Laminate and spectacle lens

Abstract

The present disclosure addresses the problem of providing a laminate with excellent scratch resistance. A laminate according to the present disclosure has a substrate, an anti-reflective layer, an intermediate layer, and a water-repellent layer in the stated order. The intermediate layer is a vapor-deposited layer formed using an intermediate layer-forming composition. The intermediate layer-forming composition contains: at least one compound X selected from the group consisting of a compound represented by formula (X1), a hydrolysate of the compound represented by formula (X1), and a hydrolytic condensate of the compound represented by formula (X1); and a compound Y, which is a compound different from the compound X, contains at least one of an amino group and an amine skeleton, and contains a silicon atom.

Description

Laminate, eyeglass lens

[0001] The present disclosure relates to a laminate and an eyeglass lens.

[0002] 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.

[0003] JP 2015-120253 A

[0004] The present disclosure relates to a laminate having, in this order, a lens substrate, an antireflection layer, an intermediate layer, and a water-repellent layer, wherein the intermediate layer is a vapor-deposited layer formed using a composition for forming an intermediate layer, and the composition for forming an intermediate layer contains 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 that is different from compound X, has at least one of an amino group and an amine skeleton, and has a silicon atom.

[0005] The present disclosure will be described in detail below. The laminate of the present disclosure has excellent scratch resistance. The following description of the components may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment.

[0006] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0007] As used herein, the "solid content" of a composition refers to components that form a layer formed using the composition, and in cases where the composition contains a solvent (e.g., an organic solvent and water), refers to all components excluding the solvent. Furthermore, liquid components are also considered to be solids as long as they form a layer using the composition. The bonding direction of divalent groups represented 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-. Furthermore, the compound may be "X-CO-O-Z" or "X-O-CO-Z".

[0008] [Laminate] The laminate has a substrate, an antireflection layer, an intermediate layer, and a water-repellent layer in this order. The laminate may have an antireflection layer, an intermediate layer, and a water-repellent layer, etc., on one surface of the substrate, or may have an antireflection layer, an intermediate layer, and a water-repellent layer, etc., on both surfaces of the substrate. The intermediate layer is preferably disposed adjacent to the antireflection layer and the water-repellent layer. In other words, the laminate preferably has a substrate, an antireflection layer, an intermediate layer disposed adjacent to the antireflection layer, and a water-repellent layer disposed adjacent to the intermediate layer, in this order.

[0009] <Substrate> The laminate has a substrate. Examples of the substrate include substrates composed of a material selected from organic materials and inorganic materials, with organic material substrates being preferred. Examples of organic materials include acrylic ester resins, methacrylic ester resins, thiourethane resins, allyl resins, episulfide resins, polycarbonates, urethane resins, polyesters, polystyrene, polyethersulfone, poly-4-methylpentene-1, and diethylene glycol bisallyl carbonate resins (CR-39), with thiourethane resins, episulfide resins, or diethylene glycol bisallyl carbonate resins being preferred.

[0010] The thiourethane resin is a resin obtained by polymerizing a polyisocyanate compound and a polythiol compound. Preferred polyisocyanate compounds include 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, and tolylene diisocyanate. Preferred polythiol compounds include 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. Preferred episulfide group-containing monomers are bis(2,3-epithiopropyl)sulfide or bis(2,3-epithiopropyl)disulfide.

[0011] Preferred substrates include lens substrates made of organic materials and inorganic materials, etc. Examples of lens substrates include finished lenses whose convex and concave surfaces are optically finished and molded to match a desired power, semi-finished lenses whose only convex surface is finished as an optical surface (for example, a spherical surface, a rotationally symmetric aspherical surface, and a progressive surface), and semi-finished lenses whose concave surface is processed and polished to match a wearer's prescription.

[0012] The thickness of the substrate is preferably 0.8 to 30.0 mm, more preferably 1.0 to 10.0 mm, from the viewpoint of ease of handling. 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.

[0013] <Anti-reflection layer> The laminate has an anti-reflection layer. The anti-reflection layer may have a single-layer structure or a multi-layer structure. The anti-reflection layer is preferably an inorganic anti-reflection layer. The inorganic anti-reflection layer means an anti-reflection layer composed of an inorganic compound. The multi-layer anti-reflection 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.

[0014] Examples of methods for forming the antireflection layer include dry methods such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, and CVD.

[0015] The thickness of the antireflection layer is preferably from 100 to 10,000 nm, more preferably from 300 to 700 nm.

[0016] <Intermediate layer> 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 an intermediate layer, or cured products thereof.

[0017] The intermediate layer is a vapor deposition layer, in other words, a layer formed by vapor deposition of a composition for forming an intermediate layer. A known vapor deposition method can be used, for example, a vacuum deposition method. The vacuum deposition method is a method in which a vapor 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 1.0 × 10 pressure during vapor deposition. －１ Pa or less, and 5.0 × 10 －２ Pa or less is more preferable, and 2.0 × 10 －２ The lower limit is not particularly limited, and is preferably 1.0 × 10 －４ Pa or higher in most cases.

[0018] Examples of methods for evaporating the evaporation source in the vacuum evaporation method include an electron beam method, a resistance heating method, a heater heating method, and an induction heating method, and the electron beam method is preferred from the viewpoint of energy conversion efficiency.

[0019] The average deposition rate during deposition is preferably 0.1 to 1.5 nm / s, more preferably 0.2 to 1.4 nm. The average deposition rate is the value obtained by dividing the thickness of the deposited film by the deposition time required to form a deposited film of the above thickness (average deposition rate (nm / s) = film thickness (nm) / deposition time (s)).

[0020] The thickness of the intermediate layer is preferably from 2 to 40 nm, more preferably from 4 to 37 nm, and even more preferably from 5 to 35 nm.

[0021] Various components that may be contained in the composition for forming an intermediate layer will be described in detail below.

[0022] (Composition for forming an intermediate layer) The composition for forming an intermediate layer contains at least one compound X 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), and a compound Y which is a compound different from compound X and has at least one of an amino group and an amine skeleton and has a silicon atom. In other words, the composition for forming an intermediate layer contains compound X and compound Y. If the composition for forming an intermediate layer does not contain compound Y, the efficiency of forming the vapor deposition layer decreases, which is not preferred. Furthermore, if the composition for forming an intermediate layer does not contain compound X, the scratch resistance decreases, which is not preferred.

[0023] -Compound X- Compound X is at least one compound selected from the group consisting of a compound represented by formula (X1), a hydrolyzed compound of formula (X1), and a hydrolyzed condensate of a compound represented by formula (X1). The hydrolyzed compound of formula (X1) refers to a compound obtained by hydrolyzing the hydrolyzable groups in the compound represented by formula (X1). The hydrolyzed compound may be one in which all of the hydrolyzable groups are hydrolyzed (complete hydrolyzed product), or one in which only a portion of the hydrolyzable groups are hydrolyzed (partial hydrolyzed product). In other words, the hydrolyzed compound may be a complete hydrolyzed product, a partial hydrolyzed product, or a mixture thereof. The hydrolyzed condensate of a compound represented by formula (X1) refers to a compound obtained by hydrolyzing the hydrolyzable groups in the compound represented by formula (X1) and condensing the resulting hydrolyzed product. The hydrolyzed condensate may be one in which all of the hydrolyzable groups are hydrolyzed and the entire hydrolyzed product is condensed (complete hydrolyzed condensate), or one in which only a portion of the hydrolyzable groups are hydrolyzed and only a portion of the hydrolyzed product is condensed (partial hydrolyzed condensate). That is, the hydrolysis-condensation product may be any of a complete hydrolysis-condensation product, a partial hydrolysis-condensation product, and a mixture thereof.

[0024]

[0025] In formula (X1), R ｎ１ represents an alkyl group having an amino group and optionally having —NH—. ｘ１ represents a hydroxyl group or a hydrolyzable group. ｘ２ represents a hydrocarbon group. mx represents an integer of 1 to 3. R ｘ１ If there are multiple ｘ１ R may be the same or different. ｘ２ If there are multiple ｘ２ They may be the same or different.

[0026] In formula (X1), R ｎ１represents an alkyl group having an amino group and optionally having —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 amino group (—NH ２ The number of —NH— groups that the alkyl group may have is preferably 0 to 5, more preferably 0 to 3, and still more preferably 0 or 1. The total number of the amino groups and —NH— groups that the alkyl group may have is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 or 2.

[0027] In formula (X1), R ｘ１ represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group, with an alkoxy group or a halogen atom being preferred, and an alkoxy group being more preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, with a methoxy group or an ethoxy group being more preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.

[0028] In formula (X1), R ｘ２ represents a hydrocarbon group. The hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The hydrocarbon group is preferably an alkyl group. R ｘ２ Among these, alkyl groups having 1 to 5 carbon atoms are preferred.

[0029] In formula (X1), mx represents an integer of 1 to 3. mx is preferably 2 or 3, and more preferably 3.

[0030] The compound represented by formula (X1) is preferably a compound represented by formula (X2).

[0031]

[0032] In formula (X2), L ｘ１ and L ｘ３ each independently represents an alkylene group having 1 to 10 carbon atoms. ｘ２ represents a single bond or —NH—. ｘ３ represents a hydroxyl group or a hydrolyzable group. ｘ４ represents a hydrocarbon group, and nx represents an integer of 1 to 3. ｘ３ , R ｘ４ and nx are R in formula (X1), ｘ１ , R ｘ２ and mx, and the preferred embodiments are also the same. ｘ３ If there are multiple ｘ３ R may be the same or different. ｘ４ If there are multiple ｘ４ They may be the same or different.

[0033] In formula (X2), L ｘ１ and L ｘ３ each independently represents 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. ｘ１ and L ｘ２ The total number of carbon atoms is preferably 2 to 15, and more preferably 3 to 10.

[0034] 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.

[0035] 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.

[0036] Compound Y has an amine skeleton (—NR ＮPreferably, the alkyl group has an amino group (-NH ２ ) and does not have an amine skeleton (—NR Ｎ It is more preferable that the compound Y has an amino group (—NH ２ The number of amine skeletons (—NR Ｎ The number of R -) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Ｎ represents a hydrogen atom or a substituent. The substituent is preferably an alkyl group. ２ ) and the amine skeleton (—NR Ｎ The total number of (-) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.

[0037] 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.

[0038] -Si(R ｓ１ ) ｎｓ (R ｓ２ ) ３－ｎｓ (S)

[0039] In formula (S), R ｓ１ represents a hydroxyl group or a hydrolyzable group. ｓ２ represents a hydrocarbon group. ns represents an integer of 1 to 3. R in formula (S) ｓ１ , R ｓ２ and ns are R in formula (X1), ｘ１ , R ｘ２ and mx, and the preferred embodiments are also the same. ｓ１ If there are multiple ｓ１ R may be the same or different. ｓ２ If there are multiple ｓ２ They may be the same or different.

[0040] The compound Y is a monovalent reactive group, an alkylene group which may have a fluorine atom, —Si(Rｓ ) ２ It is preferable that the compound Y has at least one selected from the group consisting of a - and a sulfide bond (-S-). Examples of monovalent reactive groups include a vinyl group, an α-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 one or more. When the compound Y has a monovalent reactive group, the compound Y preferably has a monovalent reactive group at the end of the main chain. The alkylene group that may have a fluorine atom 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. When the alkylene group has a fluorine atom, the number of fluorine atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5. The alkylene group having a fluorine atom refers to an alkylene group in which one or more hydrogen atoms in the alkylene group have been substituted with fluorine atoms. All of the hydrogen atoms in the alkylene group may be substituted with fluorine atoms, or some of the hydrogen atoms may be substituted with fluorine atoms. -Si(R ｓ ) ２ -R in ｓ 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 linear, branched, or cyclic, and is preferably linear. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10. When the alkyl group has a fluorine atom, the number of fluorine atoms contained in the alkyl group is preferably 1 to 10, more preferably 1 to 5. All of the hydrogen atoms contained in the alkyl group may be replaced with fluorine atoms, or some of the hydrogen atoms may be replaced with fluorine atoms. Multiple R ｓ They may be the same or different.

[0041] Compound Y preferably contains at least one selected from the group consisting of a compound represented by formula (Y1), a hydrolyzate of a compound represented by formula (Y1), and a hydrolyzed condensate of a compound represented by formula (Y1), and more preferably contains at least one selected from the group consisting of a compound represented by formula (Y2), a hydrolyzate of a compound represented by formula (Y2), and a hydrolyzed condensate of a compound represented by formula (Y2). Note that the hydrolyzate and the hydrolyzed condensate are as described above for compound X.

[0042]

[0043] In formula (Y1), R ｙ１ and R ｙ３ R each independently represents a hydroxyl group or a hydrolyzable group. ｙ２ and R ｙ４ each independently represents a hydrocarbon group; ny1 and ny2 each independently represents an integer of 1 to 3; L ｙ１ is at least -NR Ｌ１ represents a divalent linking group having -, and the divalent linking group further has -NR Ｌ１ -, -C(R Ｌ２ ) (R Ｌ３ )- and -Si(R Ｌ４ ) (R Ｌ５ )-. Ｌ１ represents a hydrogen atom or an alkyl group. Ｌ２ ~R Ｌ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom. ｙ１ and R ｙ３ is R in formula (X1). ｘ１ The meaning and preferred embodiments are also the same as those of the formula (Y1). ｙ２ and R ｙ４ is R in formula (X1). ｘ２ The definitions and preferred embodiments of ny1 and ny2 in formula (Y1) are the same as those of mx in formula (X1), and the preferred embodiments are also the same. ｙ１ If there are multiple ｙ１ R may be the same or different. ｙ２If there are multiple ｙ２ R may be the same or different. ｙ３ If there are multiple ｙ３ R may be the same or different. ｙ４ If there are multiple ｙ４ R may be the same or different. Ｌ１ If there are multiple Ｌ１ R may be the same or different. Ｌ２ If there are multiple Ｌ２ R may be the same or different. Ｌ３ If there are multiple Ｌ３ R may be the same or different. Ｌ４ If there are multiple Ｌ４ R may be the same or different. Ｌ５ If there are multiple Ｌ５ They may be the same or different.

[0044] In formula (Y1), L ｙ１ is at least -NR Ｌ１ represents a divalent linking group having -, and the divalent linking group further has -NR Ｌ１ -, -C(R Ｌ２ ) (R Ｌ３ )- and -Si(R Ｌ４ ) (R Ｌ５ )-. Ｌ１ represents a hydrogen atom or an alkyl group. Ｌ２ ~R Ｌ５ R each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom. Ｌ１ The alkyl group represented by R may be linear, branched, or 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. Ｌ１ is preferably a hydrogen atom. Ｌ２ ~R Ｌ５ The alkyl group optionally having a fluorine atom represented by any one of the following is —Si(R ｓ ) ２ -R in ｓThe meaning and preferred embodiments are also the same as those of the alkyl group optionally having a fluorine atom represented by the following formula: ｙ１ is -NR Ｌ１ If the divalent linking group has -, it is -NR Ｌ１ - and -C(R Ｌ２ ) (R Ｌ３ )- and -Si(R Ｌ４ ) (R Ｌ５ )- and at least one group selected from the group consisting of ｙ１ As the Ｌ１ - and -C(R Ｌ２ ) (R Ｌ３ )-, and at least two (preferably 2 to 3) -NR Ｌ１ - and at least two (preferably 2 to 9) -C(R Ｌ２ ) (R Ｌ３ )- is more preferred.

[0045]

[0046] In formula (Y2), R ｙ５ and R ｙ７ R each independently represents a hydroxyl group or a hydrolyzable group. ｙ６ and R ｙ８ each independently represents a hydrocarbon group. ny3 and ny4 each independently represents an integer of 1 to 3. R Ｌ６ and R Ｌ７ each independently represents a hydrogen atom or an alkyl group. ｙ２ ~L ｙ４ each independently represents an alkylene group which may have a fluorine atom. ｙ５ and R ｙ７ is R in formula (X1). ｘ１ The meaning and preferred embodiments are also the same as those of the formula (Y2). ｙ６ and R ｙ８ is R in formula (X1). ｘ２ The definitions and preferred embodiments of ny3 and ny4 in formula (Y2) are the same as those of mx in formula (X1), and the preferred embodiments are also the same. Ｌ６ and R Ｌ７represents R in formula (Y1). Ｌ１ The same definition and preferred embodiments are also the same. ｙ５ If there are multiple ｙ５ R may be the same or different. ｙ６ If there are multiple ｙ６ R may be the same or different. ｙ７ If there are multiple ｙ７ R may be the same or different. ｙ８ If there are multiple ｙ８ They may be the same or different.

[0047] L ｙ２ ~L ｙ４ The alkylene group which may have a fluorine atom and is represented by any one of the following may be linear, branched, or cyclic, with linear being preferred. 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. When 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. It is also preferred that the alkylene group is an alkylene group which does not have a fluorine atom.

[0048] An example of compound Y is N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine (X12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0049] In the composition for forming an intermediate layer, 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 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 solid content of the composition for forming an intermediate layer. The content of compound Y is preferably 5.0 to 99.0 mass%, more preferably 10.0 to 90.0 mass%, and even more preferably 29.0 to 67.0 mass%, based on the total solid content of the composition for forming an intermediate layer. The total content of compound X and compound Y is preferably 80 mass% or more, more preferably 90 mass% or more, and even more preferably 99 mass% or more, based on the total solid content of the composition for forming an intermediate layer. The upper limit is 100 mass%.

[0050] —Organic Solvent— The composition for forming an intermediate layer may contain an organic solvent.

[0051] Examples of organic solvents 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.

[0052] The organic solvents may be used alone or in combination of two or more.

[0053] <Water-repellent layer> The laminate has a water-repellent layer. The water-repellent layer reduces the surface energy of the laminate, thereby improving the stain prevention and slip properties of the laminate and also improving the abrasion resistance of the laminate. The water-repellent layer is preferably a layer formed using a water-repellent layer-forming composition. The water-repellent layer preferably contains various components other than the organic solvent contained in the water-repellent layer-forming composition, or cured products thereof.

[0054] Methods for forming the water-repellent layer include a method of curing a coating film of a water-repellent layer-forming composition and a method of vapor-depositing the water-repellent layer-forming composition. That is, the water-repellent layer is preferably a layer obtained by applying the water-repellent layer-forming composition to a desired member to form a coating film and curing the coating film, or a vapor-deposited layer obtained by vapor-depositing the water-repellent layer-forming composition on a desired member.

[0055] More specifically, a method for curing a coating film of the water-repellent layer-forming composition includes applying the water-repellent layer-forming composition to a desired member to form a coating film, and then subjecting the coating film to a curing treatment (e.g., drying treatment) as necessary to form a water-repellent layer. Examples of methods for applying the water-repellent layer-forming composition include dipping coating, spin coating, spray coating, inkjet coating, and flow coating.

[0056] The method for depositing the composition for forming the water-repellent layer can be the same as the method for depositing the composition for forming the intermediate layer described above. The degree of vacuum during deposition of the water-repellent layer is 1.0×10 －１ Pa or less, and 5.0 × 10 －２ Pa or less is more preferable, and 2.0 × 10 －２ The lower limit is not particularly limited, and is preferably 1.0 × 10 －４ The pressure is often equal to or higher than Pa. The electron beam method or resistance heating method is preferred as a method for evaporating the evaporation source in the vacuum evaporation method for depositing the water-repellent layer. The average evaporation rate for depositing the water-repellent layer is preferably 0.1 to 1.5 nm / s, more preferably 0.2 to 1.4 nm / s. The definition of the average evaporation rate is as described above.

[0057] The thickness of the water-repellent layer is preferably from 2 to 40 nm, more preferably from 4 to 37 nm.

[0058] Various components that may be contained in the composition for forming a water-repellent layer will be described in detail below.

[0059] (Composition for forming water-repellent layer) 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.

[0060] -Organosilicon Compound A- Organosilicon compound A is a compound having at least one group selected from the group consisting of a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain, and having a silicon atom.

[0061] The perfluorooxyalkylene group may be linear, branched, or cyclic. The number of carbon atoms in the perfluorooxyalkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 3. 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.

[0062] The poly(perfluorooxyalkylene) chain may be linear, branched, or 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, more preferably 500 or less.

[0063] The poly(perfluorooxyalkylene) chain is preferably a group represented by formula (F).

[0064] -(ORf) ｍｆ - (F)

[0065] In formula (F), Rf represents a perfluoroalkylene group, and mf represents a number of 2 or more.

[0066] 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 10 or more, and more preferably 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 poly(perfluorooxyalkylene) chains 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 CF ２ CF ２ ) ｍｆ - and - (OC(CF ３ ) ２ ) ｍｆ -, -(OCF ２ ) ｍｆ -, - (OCF ２ CF ２ ) ｍｆ -or- (OCF ２ CF ２ CF ２ ) ｍｆ - is preferred.

[0067] The number of silicon atoms contained in organosilicon compound A is 1 or more, preferably 1 to 20, and more preferably 1 to 10. It is preferable that organosilicon compound A has a group represented by formula (S) which can be contained in the above-mentioned compound Y. The number of groups represented by formula (S) which can be contained in organosilicon compound A is preferably 1 to 20, and more preferably 1 to 10.

[0068] Preferably, the organosilicon compound A further has a perfluoroalkyl group. The perfluoroalkyl group may be linear, branched, or cyclic. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, even more preferably 2 to 8, and particularly preferably 2 to 5. Examples of the perfluoroalkyl group include CF ３ -(CF ２ ) ｎｆ nf represents a number of 0 to 10, preferably a number of 1 to 4.

[0069] The organosilicon compound A preferably comprises at least one selected from the group consisting of the compound represented by formula (A1), the hydrolyzate of the compound represented by formula (A1) and the hydrolysis condensate of the compound represented by formula (A1), and more preferably comprises at least one selected from the group consisting of the compound represented by formula (A2), the hydrolyzate of the compound represented by formula (A2), the hydrolyzate condensate of the compound represented by formula (A2), the compound represented by formula (A3), the hydrolyzate of the compound represented by formula (A3) and the hydrolyzate condensate of the compound represented by formula (A3).In addition, the hydrolyzate and the hydrolyzate condensate are as described above in the compound X.

[0070]

[0071] In formula (A1), R ａ１ represents a hydrogen atom or a substituent. ａ１ represents a perfluorooxyalkylene group or a poly(perfluorooxyalkylene) chain. ａ１ represents a single bond or a divalent linking group other than a poly(perfluorooxyalkylene) chain. ａ１ represents a group represented by formula (Z1) or a group having a repeating unit represented by formula (Z2). 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.

[0072] In formula (A1), R ａ１ represents a hydrogen atom or a substituent. Examples of the substituent include —O—, —NR Ｔ１ -, -C(R Ｔ２ ) (R Ｔ３ )- and -Si(R Ｔ４ ) (R Ｔ５ 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 )- is more preferred. Ｔ１represents a hydrogen atom or an alkyl group. Ｔ２ ~R Ｔ５ R each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom. Ｔ１ ~R Ｔ５ are R in formula (Y1), respectively. Ｌ１ ~R Ｌ５ The substituent is preferably a substituent having a group represented by formula (Z1) described below or an alkyl group which may have a fluorine atom, and more preferably a substituent having a group represented by formula (Z1) or a perfluoroalkyl group. Examples of the alkyl group which may have a fluorine atom include, for example, R ｓ The perfluoroalkyl group may be any of linear, branched, and cyclic. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, still more preferably 2 to 8, and particularly preferably 2 to 5. Examples of the perfluoroalkyl group include CF ３ -(CF ２ ) ｎｆ nf represents a number of 0 to 10, preferably a number of 1 to 4.

[0073] In formula (A1), L ａ１ represents a single bond or a divalent linking group other than a poly(perfluorooxyalkylene) chain. The divalent linking group other than a poly(perfluorooxyalkylene) chain is a divalent linking group other than a poly(perfluorooxyalkylene) chain, such as —O—, —COO—, —NR Ｔ１ -, -C(R Ｔ２ ) (R Ｔ３ )- and -Si(R Ｔ４ ) (R Ｔ５ )-. Ｔ１ ~R Ｔ５ Among them, the divalent linking group other than the poly(perfluorooxyalkylene) chain is —O— and —CH ２-, or a perfluorooxyalkylene group. The perfluorooxyalkylene group has the same meaning as the perfluorooxyalkylene group that the organosilicon compound A may have, and preferred embodiments are also the same.

[0074] In formula (A1), Z ａ１ represents a group represented by formula (Z1) or a group having a repeating unit represented by formula (Z2). ａ１ As the repeating unit represented by formula (Z2), a group having a repeating unit represented by formula (Z2) is preferred. ａ１ is a group having a repeating unit represented by formula (Z2), R ａ１ -Lf ａ１ -L ａ１ It is preferred that the group represented by - is located at the position.

[0075]

[0076] In formula (Z1), * represents a bonding position. ｚ１ represents a hydroxyl group or a hydrolyzable group. ｚ２ represents a hydrocarbon group. mz1 represents an integer of 1 to 3. In formula (Z2), R ｚ３ represents a hydrogen atom or a methyl group. ｚ４ represents a hydroxyl group or a hydrolyzable group. ｚ５ represents a hydrocarbon group. ｚ represents a single bond or a divalent linking group. mz2 represents an integer of 1 to 3. ｚ１ , R ｚ２ and mz1 are R in formula (X1), ｘ１ , R ｘ２ R in formula (Z2) has the same meaning as mx and has the same preferred embodiments. ｚ４ , R ｚ５ and mz2 are R in formula (X1), ｘ１ , R ｘ２ and mx, and the preferred embodiments are also the same. ｚ１ If there are multiple ｚ１ R may be the same or different. ｚ２ If there are multipleｚ２ R may be the same or different. ｚ４ If there are multiple ｚ４ R may be the same or different. ｚ５ If there are multiple ｚ５ They may be the same or different.

[0077] R ｚ３ is preferably a hydrogen atom.

[0078] In formula (Z2), L ｚ represents a single bond or a divalent linking group. ｚ Examples of the divalent linking group represented by the formula: ２ -, -NR Ｎ -, divalent hydrocarbon groups (for example, alkylene groups, alkenylene groups, arylene groups, etc.), and groups formed by combining these groups. Ｎ represents a hydrogen atom or a substituent. The substituent is preferably an alkyl group. ｚ is preferably a single bond or a divalent hydrocarbon group, more preferably a single bond or an alkylene group, and even more preferably a single bond.

[0079]

[0080] In formula (A2), Rf ａ２ represents a perfluoroalkyl group. ａ２ represents a perfluoroalkylene group. ａ３ represents an alkylene group which may have a fluorine atom. 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. 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 preferred embodiments are also the same. ma in formula (A2) has the same meaning as mf in formula (F), and preferred embodiments are also the same.

[0081] Rf ａ２ The perfluoroalkyl group represented by R ａ１Among the substituents represented by the formula (I), a perfluoroalkyl group is preferred. ａ２ The perfluoroalkylene group represented by the formula (F) is preferably a perfluoroalkylene group represented by Rf in the formula (F). ａ３ The alkylene group optionally having a fluorine atom represented by the formula (Y2) is ｙ２ ~L ｙ４ An alkylene group optionally having a fluorine atom, represented by any one of the following formulae, is preferred, an alkylene group having a fluorine atom is more preferred, and a perfluoroalkylene group is even more preferred.

[0082]

[0083] In formula (A3), Z ａ３ and Z ａ４ each independently represents a group represented by formula (Z1). １ and AL ２ each independently represents an alkylene group which may have —O—. ｆａ４ represents a perfluorooxyalkylene group. ａ３ and Z ａ４ has the same meaning as the group represented by formula (Z1) in formula (A1), and preferred embodiments are also the same.

[0084] AL １ and AL ２ The alkylene group which may have -O- represented by any one of the following may be linear, branched or cyclic, with linear being preferred. 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 number of -O- which the alkylene group may have is preferably 0 to 2, more preferably 1. L ｆａ４ The perfluorooxyalkylene group represented by the following formula has the same meaning as the perfluorooxyalkylene group that the organosilicon compound A can have, and the preferred embodiments are also the same.

[0085] Examples of organosilicon compound A 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 JP 2014-015609 A.

[0086] The number average molecular weight of 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.

[0087] The organosilicon compound A may be used alone or in combination of two or more. The content of the organosilicon compound A is preferably 1 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 80 to 100 mass %, based on the total solid content of the composition for forming a water-repellent layer.

[0088] -Organosilicon Compound B- Organosilicon compound B is a compound that does not have a poly(perfluorooxyalkylene) chain but has a silicon atom. Organosilicon compound B does not have a poly(perfluorooxyalkylene) chain. Specifically, organosilicon compound B does not have the poly(perfluorooxyalkylene) chain that the above-mentioned organosilicon compound A has.

[0089] The number of silicon atoms contained in organosilicon compound B is 1 or more, preferably 1 to 100, more preferably 1 to 10, and even more preferably 1 to 3. Organosilicon compound B preferably contains a group represented by formula (S) described above. The number of groups represented by formula (S) that organosilicon compound B can contain is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 3.

[0090] Preferably, organosilicon compound B further contains a perfluoroalkyl group. Examples of the perfluoroalkyl group include the perfluoroalkyl groups that organosilicon compound A can contain.

[0091] The organosilicon compound B preferably contains at least one selected from the group consisting of a compound represented by formula (B), a hydrolyzate of a compound represented by formula (B), and a hydrolysis condensate of a compound represented by formula (B). The hydrolyzate and the hydrolysis condensate are as described above for compound X.

[0092]

[0093] In formula (B), R ｂ１ represents an alkyl group having a fluorine atom. ｂ represents a divalent linking group other than a perfluorooxyalkylene group or a poly(perfluorooxyalkylene) chain. ｂ２ represents a hydroxyl group or a hydrolyzable group. ｂ３ represents a hydrocarbon group. mb1 represents an integer of 1 to 3. R in formula (B) ｂ２ , R ｂ３ and mb1 are R in formula (X1), ｘ１ , R ｘ２ and mx, and the preferred embodiments are also the same.

[0094] In formula (B), 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 alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10. The alkyl group preferably has 1 to 30 fluorine atoms, more preferably 5 to 20. The alkyl group having a fluorine atom is preferably a perfluoroalkyl group.

[0095] In formula (B), L ｂ represents a divalent linking group other than a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain. Examples of the divalent linking group other than a perfluorooxyalkylene group and a poly(perfluorooxyalkylene) chain include L in formula (A1). ａ１Among the groups represented by the formula (I), divalent linking groups other than perfluorooxyalkylene groups and poly(perfluorooxyalkylene) chains are exemplified, and divalent linking groups other than perfluorooxyalkylene groups and poly(perfluorooxyalkylene) chains include -O-, -CH ２ - and -CF ２ A divalent linking group having at least one selected from the group consisting of - is preferred.

[0096] Examples of organosilicon compound B 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.

[0097] The organosilicon compound B may be used alone or in combination of two or more. The content of the organosilicon compound B is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, and even more preferably 10 to 20 mass %, based on the total solid content of the composition for forming a water-repellent layer.

[0098] The water-repellent layer-forming composition preferably contains an organosilicon compound A and an organosilicon compound B. The total content of organosilicon compound A and organosilicon compound B is preferably 50 to 100 mass% relative to the total solids content of the water-repellent layer-forming composition, more preferably 80 to 100 mass%, and even more preferably 95 to 100 mass%. When the water-repellent layer (or the water-repellent layer-forming composition) contains organosilicon compound A and organosilicon compound B, the mass ratio of the content of organosilicon compound B to the content of organosilicon compound A (content of organosilicon compound B / content of 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.

[0099] -Organic Solvent- The composition for forming a water-repellent layer may contain an organic solvent.

[0100] As the organic solvent, a fluorine-based organic solvent is preferred. Examples of fluorinated ether-based organic solvents include hydrofluoroethers such as fluoroalkyl (preferably, a perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl ethers, with ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether being preferred. Examples of fluorinated amine-based organic solvents include amines in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, with tertiary amines in which all hydrogen atoms of ammonia are substituted with fluoroalkyl groups (preferably, perfluoroalkyl groups) being preferred (e.g., tris(heptafluoropropyl)amine, Fluorinert (registered trademark) FC-3283, manufactured by 3M). Examples of fluorinated hydrocarbon-based organic solvents include fluorinated aliphatic hydrocarbon-based solvents such as 1,1,1,3,3-pentafluorobutane (e.g., Solv 55, manufactured by Solvex), and fluorinated aromatic hydrocarbon-based solvents such as 1,3-bis(trifluoromethylbenzene).

[0101] Examples of fluorine-based organic solvents include hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC), and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by AGC).

[0102] The organic solvents may be used alone or in combination of two or more.

[0103] -Additives- The composition for forming a water-repellent layer may contain additives, such as silanol condensation catalysts, antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, mildew inhibitors, antibacterial agents, anti-biofouling agents, deodorizers, pigments, flame retardants, and antistatic agents.

[0104] <Primer layer> The laminate may have a primer layer. The primer layer is preferably disposed between the substrate and the hard coat layer. In this case, adhesion between the substrate and the hard coat layer is likely to be improved, and the impact resistance of the laminate can be improved.

[0105] The primer layer preferably contains a resin. The resin may be in particulate form. Examples of the resin include urethane resin, epoxy resin, phenol resin, polyimide, polyester, bismaleimide resin, and polyolefin, with urethane resin being preferred. The primer layer may contain an additive such as a surfactant.

[0106] As a method for forming a primer layer, for example, a method can be mentioned in which a primer layer-forming composition containing a resin is applied to a desired member to form a coating film, and the coating film is subjected to a curing treatment (for example, drying treatment) as necessary to form a primer layer. In other words, the primer layer is preferably a layer obtained by applying a primer layer-forming composition to a desired member to form a coating film, and then curing the coating film. As a method for applying a primer layer-forming composition, for example, a method can be mentioned in which the above-mentioned intermediate layer-forming composition is applied.

[0107] The thickness of the primer layer is preferably 0.3 to 2.0 μm.

[0108] <Hard Coat Layer> 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 antireflection layer. When the laminate has a hard coat layer, the scratch resistance of the laminate can be improved. The hard coat layer preferably exhibits a pencil hardness of H or more in accordance with JIS K5600.

[0109] As a method for forming a hard coat layer, for example, a method can be mentioned in which a composition for forming a hard coat layer containing an inorganic compound is applied to a desired member to form a coating film, and the coating film is subjected to a curing treatment (for example, a light irradiation treatment and a drying treatment) as necessary to form a hard coat layer. In other words, the hard coat layer is preferably a layer obtained by applying a composition for forming a hard coat layer to a desired member to form a coating film, and then curing the coating film. As a method for applying a composition for forming a hard coat layer to a substrate, for example, a method can be mentioned in which the above-mentioned composition for forming an intermediate layer is applied.

[0110] 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 light irradiation can be, for example, ultraviolet light or visible light. The light source can be, for example, a high-pressure mercury lamp. The cumulative light amount used for light irradiation can be 100 to 10,000 mJ / cm from the viewpoints of productivity and curability of the coating film. ２ is preferred, and 100 to 5000 mJ / cm ２ is more preferred.

[0111] The thickness of the hard coat layer is preferably from 1 to 20 μm, more preferably from 2 to 18 μm.

[0112] 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. In this specification, silsesquioxanes are not included in the inorganic oxides.

[0113] The inorganic oxide is preferably a metal oxide particle. Examples of the metal oxide particle 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, as well as composite metal oxide particles thereof. Composite metal oxide particles are oxide particles containing two or more metals (metal atoms). The inorganic oxide particle is preferably a SiO ２ (silicon oxide), Al ２ O ３ (aluminum oxide), SnO ２ (tin oxide), ZrO ２ (zirconium oxide) and TiO ２ (titanium oxide), and SiO ２ and ZrO ２ More preferably, the material contains one or more selected from the group consisting of SiO ２ It is more preferable that the inorganic oxide particles contain SiO. Commercially available inorganic oxide particles may be used. ２ , Al ２ O ３ , SnO ２ , ZrO ２ , TiO ２and composite oxide particles thereof, dispersed in water or an organic solvent.

[0114] Silsesquioxanes are silane compounds having a basic skeleton represented by formula (Q) that can be obtained by hydrolyzing trifunctional silane compounds such as alkoxysilanes, chlorosilanes, and silanols. Examples of silsesquioxane structures include irregular structures such as random structures, ladder structures, cage (fully condensed cage) structures, and incomplete cage structures (partially cleaved cage structures in which some silicon atoms are missing from the cage structure and some silicon-oxygen bonds in the cage structure are cleaved).

[0115] R Ｑ -SiO ３／２ (Q) In formula (Q), R Ｑ represents a monovalent organic group.

[0116] Examples of silsesquioxanes include the SQ series (eg, AC-SQ series and MAC-SQ series, manufactured by Toagosei Co., Ltd.).

[0117] The inorganic compound may be surface-treated. Examples of the surface treatment include the introduction of various functional groups and treatment using a known surface modifier. Examples of the functional group introduced onto the surface of the inorganic compound include a polymerizable group, and a (meth)acrylate group is preferred. When the inorganic compound has a (meth)acrylate group on the surface, it is preferred because it easily reacts with resin particles that may be contained in the composition.

[0118] The average particle size of the inorganic compound is preferably 0.5 to 200 nm, more preferably 1 to 50 nm.

[0119] When the composition for forming a hard coat layer contains an inorganic compound, the content of the inorganic compound is preferably 10.0 to 80.0 mass %, more preferably 20.0 to 70.0 mass %, and still more preferably 30.0 to 60.0 mass %, based on the total solid content of the composition for forming a hard coat layer.

[0120] <Method for manufacturing laminate> Examples of the method for manufacturing the laminate of this embodiment include known manufacturing methods. Specifically, examples of the method for manufacturing a laminate include a step of forming an antireflection layer on at least one side of a substrate, a step of forming an intermediate layer by vapor-depositing a composition for forming an intermediate layer on the antireflection layer, and a step of forming a water-repellent layer on the intermediate layer. The method for forming each layer is as described above.

[0121] <Uses of Laminate> The laminate can be applied to various applications. When a lens substrate is used as the substrate, it is preferably used as an eyeglass lens. Other applications of the laminate include, for example, a front panel (window film) in a flexible display device. 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 disposed on the viewing side of the organic electroluminescent display panel and configured to be foldable. The laminate for a flexible display device may further include a polarizing plate (preferably a circular polarizing plate) and a touch sensor. In the laminate for a flexible display device, the laminate (window film), polarizing plate, and touch sensor are preferably stacked in this order from the viewing side, and the laminate (window film), touch sensor, and polarizing plate are preferably stacked in this order from the viewing side. The presence of a polarizing plate on the viewing side of the touch sensor is preferable because it makes the touch sensor pattern less visible, improving the visibility of the displayed image. Each component can be stacked using an adhesive, pressure-sensitive adhesive, or the like.

[0122] [Eyeglass Lens] The eyeglass lens is a lens having the laminate described above, and the substrate of the laminate is a lens substrate. The components constituting the eyeglass lens are as described above.

[0123] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples in any way.

[0124] Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-2 Laminates of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-2 were prepared according to the following procedure.

[0125] <Preparation of Substrate> A coating liquid was applied by spin coating to the surface of Nikon-Essilor's NL3-SP (size 75 mmφ, center thickness 1.1 mm), followed by heat curing to laminate, in this order, a urethane-based impact resistance improving coating (primer layer) with a thickness of approximately 1 μm and a silicone-based scratch resistance improving hard coating with a thickness of approximately 15 μm, to obtain a substrate. Next, a multilayer antireflection coating (antireflection layer) made of inorganic oxides (silica and zirconia) with a thickness of approximately 0.4 μm was formed on the silicone-based scratch resistance improving hard coating (hard coating layer) by vacuum deposition to obtain a substrate with an antireflection layer.

[0126] <Formation of Intermediate Layer> A composition for forming an intermediate layer 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 electron beam output set so as to give an average deposition rate of 0.7 nm / s, and a vacuum of 1.0×10 －２ The film was evaporated at 1000 Pa to form an intermediate layer having a thickness shown in Table 1. This resulted in a substrate having an intermediate layer on an antireflection layer. The average evaporation rate was calculated by dividing the thickness of the evaporated film (evaporated layer) by the evaporation time required to form the evaporated film having the above thickness (average evaporation rate (nm / s) = film thickness (nm) / evaporation time (s)). The above film thickness was measured using a quartz crystal film thickness meter (manufactured by INFICON) calibrated to indicate the film thickness on the substrate.

[0127] <Formation of Water-Repellent Layer> When the total of all components is taken as 100% by mass, OPTOOL (registered trademark) UF503 (manufactured by Daikin Industries, Ltd.) is 0.425% by mass, FAS13E (C ６ F １３ -C ２ H ４ -Si(OC ２ H ５ ) ３ , manufactured by Tokyo Chemical Industry Co., Ltd.) at 0.05% by mass, organic solvent FC-3283 (C ９ F ２１The components were mixed so that the balance was Fluorinert N, manufactured by 3M Co., Ltd., to prepare a composition for forming a water-repellent layer. The composition for forming a water-repellent layer was applied to a substrate having an intermediate layer on the anti-reflection layer using a dip coater (DT-0001-S3 manufactured by SDI Co., Ltd.) under conditions of a liquid immersion time of 10 seconds and a pull-up 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.

[0128] Examples 2-1 to 2-2 and Comparative Example 2-1 Preparation of Substrate A coating solution was applied by immersion to the surface of a Nikon-Essilor NL3-SP (size 75 mmφ, center thickness 1.1 mm), followed by heat curing to form a substrate by laminating, in this order, a urethane-based impact resistance improving coating (primer layer) having a thickness of approximately 1 μm and a silicone-based scratch resistance improving hard coating having a thickness of approximately 2 μm. Next, a multilayer antireflection coating (antireflection layer) made of inorganic oxides (silica and zirconia) having a thickness of approximately 0.4 μm was formed on the silicone-based scratch resistance improving hard coating (hard coating layer) by vacuum deposition to obtain a substrate with an antireflection layer.

[0129] <Formation of Intermediate Layer> An intermediate layer was formed on the antireflection layer of the obtained substrate with an antireflection layer in accordance with the procedure for forming the intermediate layer described above in [Examples 1-1 to 1-12 and Comparative Examples 1-1 and 1-2], except that the composition and film thickness of the composition for forming the intermediate layer were set to the values ​​shown in Table 1.

[0130] <Formation of Water-Repellent Layer> OPTOOL (registered trademark) DSX (solid content concentration 20% by mass, manufactured by Daikin Industries, Ltd.) and KY-130 (solid content concentration 20% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed so that the solid content of OPTOOL (registered trademark) DSX / solid content of KY-130 was 25 / 75 (mass ratio) to obtain a mixed solution. Next, the metal container containing the mixed solution was heat-treated at 120°C for 20 minutes to volatilize the solvent, thereby preparing a composition for forming a water-repellent layer. Using a vacuum deposition device (manufactured by Satisloh, model number 1200-DLX-2), the output of resistance heating was set so that the average deposition rate was 0.1 nm / s, and a vacuum of 4.0 x 10 was applied. －３At 1000 Pa, a water-repellent layer having 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.

[0131] Examples 3-1 to 3-3 Laminates were prepared in accordance with the procedures for preparing laminates described in Examples 2-1 to 2-2 and Comparative Example 2-1, except that the composition for forming an intermediate layer and the film thickness of the intermediate layer were set to the values ​​shown in Table 1, 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.), and trimethoxy(3,3,3-trifluoropropyl)silane (manufactured by Tokyo Chemical Industry Co., Ltd.) were used to prepare the composition for forming a water-repellent layer, and the composition for forming a water-repellent layer was set to a mass ratio of OPTOOL (registered trademark) DSX solid content / KY-130 solid content / trimethoxy(3,3,3-trifluoropropyl)silane = 20 / 60 / 20.

[0132] Examples 4-1 to 4-4 Laminates were prepared in accordance with the procedures for preparing laminates described in Examples 2-1 to 2-2 and Comparative Example 2-1, except that the composition for forming an intermediate layer and the film thickness of the intermediate layer were set to the values ​​shown in Table 1, OPTOOL (registered trademark) DSX (solid content concentration 20% by mass, manufactured by Daikin Industries, Ltd.), KY-130 (solid content concentration 20% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), and X-71-186 (solid content concentration 20% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) were used to prepare the composition for forming a water-repellent layer, and the composition for forming a water-repellent layer was set to a mass ratio of OPTOOL (registered trademark) DSX solid content / KY-130 solid content / X-71-186 solid content = 20 / 60 / 20.

[0133] [Evaluation] <Abrasion Resistance> The abrasion resistance of the laminate was evaluated according to the following procedure. First, the visible light transmittance of the laminate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science) and converted based on the definition of a 2-degree field of view (light source: Illuminant C) in JIS Z8701 to obtain the luminous transmittance YA (%). Next, an 8 mm x 120 mm rubber sheet and an abrasive-containing plastic sheet of the same size were stacked and fixed in this order to the flat surface of a pressing unit having a metal flat surface. The pressing unit was set so that the abrasive-containing plastic sheet fixed to the pressing unit was in contact with the surface of the water-repellent layer side of the laminate. At this time, the abrasive-containing plastic sheet and the laminate were adjusted to be parallel. After the above adjustment, a load of 1 kg was applied to the pressing unit, and with the laminate fixed, the abrasive-containing plastic sheet and the rubber sheet were moved back and forth in a linear direction at a speed of 100 times / 67 seconds. The reciprocating motion was carried out 100 times, with the relative movement distance between the laminate and the abrasive-containing plastic sheet being 30 mm. After the reciprocating motion, the laminate alone was rotated 45° counterclockwise and repositioned, and the abrasive-containing plastic sheet and rubber sheet were reciprocated under the same conditions as above. The rotation and repositioning of the laminate and the reciprocating motion were carried out two more times, for a total of 400 reciprocating motions. 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 better the scratch resistance of the laminate; in practice, a Y value difference of 3.5 or less is preferable.

[0134] [Results] Table 1 shows the composition of the intermediate layer-forming composition, the thickness of the intermediate layer, and the evaluation results.

[0135]

[0136] Details of the compounds shown in the table are given below: X-12-5263HP (the compound shown below, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-603 (the compound shown below, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-6803 (the compound shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0137]

[0138] The evaluation results confirmed that the laminate of the present disclosure has excellent scratch resistance.

Claims

1. A laminate having a base material, an anti-reflective layer, an intermediate layer, and a water-repellent layer in this order, The aforementioned intermediate layer is a vapor-deposited layer formed using an intermediate layer forming composition. The intermediate layer forming composition comprises at least one compound X selected from the group consisting of a compound represented by formula (X1), a hydrolysate of the compound represented by formula (X1), and a hydrolyzed condensate of the compound represented by formula (X1), A laminate comprising compound Y, which is a different compound from compound X, and which has at least one of an amino group and an amine skeleton, and also has a silicon atom. 【Chemistry 1】 In formula (X1), R ｎ１ R represents an alkyl group having an amino group and possibly having -NH-. ｘ１ R represents a hydroxyl group or a hydrolyzable group. ｘ２ represents a hydrocarbon group. mx represents an integer from 1 to 3.

2. The laminate according to claim 1, wherein the content of compound X in the intermediate layer forming composition is 33.0 to 71.0% by mass relative to the total content of compound X and compound Y.

3. The laminate according to claim 1 or 2, wherein the compound Y comprises at least one selected from the group consisting of a compound represented by formula (Y1), a hydrolysate of the compound represented by formula (Y1), and a hydrolyzed condensate of the compound represented by formula (Y1). 【Chemistry 2】 In formula (Y1), 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 from 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 that may have a fluorine atom.

4. Having the laminate according to claim 1 or 2, An eyeglass lens in which the substrate of the laminate is a lens substrate.

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