Method for producing laminate, and method for producing eyewear lens

Abstract

The present invention addresses the problem of providing: a method for producing a laminate having excellent wear resistance; and a method for producing an eyewear lens. The method for producing a laminate according to the present invention comprises a step 1 a for forming an intermediate layer (c) on an anti-reflection layer in a substrate (s) having the anti-reflection layer by vapor deposition and a step 2 for forming a water-repellent layer (r) on the intermediate layer (c), in which the intermediate layer (c) is a vapor deposition layer of an organosilicon compound (C) having a silicon atom and also having an amino group and / or an amine skeleton, the water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) having such a structure that a monovalent group having a perfluoroether structure is bound to a silicon atom through a linking group or without a linking group and a hydrolysable group is bound to a silicon atom through a linking group or without a linking group, and the average vapor deposition rate during the formation of the intermediate layer (c) is 0.2 nm / s or more and less than 1.2 nm / s.

Description

Manufacturing method of laminate, manufacturing method of eyeglass lens

[0001] The present disclosure relates to a method for manufacturing a laminate and a method for manufacturing 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. It also discloses that a fluorine-based compound having a polyperfluoropolyether chain is preferably used to form the surface layer (Z), and that a silane compound such as 3-acryloxypropyltrimethoxysilane is preferably used to form the primer layer (Y).

[0003] JP 2015-120253 A

[0004] The present disclosure relates to a method for producing a laminate, comprising: step 1 of forming an intermediate layer (c) by vapor deposition on an antireflection layer of a substrate (s) having an antireflection layer; and step 2 of forming a water-repellent layer (r) on the intermediate layer (c); the intermediate layer (c) is a vapor-deposited layer of an organosilicon compound (C) having a silicon atom and an amino group and / or an amine skeleton; the water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) in which a monovalent group having a perfluoropolyether structure is bonded to the silicon atom with or without a linking group, and a hydrolyzable group is bonded to the silicon atom with or without a linking group; and the average vapor deposition rate when forming the intermediate layer (c) on the antireflection layer by vapor deposition is 0.2 nm / s or more and less than 1.2 nm / s.

[0005] The method for producing a laminate according to the present disclosure will be described in detail below. It is desirable for a laminate to exhibit excellent abrasion resistance in order to maintain water repellency, and there is a need for a production method that can produce a laminate exhibiting the above properties with high productivity. The method for producing a laminate according to the present disclosure can produce a laminate exhibiting excellent abrasion resistance with high productivity. In this disclosure, "productively producible" means that when a plurality of laminates are produced, the difference in abrasion resistance between the laminates is small. A small difference in abrasion resistance between the laminates means that a laminate exhibiting consistent properties can be stably produced, i.e., the productivity is excellent.

[0006] The following description of the constituent elements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0007] Below, we will first explain each step of the manufacturing method of the present disclosure (hereinafter also referred to as the present manufacturing method), and then we will explain the laminate manufactured by the present manufacturing method (hereinafter also simply referred to as the laminate).

[0008] [Step 1] This production method includes Step 1, in which an intermediate layer (c) is formed by vapor deposition on the antireflection layer of a substrate (s) having an antireflection layer. The average vapor deposition rate when forming the intermediate layer (c) is 0.2 nm / s or more and less than 1.2 nm / s. The materials and components used in this step, as well as the procedure, are described below.

[0009] [Substrate (s) Having an Antireflection Layer] The material of the portion of the substrate (s) having an antireflection layer other than the antireflection layer (ar) is not particularly limited and may be either an organic material or an inorganic material, as long as the antireflection layer (ar) is provided on at least one side surface. Examples of organic materials include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, and vinyl resins (polyethylene, polyvinyl chloride, polystyrene, vinylbenzyl chloride resins, polyvinyl alcohol, etc.); and thermosetting resins such as phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, as well as alloys containing these metals, ceramics, and glass.

[0010] The laminate can be suitably used, for example, in eyeglass lenses. In this case, the substrate (s) having an antireflection layer is preferably one in which an antireflection layer (ar) is formed on a glass layer (sg) or a resin layer (sp). The antireflection layer (ar) is preferably formed at least on the intermediate layer (c) side. Examples of materials contained in the resin layer (sp) include allyl diglycol carbonate resin, polycarbonate resin, thiourethane resin, episulfide resin, etc. A primer layer and / or a hard coat layer may be formed between the glass layer (sg) or the resin layer (sp) and the antireflection layer (ar). The primer layer is a layer that improves the adhesion between the two layers laminated via the primer layer, and known materials can be used. The hard coat layer is a layer that imparts scratch resistance to the glass layer (sp) or the resin layer (sg) and exhibits a pencil hardness of H or higher according to the test method specified in JIS K5600. As the hard coat layer, known hard coat layers can be used, such as organic hard coat layers, inorganic hard coat layers, and organic-inorganic hybrid hard coat layers. The primer layer and hard coat layer can be formed, for example, by applying a precursor composition to a substrate and curing it, and the method for forming a water-repellent layer (r) described below can be used. The antireflection layer (ar) is a layer that has the function of preventing the reflection of incident light. Specifically, it is preferably a layer that exhibits reflective characteristics with a reflectance reduced to approximately 5.0% or less in the visible light region of 530 nm. The structure of the antireflection layer (ar) is not particularly limited, and it may be a single-layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which low-refractive index layers and high-refractive index layers are alternately laminated is preferred. Examples of materials constituting the high-refractive index layer include oxides of titanium, zirconium, aluminum, tantalum, and lanthanum, and examples of materials constituting the low-refractive index layer include silica. The multilayer antireflection layer (ar) can be made of a material such as SiO ２ and ZrO ２ are alternately laminated, and the outermost layer opposite to the glass layer (sg) or resin layer (sp) is SiO ２The antireflection layer (ar) can be formed by, for example, a vapor deposition method.

[0011] The thickness of the substrate (s) is, for example, 0.9 to 10 mm. If the thickness of the substrate (s) is not uniform, the thickness at the center of gravity of the substrate (s) should be within the above range.

[0012] [Organosilicon Compound (C)] The organosilicon compound (C) is an organosilicon compound having a silicon atom and an amino group and / or an amine skeleton. A hydroxyl group or a hydrolyzable group is preferably bonded to the silicon atom of the organosilicon compound (C). Examples of the hydrolyzable group bonded to the silicon atom contained in the organosilicon compound (C) include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc., with an alkoxy group being preferred, and an alkoxy group having 1 to 4 carbon atoms being more preferred.

[0013] Examples of the organosilicon compound (C) include an organosilicon compound (C1) represented by the following formula (c1), an organosilicon compound (C2) represented by the following formula (c2), and an organosilicon compound (C3) represented by the following formula (c3).

[0014] <Organosilicon Compound (C1)>

[0015]

[0016] In the above formula (c1), R ｘ１１ , R ｘ１２ , R ｘ１３ , R ｘ１４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｘ１１ If there are multiple R ｘ１１ may be different from each other, and R ｘ１２ If there are multiple R ｘ１２ may be different from each other, and R ｘ１３ If there are multiple R ｘ１３ may be different from each other, and R ｘ１４ If there are multiple R ｘ１４ may be different from each other, ｘ１１ , Rfｘ１２ , Rf ｘ１３ , Rf ｘ１４ are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ｘ１１ When there are multiple Rf ｘ１１ may be different from each other, and Rf ｘ１２ When there are multiple Rf ｘ１２ may be different from each other, and Rf ｘ１３ When there are multiple Rf ｘ１３ may be different from each other, and Rf ｘ１４ When there are multiple Rf ｘ１４ may be different from each other, ｘ１５ is an alkyl group having 1 to 20 carbon atoms, and R ｘ１５ If there are multiple R ｘ１５ may be different from each other, １１ is a hydrolyzable group, and X １１ If there are multiple Xs, １１ may be different from each other, １１ is —NH— or —S—, and Y １１ If there are multiple Y １１ may be different from each other, １１ represents a vinyl group, an α-methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group, a ureido group, or a mercapto group; p1 represents an integer of 1 to 20; p2, p3, and p4 each independently represent an integer of 0 to 10; p5 represents an integer of 1 to 10; p6 represents an integer of 1 to 3; Z １１ If is not an amino group, Y １１ At least one of Y is —NH—; １１ If all are -S-, then Z １１ is an amino group, and Z １１ -, -Si(X １１ ) ｐ６ (R ｘ１５ ) ３－ｐ６ , p1 −{C(R ｘ１１ ) (R ｘ１２)}-, p2 -{C(Rf ｘ１１ ) (Rf ｘ１２ )}-, p3 -{Si(R ｘ１３ ) (R ｘ１４ )}-, p4 -{Si(Rf ｘ１３ ) (Rf ｘ１４ )}-, p5 -Y １１ - is Z １１ - and -Si(X １１ ) ｐ６ (R ｘ１５ ) ３－ｐ６ are at the ends, and they can be bonded in any order as long as --O-- is not linked to --O--.

[0017] R ｘ１１ , R ｘ１２ , R ｘ１３ , and R ｘ１４ is preferably a hydrogen atom.

[0018] Rf ｘ１１ , Rf ｘ１２ , Rf ｘ１３ , and Rf ｘ１４ are preferably each independently a fluorine atom or an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom.

[0019] R ｘ１５ is preferably an alkyl group having 1 to 5 carbon atoms.

[0020] X １１ is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and further preferably a methoxy group or an ethoxy group.

[0021] Y １１ is preferably —NH—.

[0022] Z １１ is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, and even more preferably an amino group.

[0023] p1 is preferably 1 to 15, more preferably 2 to 10. p2, p3, and p4 are each independently preferably 0 to 5, more preferably all 0 to 2. p5 is preferably 1 to 5, more preferably 1 to 3. p6 is preferably 2 or 3, more preferably 3.

[0024] The organosilicon compound (C1) is a compound represented by the formula (c1) above, wherein R ｘ１１ and R ｘ１２ are all hydrogen atoms, and Y １１ is —NH—, and X １１ is an alkoxy group (particularly a methoxy group or an ethoxy group), and Z １１ is an amino group or a mercapto group, p1 is 1 to 10, p2, p3 and p4 are all 0, p5 is 1 to 5 (particularly 1 to 3), and p6 is 3.

[0025] The organosilicon compound (C1) is preferably a compound represented by the following formula (c1-2):

[0026]

[0027] In the above formula (c1-2), X １２ is a hydrolyzable group, and X １２ If there are multiple Xs, １２ may be different from each other, １２ is —NH—, and Z １２ is an amino group or a mercapto group, R ｘ１６ is an alkyl group having 1 to 20 carbon atoms, and R ｘ１６ If there are multiple R ｘ１６ may be different from each other, p is an integer of 1 to 3, q ​​is an integer of 2 to 5, and r is an integer of 0 to 5.

[0028] X １２ is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, and more preferably an alkoxy group.

[0029] Z １２ is preferably an amino group.

[0030] R ｘ１６ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0031] p is preferably an integer of 2 or 3, and more preferably 3.

[0032] q is preferably an integer of 2 to 3, and r is preferably an integer of 2 to 4.

[0033] <Organosilicon Compound (C2)>

[0034]

[0035] In the above formula (c2), R ｘ２０ and R ｘ２１ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｘ２０ If there are multiple R ｘ２０ may be different from each other, and R ｘ２１ If there are multiple R ｘ２１ may be different from each other, ｘ２０ and Rf ｘ２１ are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ｘ２０ When there are multiple Rf ｘ２０ may be different from each other, and Rf ｘ２１ When there are multiple Rf ｘ２１ may be different from each other, ｘ２２ and R ｘ２３ are each independently an alkyl group having 1 to 20 carbon atoms, and R ｘ２２ and R ｘ２３ If there are multiple R ｘ２２ and R ｘ２３ may be different from each other, ２０ and X ２１ are each independently a hydrolyzable group, and X ２０ and X ２１ If there are multiple Xs, ２０ and X ２１may be different from each other, p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units enclosed in parentheses with p20 or p21 has an amine skeleton -NR １００ -, and R in the amine skeleton １００ represents a hydrogen atom or an alkyl group, p22 and p23 each independently represent an integer of 1 to 3, and p20 -{C(R ｘ２０ ) (R ｘ２１ )}-, p21 -{C(Rf ｘ２０ ) (Rf ｘ２１ )))-, p20 or p21 do not have to be consecutive, and can be bonded in any order, and both ends are -Si(X ２０ ) ｐ２２ (R ｘ２２ ) ３－ｐ２２ and -Si(X ２１ ) ｐ２３ (R ｘ２３ ) ３－ｐ２３ This becomes:

[0036] R ｘ２０ and R ｘ２１ is preferably a hydrogen atom.

[0037] Rf ｘ２０ and Rf ｘ２１ Preferably, each of and independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom.

[0038] R ｘ２２ and R ｘ２３ is preferably an alkyl group having 1 to 5 carbon atoms.

[0039] X ２０ and X ２１ is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and further preferably a methoxy group or an ethoxy group.

[0040] Amine skeleton -NR １００As described above, at least one - may be present in the molecule, and any of the repeating units enclosed in parentheses with p20 or p21 attached thereto may be substituted with the amine skeleton, but it is preferable that the - be part of the repeating unit enclosed in parentheses with p20 attached thereto. A plurality of the amine skeletons may be present, and in such a case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. In this case, it is preferable that an alkylene group be present between adjacent amine skeletons, and the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5. The number of carbon atoms in the alkylene group between adjacent amine skeletons is included in the total number of p20 or p21.

[0041] Amine skeleton -NR １００ -In R １００ When —NR is an alkyl group, it preferably has 5 or less carbon atoms, more preferably 3 or less carbon atoms. １００ - is -NH-(R １００ is preferably a hydrogen atom).

[0042] p20 is preferably 1 to 15, more preferably 1 to 10, excluding the number of repeating units replaced with an amine skeleton.

[0043] p21 is preferably 0 to 5, more preferably 0 to 2, excluding the number of repeating units replaced with an amine skeleton.

[0044] p22 and p23 are preferably 2 to 3, more preferably 3.

[0045] The organosilicon compound (C2) is a compound represented by the formula (c2) above, wherein R ｘ２０ and R ｘ２１ are all hydrogen atoms, and X ２０ and X ２１ is an alkoxy group (particularly a methoxy group or an ethoxy group), and the repeating unit enclosed in parentheses with p20 has at least one amine skeleton -NR １００ - is replaced by R １００is a hydrogen atom, p20 is 1 to 10 (excluding the number of repeating units replaced with an amine skeleton), p21 is 0, and p22 and p23 are 3.

[0046] The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2):

[0047]

[0048] In the above formula (c2-2), X ２２ and X ２３ are each independently a hydrolyzable group, and X ２２ and X ２３ If there are multiple Xs, ２２ and X ２３ may be different from each other, ｘ２４ and R ｘ２５ are each independently an alkyl group having 1 to 20 carbon atoms, and R ｘ２４ and R ｘ２５ If there are multiple R ｘ２４ and R ｘ２５ may be different from each other, ｗ H ２ｗ - is a group in which at least one of the methylene groups is an amine skeleton -NR １００ - is replaced by R １００ represents a hydrogen atom or an alkyl group; w represents an integer of 1 to 30 (excluding the number of methylene groups substituted for the amine skeleton); and p24 and p25 each independently represent an integer of 1 to 3.

[0049] X ２２ and X ２３ is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably an alkoxy group having 1 to 4 carbon atoms (particularly a methoxy group or an ethoxy group).

[0050] Amine skeleton -NR １００There may be a plurality of -'s, and in such a case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. In this case, it is preferable that an alkylene group be present between adjacent amine skeletons. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 5. The number of carbon atoms in the alkylene group between adjacent amine skeletons is included in the total number of w.

[0051] Amine skeleton -NR １００ -In R １００ When —NR is an alkyl group, it preferably has 5 or less carbon atoms, more preferably 3 or less carbon atoms. １００ - is -NH-(R １００ is preferably a hydrogen atom).

[0052] R ｘ２４ and R ｘ２５ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0053] p24 and p25 are preferably integers of 2 to 3, and more preferably 3.

[0054] w is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.

[0055] <Organosilicon Compound (C3)>

[0056]

[0057] In the above formula (c3), Z ３１ , Z ３２ are each independently a reactive functional group other than a hydrolyzable group or a hydroxy group. Examples of the reactive functional group include a vinyl group, an α-methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an epoxy group, a ureido group, and a mercapto group. Z ３１ , Z ３２ As the alkyl group, an amino group, a mercapto group, or a methacryloyl group is preferred, and an amino group is particularly preferred.

[0058] R ｘ３１ , R ｘ３２ , R ｘ３３ , R ｘ３４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｘ３１ If there are multiple R ｘ３１ may be different from each other, and R ｘ３２ If there are multiple R ｘ３２ may be different from each other, and R ｘ３３ If there are multiple R ｘ３３ may be different from each other, and R ｘ３４ If there are multiple R ｘ３４ may be different from each other. ｘ３１ , R ｘ３２ , R ｘ３３ , R ｘ３４ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom.

[0059] Rf ｘ３１ , Rf ｘ３２ , Rf ｘ３３ , Rf ｘ３４ are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ｘ３１ When there are multiple Rf ｘ３１ may be different from each other, and Rf ｘ３２ When there are multiple Rf ｘ３２ may be different from each other, and Rf ｘ３３ When there are multiple Rf ｘ３３ may be different from each other, and Rf ｘ３４ When there are multiple Rf ｘ３４ may be different from each other. ｘ３１ , Rf ｘ３２ , Rf ｘ３３ , Rf ｘ３４ is preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom.

[0060] Y ３１ is -NH-, -N(CH ３)- or -O-, and Y ３１ If there are multiple Y ３１ may be different from each other. ３１ is preferably —NH—.

[0061] X ３１ , X ３２ , X ３３ , X ３４ are each independently -OR ｃ (R ｃ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino group １－３ Alkyldi-C １－３ an alkoxysilyl group), and X ３１ If there are multiple Xs, ３１ may be different from each other, and X ３２ If there are multiple Xs, ３２ may be different from each other, and X ３３ If there are multiple Xs, ３３ may be different from each other, and X ３４ If there are multiple Xs, ３４ may be different from each other. ３１ , X ３２ , X ３３ , X ３４ is R ｃ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; ｃ Preferably, R ｃ is more preferably a hydrogen atom.

[0062] p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, p36 is an integer of 1 to 10, and p37 is 0 or 1. p31 is preferably 1 to 15, more preferably 3 to 13, and even more preferably 5 to 10. p32, p33, and p34 are each independently preferably 0 to 5, and more preferably all are 0 to 2. p35 is preferably 1 to 5, and more preferably 1 to 3. p36 is preferably 1 to 5, and more preferably 1 to 3. p37 is preferably 1.

[0063] The organosilicon compound (C3) is Z３１ and Z ３２ At least one of Y is an amino group, or ３１ At least one of is -NH- or -N(CH ３ )- and the terminal is Z ３１ - and Z ３２ -, and unless -O- is linked to -O-, p31 -{C(R ｘ３１ ) (R ｘ３２ )}-, p32 -{C(Rf ｘ３１ ) (Rf ｘ３２ )}-, p33 -{Si(R ｘ３３ ) (R ｘ３４ )}-, p34 -{Si(Rf ｘ３３ ) (Rf ｘ３４ )}-, p35 -Y ３１ -, p36 -{Si(X ３１ ) (X ３２ )-O}-, p37 -{Si(X ３３ ) (X ３４ )}- are arranged in any order and bonded together. ｘ３１ ) (R ｘ３２ )}- is -{C(R ｘ３１ ) (R ｘ３２ )))- do not need to be bonded consecutively, and may be bonded via other units in between, as long as there are a total of p31. The same applies to the units grouped by p32 to p37.

[0064] The organosilicon compound (C3) is a compound represented by the formula (c3) above, wherein Z ３１ and Z ３２ is an amino group, and R ｘ３１ and R ｘ３２ is a hydrogen atom, p31 is 3 to 13 (preferably 5 to 10), and R ｘ３３ and R ｘ３４ are all hydrogen atoms, and Rf ｘ３１ ~Rf ｘ３４ are each a fluorine atom or an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, p32 to p34 are each a fluorine atom, and Y ３１ is —NH—, p35 is 0 to 5 (preferably 0 to 3), and X ３１ ~X３４ are both —OH, p36 is 1 to 5 (preferably 1 to 3), and p37 is 1.

[0065] The organosilicon compound (C3) is preferably a compound represented by the following formula (c3-2):

[0066]

[0067] In the above formula (c3-2), Z ３１ , Z ３２ , X ３１ , X ３２ , X ３３ , X ３４ , Y ３１ have the same meanings as those in formula (c3), p41 to p44 each independently represent an integer of 1 to 6, and p45 and p46 each independently represent 0 or 1.

[0068] In formula (c3-2), Z ３１ and Z ３２ is preferably an amino group, a mercapto group, or a methacryloyl group, and particularly preferably an amino group. ３１ , X ３２ , X ３３ , X ３４ is R ｃ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; ｃ Preferably, R ｃ It is more preferable that Y is a hydrogen atom. ３１ is preferably —NH—. p41 to p44 are preferably 2 or more, and preferably 5 or less, and more preferably 4 or less. Both p45 and p46 are preferably 0.

[0069] The organosilicon compound (C) is preferably at least one selected from the group consisting of organosilicon compounds (C1) and organosilicon compounds (C2), more preferably organosilicon compound (C2), and even more preferably a compound represented by formula (c2-2).

[0070] The organosilicon compound (C) may be used alone or in combination of two or more.

[0071] [Procedure of Step 1] Step 1 is a step of forming an intermediate layer (c) by vapor deposition on the antireflection layer of a substrate (s) having an antireflection layer. The intermediate layer (c) is a vapor-deposited layer of an organosilicon compound (C) having a silicon atom and an amino group and / or an amine skeleton. The organosilicon compound (C) used for vapor deposition is as described above.

[0072] As the deposition method, a known method can be used, for example, a vacuum deposition method. In the vacuum deposition method, a deposition source is evaporated in a vacuum chamber and attached to the surface of a substrate. In the vacuum deposition method, the degree of vacuum during deposition 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 Pa or higher in most cases.

[0073] Examples of methods for evaporating the deposition source in vacuum deposition include electron beam, resistance heating, heater heating, and induction heating, with the electron beam being preferred from the viewpoint of energy conversion efficiency. The output of the electron beam may be appropriately adjusted depending on the raw materials and substrate used, the deposition apparatus, the degree of vacuum, the irradiation area, and the average deposition rate, and a beam current of, for example, 6 to 36 mA is preferred.

[0074] The average deposition rate when vapor-depositing the organosilicon compound (C) onto the antireflection layer of the substrate (s) having an antireflection layer is 0.2 nm / s or more but less than 1.2 nm / s (0.20 nm / s or more but less than 1.20 nm / s), preferably 0.2 nm / s to 1.15 nm / s, and more preferably 0.2 nm / s to 1.1 nm / s. The average deposition rate is the value obtained by dividing the thickness of the vapor-deposited film by the deposition time required to form a vapor-deposited film of the above thickness (average deposition rate (nm / s) = film thickness (nm) / deposition time (s)). If the average deposition rate is 1.2 nm / s or more, abrasion resistance and productivity decrease, while if the average deposition rate is less than 0.2 nm / s, productivity decreases, which is undesirable.

[0075] [Intermediate layer (c)] The intermediate layer (c) is a vapor-deposited layer of the organosilicon compound (C). The vapor deposition method is as described above. The intermediate layer (c) has silicon atoms and an amino group or an amine skeleton (—NR １００ - and R １００ is a hydrogen atom or an alkyl group), and the intermediate layer (c) has an amino group or an amine skeleton. In a preferred embodiment, a hydrolyzable group or a hydroxy group is bonded to the silicon atom of the organosilicon compound (C), and Si-OH groups produced by hydrolysis of the Si-OH groups and / or the hydrolyzable groups bonded to the silicon atoms of the organosilicon compound (C) undergo dehydration condensation with each other, so that the intermediate layer (c) preferably has a condensation structure derived from the organosilicon compound (C). The intermediate layer (c) can function as a primer layer for the water-repellent layer (r).

[0076] The thickness of the intermediate layer (c) is, for example, about 1 to 1000 nm, preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm, and is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 50 nm or less.

[0077] [Step 2] This production method includes Step 2, in which a water-repellent layer (r) is formed on the intermediate layer (c) obtained in Step 1. The water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) in which a monovalent group having a perfluoropolyether structure is bonded to a silicon atom via a linking group or not, and a hydrolyzable group is bonded to the silicon atom via a linking group or not. Among these, the mixed composition (ca) is preferably a mixed composition of an organosilicon compound (A) and an organosilicon compound (B) described below. The materials and procedures used in this step are described below.

[0078] <Organosilicon Compound (A)> The organosilicon compound (A) is a compound in which a monovalent group having a perfluoropolyether structure is bonded to a silicon atom via a linking group or not, and a hydrolyzable group is bonded to the silicon atom via a linking group or not. The water-repellent layer (r) is obtained by applying and curing the mixed composition (ca), and has a structure derived from the organosilicon compound (A). As described above, the organosilicon compound (A) has a hydrolyzable group bonded to a silicon atom (which may be bonded via a linking group), and the -SiOH groups (Si and OH may be bonded via a linking group) of the organosilicon compound (A) generated by hydrolysis undergo dehydration condensation, so the water-repellent layer (r) usually has a condensation structure derived from the organosilicon compound (A). Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group.

[0079] The perfluoropolyether structure can also be referred to as a perfluorooxyalkylene group. The perfluoropolyether structure has liquid repellency such as water repellency or oil repellency. The number of carbon atoms contained in the longest linear chain portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the carbon number is not particularly limited, and may be, for example, about 200. It is preferable that the monovalent group having a perfluoropolyether structure of the organosilicon compound (A) further has a perfluoroalkyl group at the free end.

[0080] The water-repellent layer (r) can also be shown as a layer having a perfluoropolyether structure and a polysiloxane skeleton, and preferably further has a perfluoroalkyl group. The water-repellent layer (r) preferably has a structure in which a monovalent group having a perfluoropolyether structure and a perfluoroalkyl group at the free end is bonded to a silicon atom of a part of the polysiloxane skeleton. The presence of the perfluoroalkyl group at the free end improves the water repellency of the water-repellent layer (r).

[0081] The number of carbon atoms in the perfluoroalkyl group (particularly the number of carbon atoms in the longest straight chain portion) is, for example, preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. There is no particular upper limit on the number of carbon atoms, and even a group of about 20 carbon atoms will exhibit excellent water repellency.

[0082] The perfluoroalkyl group may be bonded to a hydrocarbon group and / or a group in which at least some of the hydrogen atoms of the hydrocarbon group have been substituted with fluorine atoms to form a fluorine-containing group such as a fluoroalkyl group, for example, CF ３ (CF ２ ) ｍ - (CH ２ ) ｎ -, CF ３ (CF ２ ) ｍ -C ６ H ４ - (wherein m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4), and CF ３ (CF ２ ) ｍ - (CH ２ ) ｎ - (wherein m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4) is preferred. It is more preferred that the perfluoroalkyl group is directly bonded to the perfluoropolyether structure.

[0083] In organosilicon compound (A), the monovalent group with perfluoropolyether structure and silicon atom can be bonded via suitable linking group, or the monovalent group with the above-mentioned perfluoropolyether can be directly bonded to silicon atom without this linking group.As linking group, for example, can be enumerated hydrocarbon group such as alkylene group, aromatic hydrocarbon group, (poly) alkylene glycol group, or the group in which part of their hydrogen atom is replaced by F or substituent, and the group in which these are suitably bonded.The carbon number of linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less.

[0084] The hydrolyzable group functions to bond the organosilicon compounds (A) together or to bond the organosilicon compound (A) to active hydrogen (such as a hydroxyl group) on the surface of the substrate through a hydrolysis / dehydration condensation reaction. Examples of such hydrolyzable groups include alkoxy groups (particularly alkoxy groups having 1 to 4 carbon atoms), hydroxy groups, acetoxy groups, and halogen atoms (particularly chlorine atoms). Preferred hydrolyzable groups are alkoxy groups and halogen atoms, with methoxy groups, ethoxy groups, and chlorine atoms being particularly preferred.

[0085] The hydrolyzable group may be bonded to the silicon atom via a linking group, or may be bonded directly to the silicon atom without a linking group. The number of hydrolyzable groups bonded to the silicon atom may be one or more, and may be two or three, preferably two or three, and particularly preferably three. When two or more hydrolyzable groups are bonded to the silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but it is preferable that the same hydrolyzable group is bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to the silicon atom is usually four, but may be two or three (particularly three). When the number is three or less, the remaining bonds may be bonded to monovalent groups other than hydrolyzable groups, for example, alkyl groups (particularly alkyl groups having 1 to 4 carbon atoms), H, NCO, etc.

[0086] The monovalent group having a perfluoropolyether structure in the organosilicon compound (A) may be linear or may have a side chain, but is preferably linear.

[0087] An example of the organosilicon compound (A) is a compound represented by the following formula (a):

[0088]

[0089] In the above formula (a), D １ is a monovalent group having a perfluoropolyether structure, and D １ D in ２ The end that bonds to is -CF ２ -O-*, -CFD ９ -* (* is D ２ side bond), D ２is a single bond or a divalent hydrocarbon group not substituted with a fluorine atom, and D ３ is a trivalent hydrocarbon group not substituted with fluorine atoms, and some of the methylene groups of the hydrocarbon group may be replaced with oxygen atoms; D ４ is a hydrogen atom or a fluorine atom, and D ５ is a single bond or a divalent hydrocarbon group, and D ６ is a monovalent group other than a hydrolyzable group, and D ７ is a divalent group or a single bond, and D ８ is a hydrolyzable group, and D ９ is a hydrogen atom, a fluorine atom, or a hydrocarbon group, n1 is 1 to 30, and n2 is 1 to 3. D ８ Examples of the hydrolyzable group include those mentioned above.

[0090] The organosilicon compound (A) is preferably a compound represented by the following formula (a1):

[0091]

[0092] In the above formula (a1), Rf ａ１ is a divalent perfluoropolyether structure having oxygen atoms at both ends, and R １１ , R １２ , and R １３ are each independently (i.e., R １１ and R １２ and R １３ may be the same or different) are alkyl groups having 1 to 20 carbon atoms, R １１ If there are multiple R １１ may be different from each other, and R １２ If there are multiple R １２ may be different from each other, and R １３ If there are multiple R １３ may be different from each other, １ , E ２ , E ３ , E ４ , and E ５ are each independently a hydrogen atom or a fluorine atom, E １ If there are multiple E１ may be different from each other, and E ２ If there are multiple E ２ may be different from each other, and E ３ If there are multiple E ３ may be different from each other, and E ４ If there are multiple E ４ may be different from each other, １ and G ２ are each independently a divalent to decavalent organosiloxane group having a siloxane bond, １ , J ２ , and J ３ are each independently a hydrolyzable group or -(CH ２ ) ｅ６ -Si(OR １４ ) ３ and e6 is 1 to 5, and R １４ is a methyl group or an ethyl group, J １ If there are multiple J １ may be different from each other, ２ If there are multiple J ２ may be different from each other, ３ If there are multiple J ３ may be different from each other, １ and L ２ are each independently a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, or a fluorine atom, and L １ If there are multiple L １ may be different from each other, and L ２ If there are multiple L ２ may be different from each other, d11 is 1 to 9, d12 is 0 to 9, a10 and a14 are each independently 0 to 10, a11 and a15 are each independently 0 or 1, a12 and a16 are each independently 0 to 9, a13 is 0 or 1, a21, a22, and a23 are each independently 0 to 2, and e1, e2, and e3 are each independently 1 to 3.

[0093] As represented by the above formula (a1), the organosilicon compound (A) is ａ１ and has a perfluoropolyether structure represented by J ２ or a hydrolyzable group represented by -(CH ２ ) ｅ６ -Si(OR １４ ) ３ (However, R １４ The perfluoropolyether structure is a structure in which all hydrogen atoms of a polyoxyalkylene group are replaced with fluorine atoms, and can be called a perfluorooxyalkylene group, and can impart water repellency to the resulting coating. ２ The organosilicon compounds (A) are compounds that can become the matrix of the resulting coating by bonding with each other or with other monomers through a polymerization reaction (particularly a polycondensation reaction).

[0094] Rf ａ１ is -O-(CF ２ CF ２ O) ｅ４ -, or -O-(CF ２ CF ２ CF ２ O) ｅ５ Preferably, e4 and e5 are each 15 to 80.

[0095] R １１ , R １２ , and R １３ are each preferably an alkyl group having 1 to 10 carbon atoms.

[0096] L １ and L ２ are preferably each independently a divalent linking group containing a fluorine atom and having 1 to 5 carbon atoms.

[0097] G １ and G ２ are each preferably independently a divalent to pentavalent organosiloxane group having a siloxane bond.

[0098] J １ , J ２ , and J ３are each independently a methoxy group, an ethoxy group, or -(CH ２ ) ｅ６ -Si(OR １４ ) ３ is preferred.

[0099] a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), a14 is preferably 1 to 6 (more preferably 1 to 3), a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all 0), d11 is preferably 1 to 5 (more preferably 1 to 3), d12 is preferably 0 to 3 (more preferably 0 or 1), and e1 to e3 are all preferably 3. Also, a13 is preferably 1.

[0100] The organosilicon compound (A) is a compound represented by the formula (a1) above, ａ１ -O-(CF ２ CF ２ CF ２ O) ｅ５ -, e5 is 35 to 50, and L １ and L ２ are each a perfluoroalkylene group having 1 to 3 carbon atoms, and E １ , E ２ , and E ３ are all hydrogen atoms, and E ４ , and E ５ is a hydrogen atom or a fluorine atom, and J １ , J ２ , and J ３ are all methoxy groups or ethoxy groups (particularly methoxy groups), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 2 to 5, a15 is 0, a16 is 0 to 6, a21 to a23 are each independently 0 or 1 (more preferably, a21 to a23 are all 0), d11 is 1, d12 is 0 or 1, and e1 to e3 are all 3.

[0101] The organosilicon compound (A) is a compound represented by the formula (a1) above, ａ１ -O-(CF ２ CF２ CF ２ O) ｅ５ -, e5 is 25 to 40, and L １ is a divalent linking group having 3 to 6 carbon atoms containing a fluorine atom and an oxygen atom, and L ２ is a perfluoroalkylene group having 1 to 3 carbon atoms, and E ２ , E ３ are all hydrogen atoms, and E ５ is a fluorine atom, and J ２ Ga-(CH ２ ) ｅ６ -Si(OCH ３ ) ３ It is also preferable to use a compound in which e6 is 2 to 4, a10 is 1 to 3, a11 is 0, a12 is 0, a13 is 0, a14 is 2 to 5, a15 is 0, a16 is 0, a21 to a23 are each independently 0 or 1 (more preferably, a21 to a23 are all 0), d11 is 1, d12 is 0, and e2 is 3.

[0102] The organosilicon compound (A) is also preferably a compound represented by the following formula (a2-1):

[0103]

[0104] In the above formula (a2-1), Rf ａ２１ is a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ａ２２ , Rf ａ２３ , Rf ａ２４ , and Rf ａ２５ are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ａ２２ When there are multiple Rf ａ２２ may be different from each other, and Rf ａ２３ When there are multiple Rf ａ２３ may be different from each other, and Rf ａ２４ When there are multiple Rf ａ２４ may be different from each other, and Rf ａ２５ When there are multiple Rfａ２５ may be different from each other, ２０ , R ２１ , R ２２ , and R ２３ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ２０ If there are multiple R ２０ may be different from each other, and R ２１ If there are multiple R ２１ may be different from each other, and R ２２ If there are multiple R ２２ may be different from each other, and R ２３ If there are multiple R ２３ may be different from each other, ２４ is an alkyl group having 1 to 20 carbon atoms, and R ２４ If there are multiple R ２４ may be different from each other, １ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M １ If there are multiple M １ may be different from each other, ２ is a hydrogen atom or a halogen atom, M ３ is —O—, —C(═O)—O—, —O—C(═O)—, —NR—, —NRC(═O)—, or —C(═O)NR— (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and M ３ If there are multiple M ３ may be different from each other, ４ is a hydrolyzable group, and M ４ If there are multiple M ４ may be different from one another, f11, f12, f13, f14, and f15 are each independently an integer of 0 to 600, and the sum of f11, f12, f13, f14, and f15 is 13 or more, f16 is an integer of 1 to 20, f17 is an integer of 0 to 2, g1 is an integer of 1 to 3, and Rf ａ２１ -, M ２ -, f11 -{C(R２０ ) (R ２１ )}-, f12 -{C(Rf ａ２２ ) (Rf ａ２３ )}-, f13 -{Si(R ２２ ) (R ２３ )}-, f14 -{Si(Rf ａ２４ ) (Rf ａ２５ )}-, f15 -M ３ -, and f16 -[CH ２ C (M １ ) {(CH ２ ) ｆ１７ -Si(M ４ ) ｇ１ (R ２４ ) ３－ｇ１}]- is Rf ａ２１ -, M ２ The - is at the end, and they are arranged in an order to form at least a part of a perfluoropolyether structure, and they are bonded in any order as long as -O- is not linked to -O- to -F. That is, the formula (a2-1) does not necessarily include f11 -{C(R ２０ ) (R ２１ )}- are consecutive, and f12 -{C(Rf ａ２２ ) (Rf ａ２３ )}- are consecutive, and f13 -{Si(R ２２ ) (R ２３ )}- are consecutive, and f14 -{Si(Rf ａ２４ ) (Rf ａ２５ ) )) - is consecutive, and f15 -M ３ - is continuous, and f16 -[CH ２ C (M １ ) {(CH ２ ) ｆ１７ -Si(M ４ ) ｇ１ (R ２４ ) ３－ｇ１}] - does not mean that they are consecutive and lined up in this order, but -C(R ２０ ) (R ２１ )—Si(Rf ａ２４ ) (Rf ａ２５ )-CH ２ C (M １ ) {(CH ２ ) ｆ１７ -Si(M ４ ) ｇ１ (R２４ ) ３－ｇ１}-C(Rf ａ２２ ) (Rf ａ２３ )-M ３ -Si(R ２２ ) (R ２３ )-C(Rf ａ２２ ) (Rf ａ２３ ) - and so on, each of which can be arranged in any order.

[0105] Rf ａ２１ is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

[0106] Rf ａ２２ , Rf ａ２３ , Rf ａ２４ , and Rf ａ２５ are preferably each independently a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and more preferably all are fluorine atoms.

[0107] R ２０ , R ２１ , R ２２ , and R ２３ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably all are hydrogen atoms.

[0108] R ２４ is preferably an alkyl group having 1 to 5 carbon atoms.

[0109] M １ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably all are hydrogen atoms.

[0110] M ２ is preferably a hydrogen atom.

[0111] M ３ is preferably —C(═O)—O—, —O—, or —O—C(═O)—, and more preferably all are —O—.

[0112] M ４is preferably an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom.

[0113] Preferably, f11, f13, and f14 are each 1 / 2 or less, more preferably 1 / 4 or less, of f12, still more preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.

[0114] Preferably, f15 is at least 1 / 5 of the total value of f11, f12, f13, and f14, and is at most the total value of f11, f12, f13, and f14.

[0115] f12 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200 (still more preferably 30 to 150, particularly 50 to 150, and most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, and even more preferably 10 to 200 (still more preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200.

[0116] f16 is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 10.

[0117] f17 is preferably 0 to 1.

[0118] g1 is preferably 2 or 3, and more preferably 3.

[0119] f11 -{C(R ２０ ) (R ２１ )}-, f12 -{C(Rf ａ２２ ) (Rf ａ２３ )}-, f13 -{Si(R ２２ ) (R ２３ )}-, f14 -{Si(Rf ａ２４ ) (Rf ａ２５ )}-, and f15 -M ３The order of - in the formula is arbitrary as long as it is arranged in an order that forms at least a part of a perfluoropolyether structure, but preferably, the repeating unit enclosed in parentheses with f12 attached at the most fixed end side (the side that bonds to the silicon atom) (i.e., -{C(Rf ａ２２ ) (Rf ａ２３ )}-) is a repeating unit enclosed in parentheses with f11 at the most free end (i.e., -{C(R ２０ ) (R ２１ )}-) located closer to the free end, more preferably the repeating unit enclosed in parentheses with f12 and f14 located closest to the fixed end (i.e., -{C(Rf ａ２２ ) (Rf ａ２３ )}-, and -{Si(Rf ａ２４ ) (Rf ａ２５ )}-) is a repeating unit enclosed in parentheses with the most free end f11 and f13 (i.e., -{C(R ２０ ) (R ２１ )}-, and -{Si(R ２２ ) (R ２３ )-) is located closer to the free end.

[0120] In the above formula (a2-1), Rf ａ２１ is a perfluoroalkyl group having 1 to 5 carbon atoms, and Rf ａ２２ , Rf ａ２３ , Rf ａ２４ , Rf ａ２５ are all fluorine atoms, and M ３ are all -O-, and M ４ are all methoxy groups, ethoxy groups or chlorine atoms (particularly methoxy groups or ethoxy groups), and M １ , M ２ are all hydrogen atoms, f11 is 0, f12 is 30 to 150 (more preferably 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (particularly 0), g1 is 3, and f16 is 1 to 10.

[0121] The organosilicon compound (A) is also preferably a compound represented by the following formula (a2-2):

[0122]

[0123] In the above formula (a2-2), Rf ａ２６ , Rf ａ２７ , Rf ａ２８ , and Rf ａ２９ are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ａ２６ When there are multiple Rf ａ２６ may be different from each other, and Rf ａ２７ When there are multiple Rf ａ２７ may be different from each other, and Rf ａ２８ When there are multiple Rf ａ２８ may be different from each other, and Rf ａ２９ When there are multiple Rf ａ２９ may be different from each other, ２５ , R ２６ , R ２７ , and R ２８ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ２５ If there are multiple R ２５ may be different from each other, and R ２６ If there are multiple R ２６ may be different from each other, and R ２７ If there are multiple R ２７ may be different from each other, and R ２８ If there are multiple R ２８ may be different from each other, ２９ , and R ３０ are each independently an alkyl group having 1 to 20 carbon atoms, and R ２９ If there are multiple R ２９ may be different from each other, and R ３０ If there are multiple R ３０ may be different from each other, ７ is —O—, —C(═O)—O—, —O—C(═O)—, —NR—, —NRC(═O)—, or —C(═O)NR—, where R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and M ７If there are multiple M ７ may be different from each other, ５ , M ９ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M ５ If there are multiple M ５ may be different from each other, and M ９ If there are multiple M ９ may be different from each other, ６ , and M １０ are each independently a hydrogen atom or a halogen atom, ８ , and M １１ are each independently a hydrolyzable group, M ８ If there are multiple M ８ may be different from each other, and M １１ If there are multiple M １１ may be different from one another, f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the sum of f21, f22, f23, f24, and f25 is 13 or more, f26 and f28 are each independently an integer of 1 to 20, f27 and f29 are each independently an integer of 0 to 2, g2 and g3 are each independently an integer of 1 to 3, and M １０ -, M ６ -, f21 -{C(R ２５ ) (R ２６ )}-, f22 -{C(Rf ａ２６ ) (Rf ａ２７ )}-, f23 -{Si(R ２７ ) (R ２８ )}-, f24 -{Si(Rf ａ２８ ) (Rf ａ２９ )}-, f25 pieces of -M ７ -, f26 -[CH ２ C (M ５ ) {(CH ２ ) ｆ２７ -Si(M ８ ) ｇ２ (R ２９ ) ３－ｇ２}], and f28 -[CH２ C (M ９ ) {(CH ２ ) ｆ２９ -Si(M １１ ) ｇ３ (R ３０ ) ３－ｇ３}] is M １０ -, M ６ The repeating units are arranged in any order so as to form a perfluoropolyether structure at least in part, with - at the end, and as long as -O- is not consecutive with -O-. The fact that the repeating units are arranged in any order and bonded is the same as that explained in the above formula (a2-1), and is not limited to the meaning that the respective repeating units are consecutively arranged in the order described in the above formula (a2-2).

[0124] In the above formula (a2-2), Rf ａ２６ , Rf ａ２７ , Rf ａ２８ , and Rf ａ２９ are all fluorine atoms, and M ７ are all -O-, and M ８ and M １１ are all methoxy groups, ethoxy groups or chlorine atoms (particularly methoxy groups or ethoxy groups), and M ５ , M ６ , M ９ , and M １０ are all hydrogen atoms, f21 is 0, f22 is 30 to 150 (more preferably 80 to 140), f25 is 30 to 60, f23 and f24 are 0, f27 and f29 are 0 to 1 (particularly preferably 0), g2 and g3 are 3, and f26 and f28 are 1 to 10.

[0125] More specifically, the organosilicon compound (A) includes a compound represented by the following formula (a3).

[0126]

[0127] In the above formula (a3), R ３０ is a perfluoroalkyl group having 2 to 6 carbon atoms, and R ３１ and R ３２ are each independently a perfluoroalkylene group having 2 to 6 carbon atoms, and R ３３ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R３４ is an alkyl group having 1 to 3 carbon atoms. ３０ , R ３１ , R ３２ , R ３３ The number of carbon atoms in each of the groups is preferably 2 to 4, and more preferably 2 to 3. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. h1 is preferably 10 to 60, and more preferably 20 to 50, h2 is preferably 1 to 4, and more preferably 1 to 3, and h3 is preferably 1 to 8, and more preferably 1 to 6.

[0128] The organosilicon compound (A) may also include a compound represented by the following formula (a4):

[0129]

[0130] In the above formula (a4), R ４０ is a perfluoroalkyl group having 2 to 5 carbon atoms, and R ４１ is a perfluoroalkylene group having 2 to 5 carbon atoms, and R ４２ is a fluoroalkylene group in which some of the hydrogen atoms of an alkylene group having 2 to 5 carbon atoms are substituted with fluorine, and R ４３ , R ４４ are each independently an alkylene group having 2 to 5 carbon atoms, and R ４５ is a methyl group or an ethyl group. k1, k2, and k3 each independently represent an integer of 1 to 5.

[0131] 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, and is preferably 40,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.

[0132] Examples of the organosilicon compound (A) include a compound represented by the following formula (1) or a compound having a similar structure to this compound, such as Optool (registered trademark) UF503 manufactured by Daikin Industries, Ltd.

[0133]

[0134] Examples of the compound represented by formula (1) above include those synthesized by the methods described in Synthesis Examples 1 and 2 of JP 2014-15609 A, in which r is 43, s is an integer of 1 to 6, and the number average molecular weight is approximately 8000.

[0135] Examples of similar structures include, but are not limited to, structures in which the number of carbon atoms in the hydrocarbon group of the above formula (1) or the number of carbon atoms in the hydrocarbon group substituted with fluorine atoms is different, a structure in which the perfluoropolyether structure and the silicon atom are bonded without a linking group, a structure in which another hydrocarbon group (including a hydrocarbon group in which at least some of the hydrogen atoms are substituted with fluorine atoms) is present at any position in the linking group between the perfluoropolyether structure and the silicon atom, a structure in which the silicon atom and the hydrolyzable group are bonded via a linking group, and structures in which the values ​​of r and s are different.

[0136] As the organosilicon compound (A), a compound represented by formula (a1) is preferred, a compound represented by formula (a2-1) is more preferred, and a compound represented by formula (a3) ​​is even more preferred.

[0137] The organosilicon compound (A) may be used alone or in combination of two or more.

[0138] <Organosilicon Compound (B)> The organosilicon compound (B) is a compound represented by formula (b1). The organosilicon compound (B) represented by the following formula (b1) is, as will be described later, a compound represented by formula (b1) ２ and since the -SiOH group of the organosilicon compound (B) produced by hydrolysis usually undergoes dehydration condensation with the -SiOH group of the organosilicon compound (A) produced by hydrolysis and / or the -SiOH group of the organosilicon compound (B) produced by hydrolysis, in a preferred embodiment, the water-repellent layer (r), which is the cured layer of the mixed composition (ca), has a condensation structure derived from the organosilicon compound (A) as well as a condensation structure derived from the organosilicon compound (B). Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group.

[0139]

[0140] In formula (b1), Rf ｂ１０is a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and R ｂ１１ , R ｂ１２ , R ｂ１３ , R ｂ１４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｂ１１ If there are multiple R ｂ１１ may be different from each other, and R ｂ１２ If there are multiple R ｂ１２ may be different from each other, and R ｂ１３ If there are multiple R ｂ１３ may be different from each other, and R ｂ１４ If there are multiple R ｂ１４ may be different from each other, ｂ１１ , Rf ｂ１２ , Rf ｂ１３ , Rf ｂ１４ are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, and Rf ｂ１１ When there are multiple Rf ｂ１１ may be different from each other, and Rf ｂ１２ When there are multiple Rf ｂ１２ may be different from each other, and Rf ｂ１３ When there are multiple Rf ｂ１３ may be different from each other, and Rf ｂ１４ When there are multiple Rf ｂ１４ may be different from each other, ｂ１５ is an alkyl group having 1 to 20 carbon atoms, and R ｂ１５ If there are multiple R ｂ１５ may be different from each other, １ represents -O-, -C(=O)-O-, -O-C(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms; １ If there are multiple A's, １ may be different from each other, ２is a hydrolyzable group, and A ２ If there are multiple A's, ２ may be different from each other, b11, b12, b13, b14, and b15 each independently represent an integer of 0 to 100, c represents an integer of 1 to 3, and Rf ｂ１０ -, -Si(A ２ ) ｃ (R ｂ１５ ) ３－ｃ , b11 −{C(R ｂ１１ ) (R ｂ１２ )}-, b12 -{C(Rf ｂ１１ ) (Rf ｂ１２ )}-, b13 -{Si(R ｂ１３ ) (R ｂ１４ )}-, b14 -{Si(Rf ｂ１３ ) (Rf ｂ１４ )}-, b15 -A １ - is Rf ｂ１０ -, -Si(A ２ ) ｃ (R ｂ１５ ) ３－ｃ are at the end, and they can be bonded in any order as long as they do not form a perfluoropolyether structure and -O- is not linked to -O- through -F.

[0141] Rf ｂ１０ are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).

[0142] R ｂ１１ , R ｂ１２ , R ｂ１３ , and R ｂ１４ is preferably a hydrogen atom.

[0143] R ｂ１５ is preferably an alkyl group having 1 to 5 carbon atoms.

[0144] A １ is preferably —O—, —C(═O)—O—, or —O—C(═O)—.

[0145] A ２ is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom.

[0146] b11 is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 or 2.

[0147] b12 is preferably 0 to 15, more preferably 0 to 10.

[0148] b13 is preferably 0 to 5, more preferably 0 to 2.

[0149] b14 is preferably 0 to 4, more preferably 0 to 2.

[0150] b15 is preferably 0 to 4, more preferably 0 to 2.

[0151] c is preferably 2 or 3, and more preferably 3.

[0152] The total value of b11, b12, b13, b14, and b15 is preferably 3 or more, preferably 5 or more, and is preferably 80 or less, more preferably 50 or less, and even more preferably 20 or less.

[0153] In particular, Rf ｂ１０ is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and R ｂ１１ , R ｂ１２ are all hydrogen atoms, and A ２ is preferably a methoxy group or an ethoxy group, b11 is 1 to 5, b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.

[0154] In the examples described later, when FAS13E used as compound (B) is represented by the above formula (b1), R ｂ１１ , R ｂ１２ are all hydrogen atoms, b11 is 2, b13, b14, and b15 are all 0, c is 3, A ２ is an ethoxy group, and Rf ｂ１０ -{C(Rf ｂ１１ ) (Rf ｂ１２ ) ｂ１２ - is the end, and C ６ F １３ It is determined to be -.

[0155] Specific examples of the compound represented by the formula (b1) include CF ３ -Si-(OCH ３ ) ３ , C ｊ F ２ｊ＋１ -Si-(OC ２ H ５ ) ３ (j is an integer of 1 to 12), among which C ４ F ９ -Si-(OC ２ H ５ ) ３ , C ６ F １３ -Si-(OC ２ H ５ ) ３ , C ７ F １５ -Si-(OC ２ H ５ ) ３ , C ８ F １７ -Si-(OC ２ H ５ ) ３ is preferable. ３ CH ２ O (CH ２ ) ｋ SiCl ３ , C.F. ３ CH ２ O (CH ２ ) ｋ Si(OCH ３ ) ３ , C.F. ３ CH ２ O (CH ２ ) ｋ Si(OC ２ H ５ ) ３ , C.F. ３ (CH ２ ) ２ Si(CH ３ ) ２ (CH ２ ) ｋ SiCl ３ , C.F. ３ (CH ２ ) ２ Si(CH ３ ) ２ (CH ２ )ｋ Si(OCH ３ ) ３ , C.F. ３ (CH ２ ) ２ Si(CH ３ ) ２ (CH ２ ) ｋ Si(OC ２ H ５ ) ３ , C.F. ３ (CH ２ ) ６ Si(CH ３ ) ２ (CH ２ ) ｋ SiCl ３ , C.F. ３ (CH ２ ) ６ Si(CH ３ ) ２ (CH ２ ) ｋ Si(OCH ３ ) ３ , C.F. ３ (CH ２ ) ６ Si(CH ３ ) ２ (CH ２ ) ｋ Si(OC ２ H ５ ) ３ , C.F. ３ COO (CH ２ ) ｋ SiCl ３ , C.F. ３ COO (CH ２ ) ｋ Si(OCH ３ ) ３ , C.F. ３ COO (CH ２ ) ｋ Si(OC ２ H ５ ) ３ (where k is 5 to 20, preferably 8 to 15). ３ (CF ２ ) ｍ - (CH ２ ) ｎ SiCl ３ , C.F.３ (CF ２ ) ｍ - (CH ２ ) ｎ Si(OCH ３ ) ３ , C.F. ３ (CF ２ ) ｍ - (CH ２ ) ｎ Si(OC ２ H ５ ) ３ (wherein m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4). ３ (CF ２ ) ｐ - (CH ２ ) ｑ -Si-(CH ２ CH=CH ２ ) ３ (wherein p is 2 to 10, preferably 2 to 8, and q is 1 to 5, preferably 2 to 4). ３ (CF ２ ) ｐ - (CH ２ ) ｑ SiCH ３ Cl ２ , C.F. ３ (CF ２ ) ｐ - (CH ２ ) ｑ SiCH ３ (OCH ３ ) ２ , C.F. ３ (CF ２ ) ｐ - (CH ２ ) ｑ SiCH ３ (OC ２ H ５ ) ２ (wherein p is 2 to 10, preferably 3 to 7, and q is 1 to 5, preferably 2 to 4).

[0156] The organosilicon compound (B) is preferably a compound represented by the following formula (b2):

[0157]

[0158] In the above formula (b2), R ６０ is a perfluoroalkyl group having 3 to 8 carbon atoms, and R ６１ is an alkylene group having 1 to 5 carbon atoms, and R ６２ is an alkyl group having 1 to 3 carbon atoms.

[0159] The organosilicon compound (B) may be used alone or in combination of two or more.

[0160] The mixed composition (ca) is a composition in which an organosilicon compound (A) is mixed, preferably a composition in which an organosilicon compound (A) and an organosilicon compound (B) are mixed, and is obtained by mixing the organosilicon compound (A) and, if necessary, the organosilicon compound (B). When components other than the organosilicon compound (A) and the organosilicon compound (B) are mixed, the mixed composition (ca) is obtained by mixing the organosilicon compound (A) and, if necessary, the organosilicon compound (B) and other components. The mixed composition (ca) also includes those in which the reaction has progressed after mixing, for example, during storage.

[0161] <Solvent (D)> The mixed composition (ca) preferably contains a solvent (D). As the solvent (D), it is preferable to use a fluorine-based solvent, for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent, or the like can be used, and it is particularly preferable that the solvent has a boiling point of 100°C or higher. As the fluorinated ether solvent, hydrofluoroethers such as fluoroalkyl (particularly a perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl (particularly a methyl group or an ethyl group) ether are preferred, for example, ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether can be mentioned. As the ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether, for example, Novec (registered trademark) 7200 (manufactured by 3M, molecular weight approximately 264) can be mentioned. As the fluorinated amine solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferred, and a tertiary amine in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group) is preferred, specifically tris(heptafluoropropyl)amine, such as Fluorinert (registered trademark) FC-3283 (manufactured by 3M Corporation, molecular weight approximately 521). Examples of fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane, and fluorinated aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethylbenzene). Examples of 1,1,1,3,3-pentafluorobutane include Solv 55 (manufactured by Solvex).

[0162] In addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC) and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by AGC) can be used as the fluorine-based solvent.

[0163] As the solvent (D), it is preferable to use at least a fluorinated amine solvent. Furthermore, as the solvent (D), it is preferable to use two or more fluorinated solvents, and it is preferable to use a fluorinated amine solvent and a fluorinated hydrocarbon solvent (particularly a fluorinated aliphatic hydrocarbon solvent).

[0164] <Other Components> The mixed composition (ca) may contain various additives, such as a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, an anti-mold agent, an antibacterial agent, an agent for preventing the adhesion of organisms, a deodorizer, a pigment, a flame retardant, and an antistatic agent, as long as the effects of the present disclosure are not impaired.

[0165] The content of the organosilicon compound (A) in the mixed composition (ca) is, for example, 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less, relative to 100% by mass of the entire mixed composition (ca).

[0166] The content of the organosilicon compound (B) in the mixed composition (ca) is, for example, 0.01 mass% or more, preferably 0.03 mass% or more, and preferably 0.3 mass% or less, and more preferably 0.2 mass% or less, relative to 100 mass% of the entire mixed composition (ca).

[0167] The mass ratio of the content of organosilicon compound (B) to the content of organosilicon compound (A) is preferably 0.05 or more, more preferably 0.08 or more, even more preferably 0.10 or more, and is preferably 2.0 or less, more preferably 1.0 or less, even more preferably 0.6 or less.

[0168] The amounts of the organosilicon compounds (A) and (B) can be adjusted during the preparation of the composition, or can be calculated from the results of analysis of the composition.

[0169] [Procedure of Step 2] Step 2 is a step of forming a water-repellent layer (r) on the intermediate layer (c) obtained in Step 1. As described above, the water-repellent layer (r) is a cured layer of the mixed composition (ca). The method of forming the cured layer is not particularly limited, and an example thereof includes a method of applying the mixed composition (ca) on the intermediate layer (c) obtained in Step 1, and then subjecting the applied mixed composition (ca) to a curing treatment.

[0170] The mixed composition (ca) can be prepared, for example, by mixing the respective components. The order and / or timing of mixing the respective components is not particularly limited, and for example, the organosilicon compound (A) and, if necessary, any optional components are sequentially added to a container, and then the mixture is stirred and mixed. Furthermore, when adding the respective components to the container, they may be added all at once, or may be added in portions over several times.

[0171] The stirring may be carried out using a known stirring device, for example, a mechanical stirrer, a magnetic stirrer, a homogenizer, or an ultrasonic disperser.

[0172] Examples of methods for applying the mixed composition (ca) to the intermediate layer (c) include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating.

[0173] The method for applying the mixed composition (ca) is preferably a dip coating method from the viewpoint of productivity. The immersion time in the dip coating method may be appropriately adjusted depending on the mixed composition (ca) and the substrate, but is preferably 1 to 180 seconds, more preferably 5 to 60 seconds. The pull-up speed in the dip coating method may also be appropriately adjusted depending on the mixed composition (ca) and the substrate, but is preferably 1.0 to 10.0 mm / second, more preferably 2.0 to 6.0 mm / second.

[0174] Methods for curing the mixed composition (ca) applied to the intermediate layer (c) include, for example, drying and thermal curing. The curing method may be appropriately selected depending on the composition of the mixed composition (ca). For example, the water-repellent layer (r) can be formed by curing the mixed composition (ca) applied to the intermediate layer (c) by wet heating. The curing temperature is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher. It is also preferably 100°C or lower, more preferably 80°C or lower, and even more preferably 60°C or lower. The curing humidity is preferably 30% RH or higher, more preferably 50% RH or higher, even more preferably 60% RH or higher, and preferably 90% RH or lower, and even more preferably 85% RH or lower. The curing time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 20 minutes or longer. It is also preferably 24 hours or shorter, more preferably 12 hours or shorter, even more preferably 6 hours or shorter, and particularly preferably 1 hour or shorter.

[0175] [Water-repellent layer (r)] The water-repellent layer (r) is a cured layer of the mixed composition (ca) of the organosilicon compound (A). As described above, the water-repellent layer (r) is obtained, for example, by applying and curing the mixed composition (ca), and has a structure derived from the organosilicon compound (A). The organosilicon compound (A) has a hydrolyzable group bonded to a silicon atom (which may be bonded via a linking group), and the -SiOH groups (Si and OH may be bonded via a linking group) of the organosilicon compound (A) generated by hydrolysis undergo dehydration condensation with each other, so the water-repellent layer (r) usually has a condensation structure derived from the organosilicon compound (A).

[0176] The thickness of the water-repellent layer (r) is, for example, 1 to 1000 nm.

[0177] [Step 3] The present production method preferably includes, before step 1, step 3, in which the antireflection layer of the substrate (s) having an antireflection layer is subjected to a hydrophilic treatment. Examples of hydrophilic treatment include corona treatment, plasma treatment, ultraviolet treatment, and ion cleaning treatment, with plasma treatment and ion cleaning treatment being more preferred. By performing a hydrophilic treatment such as plasma treatment, functional groups such as OH groups and COOH groups can be formed on the surface of the antireflection layer. When such functional groups are formed on the surface of the antireflection layer, the adhesion between the intermediate layer (c) and the substrate (s) having the antireflection layer can be particularly improved. Therefore, when step 3 is performed, step 1 is preferably a step of vapor-depositing an organosilicon compound (C) on the surface that has been subjected to the hydrophilic treatment. However, when the laminate is used for an eyeglass lens, it is preferable to vapor-deposit the organosilicon compound (C) without subjecting the antireflection layer of the substrate (s) to a hydrophilic treatment. Therefore, the hydrophilic treatment is preferably performed when the laminate is used for purposes other than eyeglass lenses.

[0178] [Manufacturing of Spectacle Lenses] The present manufacturing method is suitable for use in the manufacturing process of spectacle lenses. The present manufacturing method may be carried out in combination with or after other processes carried out on the laminate for manufacturing spectacle lenses. Examples of other processes include a edging process, a dyeing process, a shaping process, and an inspection process for the laminate. The laminate may be used as is as a spectacle lens.

[0179] [Laminate] The laminate produced by the present production method will be described. [Configuration of Laminate] The laminate comprises a substrate (s) having an anti-reflection layer, an intermediate layer (c) formed on the anti-reflection layer by vapor deposition, and a water-repellent layer (r) formed on the intermediate layer. The laminate may also include other components as long as they do not impair the effects of the present disclosure. Examples of other components include a primer layer, a hard coat layer, a protective film, and a hydrophobic resin film.

[0180] [Physical Properties of Laminate] After the abrasion resistance test described below is performed on the surface of the water-repellent layer (r) side of the laminate, the water contact angle and water sliding angle measured on the surface subjected to the abrasion resistance test preferably satisfy at least one of the following requirements (1) and (2), and more preferably satisfy both requirements (1) and (2): (1) The water contact angle is 110° or more. (2) The water sliding angle is 10° or less. The contact angle is also preferably 115° or more, and may be 130° or less. The sliding angle may be 0.5° or more.

[0181] The abrasion resistance test involves rubbing the surface of the water-repellent layer (r) of the laminate 20,000 times with a load of 200 g per 1.5 cm x 1.5 cm area. The rubbing is preferably performed with pulp paper, more preferably with pulp paper attached to an elastic body. Kimwipe S-200 manufactured by Nippon Paper Crecia Co., Ltd. is preferably used as the pulp paper. For example, Kimwipe S-200 is preferably used with the abrasion resistance test, with a stroke distance of 30 mm and a rubbing speed of 70 to 90 strokes per minute, and the contact angle and sliding angle are measured approximately at the center of the stroke area. When applying the load, it is sufficient to apply a pressure equivalent to a load of 200 g per 1.5 cm x 1.5 cm area. Laminates having a water-repellent layer (r) measuring less than 1.5 cm x 1.5 cm are also included within the scope of the present disclosure.

[0182] [Uses of Laminate] The laminate can be used in a variety of applications. When a spectacle lens substrate is used as the substrate, it can be suitably used as a spectacle lens. The laminate can also be preferably used as a front panel in a flexible display device, which is sometimes referred to as a window film. The flexible display device preferably comprises a laminate for a flexible display device and an organic EL display panel, with the laminate for a flexible display device being disposed on the viewing side of the organic EL display panel and configured to be foldable. The laminate for a flexible display device may further contain a polarizing plate (preferably a circular polarizing plate), a touch sensor, etc., and while these may be stacked in any order, they are preferably stacked in the order of window film (i.e., the laminate obtained by the present manufacturing method), polarizing plate, and touch sensor from the viewing side, or in the order of window film, touch sensor, and polarizing plate. The presence of a polarizing plate on the viewing side of the touch sensor is preferable because it reduces the visibility of the touch sensor pattern and improves the visibility of the displayed image. Each component can be stacked using an adhesive, pressure-sensitive adhesive, etc. The flexible display device may also include a light-shielding pattern formed on at least one surface of any one of the window film, the polarizing plate, and the touch sensor.

[0183] The present disclosure will be described in more detail below with reference to examples. The present disclosure is not limited to the following examples, and can of course be implemented with appropriate modifications within the scope of the invention, all of which are within the technical scope of the present disclosure.

[0184] Examples 1 to 4 and Comparative Examples 1 and 2 Preparation of Laminate Preparation of Substrate (s) Having Antireflection Layer A coating liquid was applied by immersion 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 coat (primer layer) having a thickness of approximately 1 μm and a silicone-based scratch resistance improving hard coat (hard coat layer) having a thickness of approximately 2 μm. Next, a multilayer antireflection coat (corresponding to the antireflection layer (ar); a layer formed by alternating silica layers and zirconia layers) having a thickness of approximately 0.4 μm made of inorganic oxides (silica and zirconia) was formed by vacuum deposition on the hard coat layer to obtain a substrate (s) having an antireflection layer.

[0185] <Step 1> As the organosilicon compound (C), a reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.), which is described in JP-A 2012-197330 and is represented by the following formula, was used.

[0186]

[0187] Using a vacuum deposition device (manufactured by Satisloh, model number 1200-DLX-2), the output of the electron beam was set so that the average deposition rate was the value shown in Table 1, and the vacuum was 1.0 × 10 －２ An organosilicon compound (C) was vapor-deposited onto the antireflection layer of a substrate (s) having an antireflection layer at 1000 Pa to form an intermediate layer (c) having a thickness of 15 to 35 nm. The average vapor deposition rate was calculated by dividing the thickness of the vapor-deposited film by the vapor deposition time required to form a vapor-deposited film of the above thickness (average vapor deposition rate (nm / s) = film thickness (nm) / vapor deposition time (s)). The above film thickness was measured using a quartz crystal film thickness meter calibrated to indicate the film thickness on the substrate.

[0188] <Step 2> OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd. was used as the organosilicon compound (A), and FAS13E(C) was used as the organosilicon compound (B). ６ F １３ -C ２ H ４ -Si(OC ２ H５ ) ３ , manufactured by Tokyo Chemical Industry Co., Ltd.), and FC-3283 (C) as solvent (D). ９ F ２１ A solution was prepared by mixing organosilicon compound (A) and Fluorinert (manufactured by 3M Co.), and the mixture was stirred at room temperature for a predetermined time to obtain a mixed composition (ca). In the mixed composition (ca), the proportion of the organosilicon compound (A) was 0.425% by mass, and the proportion of the organosilicon compound (B) was 0.05% by mass, when the entire mixed composition (ca) was taken as 100% by mass. The mixed composition (ca) was applied onto the intermediate layer (c) formed in step 1 above 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 / sec. Thereafter, wet heat curing was performed at 50°C and 80% RH for 30 minutes to form a water-repellent layer (r), which is a cured layer of the mixed composition (ca).

[0189] [Evaluation] The laminates obtained in the examples and comparative examples were evaluated by the following methods.

[0190] On the water-repellent layer (r) of the laminate, 16 sheets of Kimwipe Wiper S-200 manufactured by Nippon Paper Crecia Co., Ltd. were attached to a 15 mm square elastic body (plastic eraser model number 1156SMTR00 manufactured by Maped (France)), and a 200 g load was applied, 30 mm stroke, 90 r / min (90 back and forth per minute) 20,000 times rubbing abrasion resistance test was performed. Then, at the approximate center of the abrasion site, the water contact angle and water sliding angle after the abrasion resistance test were measured by the following method. A 1 μL water droplet was dropped on the water-repellent layer (r) of the obtained laminate, and a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM-500 / DM-SA) was used to measure the water contact angle by the sessile drop method (analysis method: ellipse fitting method). A 20 μL drop of water was dropped onto the water-repellent layer (r) of the obtained laminate, and the sliding angle of the water was measured using a contact angle measuring device (DM-500 / DM-SA, manufactured by Kyowa Interface Science Co., Ltd.) by the sliding method (analysis method: perfect circle fitting method, tilt method: continuous tilt, sliding detection: before sliding, movement judgment: forward and backward, sliding judgment distance: 10 dots).

[0191] For each of the laminates prepared under the conditions described in Examples 1 to 4 and Comparative Examples 1 and 2, the water contact angle and water sliding angle were measured after the abrasion resistance test. After the abrasion resistance test, samples that satisfied both of the following requirements (1) and (2) were judged to be good products with excellent abrasion resistance, and samples that did not satisfy at least one of the requirements were judged to be defective. (1) The water sliding angle after the abrasion resistance test was 10° or less. (2) The water contact angle after the abrasion resistance test was 110° or more.

[0192] The rate of non-defective products among the three samples evaluated was taken as the rate of non-defective products and calculated (rate of non-defective products (%) = number of non-defective samples / number of measured samples × 100). A higher rate of non-defective products indicates higher abrasion resistance and higher productivity of the laminate.

[0193] [Results] The results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1.

[0194]

[0195] As shown in Table 1, it was confirmed that the method for producing a laminate according to the present disclosure can produce a laminate having excellent abrasion resistance with good productivity.

Claims

1. A step 1 of forming an intermediate layer (c) on an antireflection layer of a substrate (s) having an antireflection layer by vapor deposition; and step 2 of forming a water-repellent layer (r) on the intermediate layer (c), the intermediate layer (c) is a vapor-deposited layer of an organosilicon compound (C) having a silicon atom and an amino group and / or an amine skeleton, the water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) in which a monovalent group having a perfluoropolyether structure is bonded to a silicon atom via or without a linking group, and a hydrolyzable group is bonded to the silicon atom via or without a linking group, The method for producing a laminate, wherein an average deposition rate during formation of the intermediate layer (c) is 0.2 nm / s or more and less than 1.2 nm / s.

2. The method for producing a laminate according to claim 1 , wherein the organosilicon compound (A) is at least one organosilicon compound represented by the following formula (a1): 【Chemistry 1】 In the above formula (a1), Rf ａ１ is a divalent perfluoropolyether structure having oxygen atoms at both ends, R １１ , R １２ , and R １３ are each independently an alkyl group having 1 to 20 carbon atoms; R １１ If there are multiple R １１ may be different from each other, R １２ If there are multiple R １２ may be different from each other, R １３ If there are multiple R １３ may be different, E １ , E ２ , E ３ , E ４ , and E ５ are each independently a hydrogen atom or a fluorine atom; E １ If there are multiple E １ may be different from each other, E ２ If there are multiple E ２ may be different from each other, E ３ If there are multiple E ３ may be different from each other, E ４ If there are multiple E ４ may be different, G １ and G ２ each independently represents a di- to decavalent organosiloxane group having a siloxane bond, J １ , J ２ , and J ３ each independently represents a hydrolyzable group or -(CH ２ ) ｅ６ -Si(OR １４ ) ３ e6 is 1 to 5; R １４ is a methyl group or an ethyl group, J １ If there are multiple J １ may be different from each other, ２ If there are multiple J ２ may be different from each other, ３ If there are multiple J ３ may be different, L １ and L ２ each independently represents a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, or a fluorine atom; L １ If there are multiple L １ may be different from each other, L ２ If there are multiple L ２ may be different, d11 is 1 to 9, d12 is 0 to 9, a10 and a14 each independently represent 0 to 10; a11 and a15 each independently represent 0 or 1; a12 and a16 each independently represent 0 to 9; a13 is 0 or 1; a21, a22, and a23 each independently represent 0 to 2; e1, e2, and e3 each independently represent 1 to 3.

3. The method for producing a laminate according to claim 1 or 2, wherein the mixed composition (ca) further contains at least one organosilicon compound (B) represented by the following formula (b1): 【Chemistry 2】 In the above formula (b1), Rf ｂ１０ is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, or a fluorine atom, R ｂ１１ , R ｂ１２ , R ｂ１３ and R ｂ１４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ｂ１１ If there are multiple R ｂ１１ may be different from each other, R ｂ１２ If there are multiple R ｂ１２ may be different from each other, R ｂ１３ If there are multiple R ｂ１３ may be different from each other, R ｂ１４ If there are multiple R ｂ１４ may be different, Rf ｂ１１ , Rf ｂ１２ , Rf ｂ１３ and Rf ｂ１４ are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, or a fluorine atom; Rf ｂ１１ When there are multiple Rf ｂ１１ may be different from each other, Rf ｂ１２ When there are multiple Rf ｂ１２ may be different from each other, Rf ｂ１３ When there are multiple Rf ｂ１３ may be different from each other, Rf ｂ１４ When there are multiple Rf ｂ１４ may be different, R ｂ１５ is an alkyl group having 1 to 20 carbon atoms, R ｂ１５ If there are multiple R ｂ１５ may be different, A １ is -O-, -C(=O)-O-, -O-C(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms; A １ If there are multiple A's, １ may be different, A ２ is a hydrolyzable group, A ２ If there are multiple A's, ２ may be different, b11, b12, b13, b14, and b15 each independently represent an integer of 0 to 100; c is an integer from 1 to 3; Rf ｂ１０ -, -Si(A ２ ) ｃ (R ｂ１５ ) ３－ｃ , b11 −{C(R ｂ１１ ) (R ｂ１２ )}-, b12 -{C(Rf ｂ１１ ) (Rf ｂ１２ )}-, b13 -{Si(R ｂ１３ ) (R ｂ１４ )}-, b14 -{Si(Rf ｂ１３ ) (Rf ｂ１４ ) ) -, b15 -A １ - is Rf ｂ１０ -, -Si(A ２ ) ｃ (R ｂ１５ ) ３－ｃ is the terminal end, and they can be bonded in any order as long as a perfluoropolyether structure is not formed and -O- is not linked to -O- through -F.

4. 4. The method for producing a laminate according to claim 3, wherein a mass ratio of said organosilicon compound (B) to said organosilicon compound (A) in said mixed composition (ca) is 0.05 to 2.

0.

5. 3. The method for producing a laminate according to claim 1, wherein at least one silicon atom in the organosilicon compound (C) has a hydrolyzable group or a hydroxyl group bonded thereto.

6. The method for producing a laminate according to claim 1 or 2, wherein the organosilicon compound (C) is an organosilicon compound represented by the following formula (c2): 【Chemistry 3】 In the above formula (c2), R ｘ２０ and R ｘ２１ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ｘ２０ If there are multiple R ｘ２０ may be different from each other, R ｘ２１ If there are multiple R ｘ２１ may be different, Rf ｘ２０ and Rf ｘ２１ are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, or a fluorine atom; Rf ｘ２０ When there are multiple Rf ｘ２０ may be different from each other, Rf ｘ２１ When there are multiple Rf ｘ２１ may be different, R ｘ２２ and R ｘ２３ are each independently an alkyl group having 1 to 20 carbon atoms; R ｘ２２ and R ｘ２３ If there are multiple R ｘ２２ and R ｘ２３ may be different, X ２０ and X ２１ are each independently a hydrolyzable group; ２０ and X ２１ If there are multiple Xs, ２０ and X ２１ may be different, p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units p20 or p21 enclosed in parentheses has an amine skeleton -NR １００ -, and R in the amine skeleton is １００ is a hydrogen atom or an alkyl group, p22 and p23 each independently represent an integer of 1 to 3; p20 pieces of -{C(R ｘ２０ ) (R ｘ２１ )}-, p21 -{C(Rf ｘ２０ ) (Rf ｘ２１ ))- does not have to be consecutive, and the p20 or p21 are bonded in any order, and both ends are -Si(X ２０ ) ｐ２２ (R ｘ２２ ) ３－ｐ２２ and -Si(X ２１ ) ｐ２３ (R ｘ２３ ) ３－ｐ２３ It becomes.

7. The method for producing a laminate according to claim 1 or 2, wherein the organosilicon compound (A) is an organosilicon compound represented by the following formula (a3), and the organosilicon compound (C) is an organosilicon compound represented by the following formula (c2-2): 【Chemistry 4】 In the above formula (a3), R ３０ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ３１ and R ３２ are each independently a perfluoroalkylene group having 2 to 6 carbon atoms; R ３３ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ３４ is an alkyl group having 1 to 3 carbon atoms. 【Chemistry 5】 In the above formula (c2-2), X ２２ and X ２３ are each independently a hydrolyzable group; X ２２ and X ２３ If there are multiple Xs, ２２ and X ２３ may be different from each other, R ｘ２４ and R ｘ２５ are each independently an alkyl group having 1 to 20 carbon atoms; R ｘ２４ and R ｘ２５ If there are multiple R ｘ２４ and R ｘ２５ may be different from each other, -C ｗ H ２ｗ At least one of the methylene groups is an amine skeleton -NR １００ - is replaced by R １００ represents a hydrogen atom or an alkyl group; w represents an integer of 1 to 30 (excluding the number of methylene groups substituted for the amine skeleton); p24 and p25 each independently represent an integer of 1 to 3.

8. 3. The method for producing a laminate according to claim 1 or 2, wherein after an abrasion resistance test in which the surface of the laminate on the water-repellent layer (r) side is rubbed 20,000 times with a load of 200 g per area of ​​1.5 cm × 1.5 cm, the properties measured on the surface of the laminate on the water-repellent layer (r) side satisfy at least one of the following requirements (1) and (2): (1) The water sliding angle is 10° or less. (2) The contact angle of water is 110° or more.

9. The method for producing a laminate according to claim 1 or 2, wherein the substrate (s) having an antireflection layer is a substrate having an antireflection layer formed on a glass layer or a resin layer.

10. The method for producing a laminate according to claim 1 or 2, wherein the step 2 is a step of forming the water-repellent layer (r) by applying the mixed composition (ca) onto the intermediate layer (c) and curing the mixture composition (ca).

11. The method includes a step 3, prior to the step 1, of subjecting the antireflection layer of the substrate (s) having the antireflection layer to a hydrophilization treatment, 3. The method for producing a laminate according to claim 1, wherein the step 1 is a step of forming the intermediate layer (c) by vapor deposition on the hydrophilized surface of the antireflection layer.

12. A method for producing a spectacle lens, comprising the method for producing the laminate according to claim 1 or 2.

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