably 1 to 30, and more preferably 1 to 10.
• the number of fluorine atoms in the alkyl group is preferably 1 to 30, and more preferably 5 to 20.
• the alkyl group having a fluorine atom is preferably a perfluoroalkyl group.
• Lb represents a divalent linking group other than a perfluorooxyalkylene group or a poly(perfluorooxyalkylene) chain.
• the divalent linking group other than a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain include, among the groups represented by L a1 in formula (A1), divalent linking groups other than a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain, and a divalent linking group other than a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain, which has at least one selected from the group consisting of -O-, -CH 2 - and -CF 2 -, is preferred.
• organosilicon compound B examples include triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.), triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (manufactured by Tokyo Chemical Industry Co., Ltd.), trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (manufactured by Tokyo Chemical Industry Co., Ltd.), and trimethoxy(3,3,3-trifluoropropyl)silane.
• the organosilicon compound B may be used alone or in combination of two or more.
• the content of the organosilicon compound B is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, and even more preferably from 10 to 20% by mass, based on the total solid content of the composition for forming a water-repellent layer.
• the composition for forming the water-repellent layer preferably contains an organosilicon compound A and an organosilicon compound B.
• the total content of the organosilicon compound A and the organosilicon compound B is preferably 50 to 100 mass %, more preferably 80 to 100 mass %, and even more preferably 95 to 100 mass %, based on the total solid content of the composition for forming a water-repellent layer.
• the mass ratio of the content of the organosilicon compound B to the content of the organosilicon compound A is preferably 0.05 or more, more preferably 0.08 or more, and even more preferably 0.10 or more.
• the upper limit is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.6 or less.
• the water-repellent layer-forming composition may contain an organic solvent.
• the organic solvent is preferably a fluorine-based organic solvent.
• fluorinated ether organic solvents include hydrofluoroethers such as fluoroalkyl (preferably a perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl ethers, and ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether is preferred.
• fluorinated amine organic solvent examples include amines in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a tertiary amine in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (preferably a perfluoroalkyl group) (e.g., tris(heptafluoropropyl)amine, Fluorinert (registered trademark) FC-3283, manufactured by 3M Corporation) is preferred.
• a fluoroalkyl group preferably a perfluoroalkyl group
• FC-3283 Fluorinert (registered trademark) FC-3283, manufactured by 3M Corporation
• fluorinated hydrocarbon organic solvent examples include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane (for example, Solve 55, manufactured by Solvex), and fluorinated aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethylbenzene).
• fluorine-based organic solvents examples include hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC), and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by AGC).
• Organic solvents may be used alone or in combination of two or more.
• the water-repellent layer-forming composition may contain additives.
• additives include silanol condensation catalysts, antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, biofouling inhibitors, deodorants, pigments, flame retardants, and antistatic agents.
• the laminate may have a primer layer.
• the primer layer is preferably disposed between the substrate and the hard coat layer. In the above case, the adhesion between the substrate and the hard coat layer is easily improved, and the impact resistance of the laminate can be improved.
• the primer layer preferably contains a resin.
• the resin may be in the form of particles. Examples of the resin include urethane resin, epoxy resin, phenol resin, polyimide, polyester, bismaleimide resin and polyolefin, and urethane resin is preferred.
• the primer layer may contain an additive such as a surfactant.
• Examples of the method for forming the primer layer include a method in which a primer layer-forming composition containing a resin is applied onto a desired member to form a coating film, and the coating film is subjected to a curing treatment (e.g., drying treatment) as necessary to form the primer layer.
• the primer layer is preferably a layer obtained by applying a primer layer-forming composition onto a desired member to form a coating film, and curing the coating film.
• the method for applying the composition for forming a primer layer may be, for example, the method for applying the composition for forming an intermediate layer described above.
• the thickness of the primer layer is preferably 0.3 to 2.0 ⁇ m.
• the laminate may have a hard coat layer.
• the hard coat layer is preferably disposed on the primer layer, and more preferably disposed between the primer layer and the anti-reflection layer.
• the scratch resistance of the laminate can be improved.
• the hard coat layer preferably exhibits a pencil hardness of H or more according to JIS K5600.
• the method for forming the hard coat layer for example, a method of applying a composition for forming a hard coat layer containing an inorganic compound onto a desired member to form a coating film, and subjecting the coating film to a curing treatment (for example, light irradiation treatment and drying treatment) as necessary to form a hard coat layer can be mentioned.
• the hard coat layer is preferably a layer obtained by applying a composition for forming a hard coat layer onto a desired member to form a coating film, and curing the coating film.
• the method for applying the composition for forming a hard coat layer onto a substrate may be, for example, the method for applying the composition for forming an intermediate layer described above.
• the conditions for the light irradiation treatment can be selected appropriately depending on the type of polymerization initiator used.
• the type of light used for the light irradiation may be, for example, ultraviolet light or visible light, and the light source may be, for example, a high-pressure mercury lamp.
• the integrated light quantity during light irradiation is preferably from 100 to 10,000 mJ/cm 2 , and more preferably from 100 to 5,000 mJ/cm 2 , from the viewpoints of productivity and curability of the coating film.
• the thickness of the hard coat layer is preferably 1 to 20 ⁇ m, and more preferably 2 to 18 ⁇ m.
• the composition for forming a hard coat layer may contain an inorganic compound.
• the inorganic compound is an inorganic compound selected from the group consisting of inorganic oxides and silsesquioxanes. Note that, in this specification, silsesquioxanes are not included in inorganic oxides.
• the inorganic oxide is preferably a metal oxide particle.
• the metal oxide particles include oxide particles of one or more metals selected from the group consisting of Ti, Zr, Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, and In, and composite metal oxide particles thereof.
• Composite metal oxide particles are oxide particles containing two or more types of metals (metal atoms).
• the inorganic oxide particles preferably contain one or more selected from the group consisting of SiO2 (silicon oxide), Al2O3 (aluminum oxide), SnO2 (tin oxide), ZrO2 (zirconium oxide) and TiO2 (titanium oxide), more preferably contain one or more selected from the group consisting of SiO2 and ZrO2 , and even more preferably contain SiO2 .
• the inorganic oxide particles may be commercially available products. Examples of commercially available inorganic oxide particles include sols in which one or more inorganic oxide particles selected from the group consisting of SiO 2 , Al 2 O 3 , SnO 2 , ZrO 2 , TiO 2 and composite oxide particles thereof are dispersed in water or an organic solvent.
• Silsesquioxane is a silane compound having a basic skeleton represented by formula (Q) and obtained by hydrolysis of a trifunctional silane compound such as alkoxysilane, chlorosilane, or silanol.
• a trifunctional silane compound such as alkoxysilane, chlorosilane, or silanol.
• Examples of the silsesquioxane structure include irregular structures such as random structures, ladder structures, cage (completely condensed cage) structures, and incomplete cage structures (partially cleaved cage structures in which some of the silicon atoms are missing from the cage structure and some of the silicon-oxygen bonds in the cage structure are broken).
• RQ represents a monovalent organic group.
• silsesquioxanes examples include the SQ series (e.g., AC-SQ series and MAC-SQ series, manufactured by Toagosei Co., Ltd.).
• the inorganic compound may be surface-treated.
• the surface treatment may be, for example, the introduction of various functional groups or the treatment using a known surface modifier.
• the functional group introduced to the surface of the inorganic compound may be, for example, a polymerizable group, and preferably a (meth)acrylate group.
• the inorganic compound has a (meth)acrylate group on the surface, it is preferred in that it easily reacts with the resin particles that the composition may contain.
• the average particle size of the inorganic compound is preferably 0.5 to 200 nm, and more preferably 1 to 50 nm.
• the inorganic compounds may be used alone or in combination of two or more.
• the content of the inorganic compound is preferably 10.0 to 80.0 mass %, more preferably 20.0 to 70.0 mass %, and even more preferably 30.0 to 60.0 mass %, based on the total solid content of the composition for forming a hard coat layer.
• Examples of a method for producing the laminate of the present embodiment include known production methods. Specifically, the method for producing a laminate includes a step of forming an anti-reflection layer on at least one side of a substrate, a step of forming an intermediate layer by depositing a composition for forming an intermediate layer on the anti-reflection layer, and a step of forming a water-repellent layer on the intermediate layer. The method for forming each layer is as described above.
• the laminate can be used in a variety of applications. When a lens substrate is used as the substrate, it is preferably used as a spectacle lens. Other applications of the laminate include, for example, front panels (window films) in flexible displays.
• the flexible display device preferably comprises a laminate for a flexible display device and an organic electroluminescent display panel, and the laminate for a flexible display device is arranged on the viewing side of the organic electroluminescent display panel and is configured to be foldable.
• the laminate for flexible display devices may further include a polarizing plate (preferably a circular polarizing plate) and a touch sensor.
• the laminate (window film), the polarizing plate, and the touch sensor are preferably laminated in this order from the viewing side, and the laminate (window film), the touch sensor, and the polarizing plate are preferably laminated in this order from the viewing side. If the polarizing plate is present on the viewing side of the touch sensor, the pattern of the touch sensor is less visible, which is preferable in that the visibility of the displayed image is improved.
• Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like.
• the spectacle lens is a lens that has the above-mentioned laminate, and the substrate of the laminate is a lens substrate.
• the components constituting the eyeglass lens are as described above.
• Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-2 The laminates of Examples 1-1 to 1-12 and Comparative Examples 1-1 and 1-2 were produced according to the following procedure.
• a coating liquid was applied by spin coating to the surface of Nikon-Essilor's NL3-SP (size 75 mm ⁇ , center thickness 1.1 mm), and the coating was heat-cured to laminate an approximately 1 ⁇ m-thick urethane-based impact resistance improving coat (primer layer) and an approximately 15 ⁇ m-thick silicone-based scratch resistance improving hard coat in this order to obtain a substrate.
• a multilayer antireflection coat made of inorganic oxides (silica and zirconia) and having a thickness of approximately 0.4 ⁇ m was formed on the silicone-based scratch resistance improving hard coat (hard coat layer) by vacuum deposition to obtain a substrate with an antireflection layer.
• An intermediate layer-forming composition having the composition shown in Table 1 below was deposited on the antireflection layer of the substrate with an antireflection layer obtained above using a vacuum deposition apparatus (manufactured by Satisloh, model number 1200-DLX-2) with the output of the electron beam set so as to give an average deposition rate of 0.7 nm/s and at a vacuum degree of 1.0 ⁇ 10 ⁇ 2 Pa to form an intermediate layer having a thickness shown in Table 1. In this way, a substrate having an intermediate layer on the antireflection layer was obtained.
• the film thickness was measured using a quartz crystal film thickness meter (manufactured by INFICON) whose calibration value was set to indicate the film thickness on the substrate.
• OPTOOL registered trademark
• UF503 manufactured by Daikin Industries, Ltd.
• FAS13E C 6 F 13 -C 2 H 4 -Si(OC 2 H 5 ) 3 , manufactured by Tokyo Chemical Industry Co., Ltd.
• organic solvent FC-3283 C 9 F 21 N, Fluorinert, manufactured by 3M Company
• the composition for forming a water-repellent layer was applied to the substrate having an intermediate layer on the anti-reflection layer using a dip coater (DT-0001-S3, manufactured by SDI Corporation) under conditions of a liquid immersion time of 10 seconds and a lifting speed of 3.5 mm/second.
• the composition was then wet-heat cured under conditions of 50°C, 80% RH, and 30 minutes to form a water-repellent layer, thereby obtaining a laminate.
• the laminate had a substrate, an anti-reflection layer, an intermediate layer, and a water-repellent layer in this order.
• Examples 2-1 to 2-2 and Comparative Example 2-1 ⁇ Preparing the substrate> A coating solution was applied by immersion to the surface of Nikon-Essilor's NL3-SP (size 75 mm ⁇ , center thickness 1.1 mm), followed by heat curing to laminate an approximately 1 ⁇ m-thick urethane-based impact resistance improving coat (primer layer) and an approximately 2 ⁇ m-thick silicone-based scratch resistance improving hard coat in this order to obtain a substrate.
• a multilayer antireflection coat made of inorganic oxides (silica and zirconia) was formed by vacuum deposition to a thickness of approximately 0.4 ⁇ m on the silicone-based scratch resistance improving hard coat (hard coat layer) to obtain a substrate with an antireflection layer.
• OPTOOL registered trademark
• DSX solid content concentration 20 mass%, manufactured by Daikin Industries, Ltd.
• KY-130 solid content concentration 20 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.
• the metal container containing the mixed solution was heat-treated at 120°C for 20 minutes to volatilize the solvent, and a water-repellent layer-forming composition was prepared.
• the output of resistance heating was set so that the average deposition rate was 0.1 nm/s, and a water-repellent layer with a thickness of 12 nm was formed on the surface of the intermediate layer of the substrate having the intermediate layer on the antireflection layer at a degree of vacuum of 4.0 ⁇ 10 -3 Pa.
• OPTOOL registered trademark
• DSX
• OPTOOL registered trademark
• DSX solid content concentration 20 mass%, manufactured by Daikin Industries, Ltd.
• the scratch resistance of the laminate was evaluated according to the following procedure. First, the visible light transmittance of the laminate was measured with a spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science) and converted based on the definition of 2-degree visual field (light source: C light source) of JIS Z8701 to obtain luminous transmittance YA (%). Next, a rubber sheet of 8 mm x 120 mm and an abrasive-containing plastic sheet of the same size were stacked and fixed in this order on the flat surface of the pressing part having a metal flat surface.
• a spectrophotometer U-4100, manufactured by Hitachi High-Tech Science
• the pressing part was set so that the abrasive-containing plastic sheet fixed to the pressing part was in contact with the surface of the laminate on the water-repellent layer side. At this time, the abrasive-containing plastic sheet and the laminate were adjusted to be parallel to each other. After the above adjustment, a load of 1 kg was applied to the pressing portion, and the abrasive-containing plastic sheet and the rubber sheet were reciprocated in a linear direction at a speed of 100 times/67 seconds with the laminate fixed. The reciprocating motion was performed 100 times so that the relative movement distance between the laminate and the abrasive-containing plastic sheet was 30 mm.
• the luminous transmittance YB (%) of the laminate after the reciprocating motion was obtained in the same manner as for the luminous transmittance YA.
• the scratch resistance was evaluated based on the "YA-YB value (Y value difference, %)" obtained by the above procedure. The smaller the Y value difference, the more excellent the scratch resistance of the laminate, and in practical terms, a Y value difference of 3.5 or less is preferable.
• Table 1 shows the composition for forming the intermediate layer, the thickness of the intermediate layer, and the evaluation results.

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