Method for manufacturing laminate and method for manufacturing ophthalmic 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 ophthalmic lens. This method for producing a laminate comprises: a step 1 in which an intermediate layer (c) is formed by vapor deposition on an anti-reflection layer of a substrate (s) having an anti-reflection layer; and a step 2 for forming a water-repellent layer (r) on the intermediate layer (c), the intermediate layer (c) being 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 a linking group or not via a linking group, and a hydrolyzable group is bonded to the silicon atom via a linking group or not via a linking group. The average vapor deposition rate when the intermediate layer (c) is formed is 0.2 nm / s or more and less than 1.2 nm / s.

Description

Technical Field

[0001] The present invention relates to a method for producing a laminate and a method for producing a spectacle lens. Background Art

[0002] Patent Document 1 discloses a hard coating film in which a hard coating layer (X), a primer layer (Y) and a surface layer (Z) are sequentially stacked on at least one surface of a substrate, wherein the surface layer (Z) has a water contact angle of 110° or more. It is also described that: in order to form the surface layer (Z), a fluorine compound having a polyperfluoropolyether chain is preferably used, and in order to form the primer layer (Y), a silane compound such as 3-acryloxypropyltrimethoxysilane is preferably used.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2015-120253 Summary of the invention

[0006] The present invention relates to a method for producing a laminate, comprising: 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 a step 2 of forming a water-repellent layer (r) on the intermediate layer (c), wherein the intermediate layer (c) is a vapor-deposited layer of an organosilicon compound (C) having silicon atoms and having an amino group and / or an amine skeleton, and the water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) having a monovalent group having a perfluoropolyether structure bonded to a silicon atom via a linking group or not, and a hydrolyzable group bonded to the silicon atom via a linking group or not, and an 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. DETAILED DESCRIPTION

[0007] Hereinafter, the method for producing the laminated body of the present invention will be described in detail.

[0008] In order to maintain water repellency, a laminate preferably exhibits excellent wear resistance, and a method for producing a laminate exhibiting such properties with good productivity is required. The method for producing a laminate of the present invention can produce a laminate having excellent wear resistance with good productivity.

[0009] It should be noted that, in the present invention, "can be manufactured with good productivity" means that when two or more laminates are manufactured, the difference in wear resistance between the laminates is small. In other words, it can be said that laminates showing certain characteristics can be stably manufactured, that is, the productivity is excellent.

[0010] Although the description of the constituent elements described below may be based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0011] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0012] Hereinafter, each step of the production method of the present invention (hereinafter also referred to as the present production method) will be described first, and then a laminated body produced by the present production method (hereinafter also referred to as the laminated body) will be described.

[0013] [Process 1]

[0014] The production method comprises step 1 of forming a vapor-deposited layer of an organosilicon compound (C), i.e., an intermediate layer (c), on an antireflection layer of a substrate (s) having an antireflection layer by vapor deposition. 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.

[0015] The materials, members, and steps used in this process are described below.

[0016] [Substrate(s) with anti-reflection layer]

[0017] The material of the part other than the anti-reflection layer (ar) of the substrate (s) having an anti-reflection layer is not particularly limited, and may be any of organic materials and inorganic materials, as long as the anti-reflection layer (ar) is provided on at least one side. As organic materials, thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, ethylene resins (polyethylene, polyvinyl chloride, polystyrene, vinylbenzyl chloride resins, polyvinyl alcohol, etc.) and the like; thermosetting resins such as phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins and the like. As inorganic materials, metals such as iron, silicon, copper, zinc, aluminum, or alloys containing these metals, ceramics, glass and the like may be cited.

[0018] The laminate can be applied to, for example, eyeglass lenses. In this case, the substrate (s) having an anti-reflection layer is preferably a substrate having an anti-reflection layer (ar) formed on a glass layer (sg) or a resin layer (sp). The anti-reflection layer (ar) is preferably formed at least on the side of the intermediate layer (c). As materials contained in the resin layer (sp), allyl diethylene glycol carbonate resin, polycarbonate resin, thiocarbamate resin, episulfide resin, etc. can be listed. A primer layer and / or a hard coating layer can be formed between the glass layer (sg) or the resin layer (sp) and the anti-reflection layer (ar).

[0019] The primer layer is a layer that improves the adhesion between two layers laminated via the primer layer, and a known material can be used.

[0020] The hard coating layer is a layer that imparts scratch resistance to the glass layer (sp) or the resin layer (sg), and shows a hardness of H or higher with a pencil hardness meter obtained by the test method specified in JIS K5600. As the hard coating layer, a known hard coating layer can be used, for example, an organic hard coating layer, an inorganic hard coating layer, and an organic-inorganic hybrid hard coating layer can be listed.

[0021] The primer layer and the hard coat layer can be formed, for example, by applying a precursor composition to a substrate and curing the resulting composition. The method for forming the water-repellent layer (r) described below can be used.

[0022] The antireflection layer (ar) is a layer having a function of preventing reflection of incident light, and specifically, is preferably a layer showing a reflection characteristic of reducing the reflectance to about 5.0% or less in the visible light region of 530 nm.

[0023] The structure of the anti-reflection layer (ar) is not particularly limited, and can be a single-layer structure or a multilayer structure. In the case of a multilayer structure, it is preferred that a low refractive index layer and a high refractive index layer are alternately stacked. As the material constituting the high refractive index layer, oxides of titanium, zirconium, aluminum, tantalum and lanthanum can be cited, and as the material constituting the low refractive index layer, silicon dioxide can be cited. As the anti-reflection layer (ar) of a multilayer structure, it is preferred that SiO2 and ZrO2 are alternately stacked and the outermost layer on the side opposite to the glass layer (sg) or the resin layer (sp) is a structure of SiO2. The anti-reflection layer (ar) can be formed, for example, by a vapor deposition method.

[0024] The thickness of the substrate (s) is, for example, 0.9 to 10 mm. When the thickness of the substrate (s) is non-uniform, the thickness at the center of gravity of the substrate (s) may be within the above range.

[0025] [Organic silicon compound (C)]

[0026] The organosilicon compound (C) is an organosilicon compound having a silicon atom and having an amino group and / or an amine skeleton.

[0027] It is preferred that a hydroxyl group or a hydrolyzable group is bonded to the silicon atom of the organosilicon compound (C).

[0028] 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, and the like. An alkoxy group is preferred, and an alkoxy group having 1 to 4 carbon atoms is more preferred.

[0029] 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).

[0030] <Organic silicon compound (C1)>

[0031]

[0032] In the above formula (c1),

[0033] R x11 , R x12 , R x13 , R x14 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R x11 When two or more R x11 Can be different, there are two or more R x12 When two or more R x12 Can be different, there are two or more R x13 When two or more R x13 Can be different, there are two or more R x14 When two or more R x14 Can be different,

[0034] R x11 , Rf x12 , Rf x13 , Rf x14 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf x11 When two or more Rf x11 Can be different, there are two or more Rf x12 When two or more Rf x12 Can be different, there are two or more Rf x13 When two or more Rf x13 Can be different, there are two or more Rf x14 When two or more Rf x14 Can be different,

[0035] R x15 is an alkyl group having 1 to 20 carbon atoms, and there are two or more R x15 When two or more R x15 Can be different,

[0036] X 11 is a hydrolyzable group, and there are two or more X 11 When two or more X 11Can be different,

[0037] Y 11 is -NH- or -S-, and there are two or more Y 11 When two or more Y 11 Can be different,

[0038] Z 11 is 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 urea group or a mercapto group,

[0039] p1 is an integer of 1 to 20, p2, p3, and p4 are each independently an integer of 0 to 10, and p5 is an integer of 1 to 10,

[0040] p6 is an integer from 1 to 3,

[0041] Z 11 When it is not an amino group, Y 11 At least one of them is -NH-, Y 11 When all are -S-, Z 11 For amino,

[0042] 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 -As long as Z 11 - and -Si(X 11 ) p6 (R x15 ) 3-p6 If -O- is a terminal and -O- is not linked to -O-, the bonds can be arranged in an arbitrary order.

[0043] R x11 , R x12 , R x13 and R x14 Preferred is a hydrogen atom.

[0044] R x11 , Rf x12 , Rf x13 and Rf x14Preferably, each independently is an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom.

[0045] R x15 An alkyl group having 1 to 5 carbon atoms is preferred.

[0046] X 11 An alkoxy group, a halogen atom, a cyano group or an isocyanate group is preferred, an alkoxy group is more preferred, and a methoxy group or an ethoxy group is further preferred.

[0047] Y 11 Preferred is -NH-.

[0048] Z 11 It 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 still more preferably an amino group.

[0049] p1 is preferably 1 to 15, more preferably 2 to 10. p2, p3 and p4 are preferably each independently 0 to 5, more preferably all 0 to 2. p5 is preferably 1 to 5, more preferably 1 to 3. p6 is preferably 2 to 3, more preferably 3.

[0050] As the organosilicon compound (C1), the following compounds are preferably used: In the above formula (c1), R x11 and R x12 are all hydrogen atoms, Y 11 -NH-, X 11 is alkoxy (especially methoxy or ethoxy), Z 11 is an amino group or a thiol group, p1 is 1 to 10, p2, p3 and p4 are all 0, p5 is 1 to 5 (especially 1 to 3), and p6 is 3.

[0051] The organosilicon compound (C1) is preferably a compound represented by the following formula (c1-2).

[0052]

[0053] In the above formula (c1-2),

[0054] X 12 is a hydrolyzable group, and there are two or more X 12 When two or more X 12 Can be different,

[0055] Y 12 For -NH-,

[0056] Z 12 is an amino group or a thiol group,

[0057] R x16 is an alkyl group having 1 to 20 carbon atoms, and there are two or more Rx16 When two or more R x16 Can be different,

[0058] p is an integer of 1-3, q is an integer of 2-5, and r is an integer of 0-5.

[0059] X 12 An alkoxy group, a halogen atom, a cyano group or an isocyanate group is preferred, and an alkoxy group is more preferred.

[0060] Z 12 An amino group is preferred.

[0061] R x16 An alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0062] p is preferably an integer of 2 to 3, and more preferably 3.

[0063] q is preferably an integer of 2-3, and r is preferably an integer of 2-4.

[0064] <Organic silicon compound (C2)>

[0065]

[0066] In the above formula (c2),

[0067] R x20 and R x21 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R x20 When two or more R x20 Can be different, there are two or more R x21 When two or more R x21 Can be different,

[0068] R x20 and Rf x21 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf x20 When two or more Rf x20 Can be different, there are two or more Rf x21 When two or more Rf x21 Can be different,

[0069] R x22 and R x23 Each independently represents an alkyl group having 1 to 20 carbon atoms, and there are two or more R x22 and R x23 When two or more R x22 and R x23 Can be different,

[0070] X 20 and X 21 Each independently is a hydrolyzable group, and there are two or more X 20 and X 21 When two or more X 20 and X 21 Can be different,

[0071] p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units indicated by p20 or p21 and enclosed in parentheses is replaced by an amine skeleton -NR 100 -, R in the above amine skeleton 100 is a hydrogen atom or an alkyl group,

[0072] p22 and p23 are each independently an integer of 1 to 3,

[0073] p20-{C(R x20 )(R x21 )}-、p21-{C(Rf x20 )(Rf x21 )}-bond in any order without the need for p20 or p21 to be consecutive, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 .

[0074] R x20 and R x21 Preferred is a hydrogen atom.

[0075] R x20 and Rf x21 Preferably, each independently is an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom.

[0076] R x22 and R x23 An alkyl group having 1 to 5 carbon atoms is preferred.

[0077] X 20 and X 21 An alkoxy group, a halogen atom, a cyano group or an isocyanate group is preferred, an alkoxy group is more preferred, and a methoxy group or an ethoxy group is further preferred.

[0078] As mentioned above, the amine backbone -NR 100-As long as at least one is present in the molecule, any one of the repeating units marked with p20 or p21 and enclosed in parentheses is replaced with the above-mentioned amine skeleton, but it is preferably a part of the repeating unit marked with p20 and enclosed in parentheses. The above-mentioned amine skeletons may exist in two or more, and the number of amine skeletons in this case is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 to 5. In addition, in this case, it is preferred to have an alkylene group between adjacent amine skeletons, and the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5. The number of carbon atoms of the alkylene group between adjacent amine skeletons is included in the total number of p20 or p21.

[0079] Amine skeleton-NR 100 -Middle, R 100 When it is an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less. Amine skeleton -NR 100 - preferably -NH-(R 100 is a hydrogen atom).

[0080] The number of p20, excluding the number of repeating units substituted with an amine skeleton, is preferably 1 to 15, more preferably 1 to 10.

[0081] Regarding p21, excluding the number of repeating units substituted with an amine skeleton, it is preferably 0 to 5, and more preferably 0 to 2.

[0082] p22 and p23 are preferably 2 to 3, and more preferably 3.

[0083] As the organosilicon compound (C2), the following compounds are preferably used: In the above formula (c2), R x20 and R x21 are all hydrogen atoms, X 20 and X 21 is an alkoxy group (particularly a methoxy group or an ethoxy group), and at least one of the repeating units enclosed in parentheses and labeled p20 is replaced by an amine skeleton -NR 100 -, R 100 is a hydrogen atom, p20 is 1 to 10 (excluding the number of repeating units replaced by an amine skeleton), p21 is 0, and p22 and p23 are 3.

[0084] The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

[0085]

[0086] In the above formula (c2-2),

[0087] X 22 and X 23 Each independently is a hydrolyzable group, and there are two or more X22 and X 23 When two or more X 22 and X 23 Can be different,

[0088] R x24 and R x25 Each independently represents an alkyl group having 1 to 20 carbon atoms, and there are two or more R x24 and R x25 When two or more R x24 and R x25 Can be different,

[0089] For -C w H 2w -, at least one of the methylene groups in a part of which is replaced by an amine skeleton -NR 100 -, R 100 is a hydrogen atom or an alkyl group,

[0090] w is an integer of 1 to 30 (excluding the number of methylene groups replaced by the amine skeleton),

[0091] p24 and p25 are each independently an integer of 1-3.

[0092] X 22 and X 23 An alkoxy group, a halogen atom, a cyano group or an isocyanate group is preferred, an alkoxy group is more preferred, and an alkoxy group having 1 to 4 carbon atoms (particularly a methoxy group or an ethoxy group) is further preferred.

[0093] Amine skeleton-NR 100 - There may be two or more amine skeletons, and the number of amine skeletons in this case is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 to 5. In addition, in this case, it is preferred to have an alkylene group between adjacent amine skeletons. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5. The number of carbon atoms of the alkylene group between adjacent amine skeletons is included in the total number of w.

[0094] Amine skeleton-NR 100 -Middle, R 100 When it is an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less. Amine skeleton -NR 100 - preferably -NH-(R 100 is a hydrogen atom).

[0095] R x24 and R x25 An alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0096] p24 and p25 are preferably integers of 2 to 3, and more preferably 3.

[0097] w is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.

[0098] <Organic silicon compound (C3)>

[0099]

[0100] In the above formula (c3),

[0101] Z 31 , Z 32 Each independently represents a reactive functional group other than a hydrolyzable group and a hydroxyl 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 urea group, and a mercapto group. 31 , Z 32 , preferably an amino group, a mercapto group or a methacryloyl group, and particularly preferably an amino group.

[0102] R x31 , R x32 , R x33 , R x34 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R x31 When two or more R x31 Can be different, there are two or more R x32 When two or more R x32 Can be different, there are two or more R x33 When two or more R x33 Can be different, there are two or more R x34 When two or more R x34 Can be different. x31 , R x32 , R x33 , R x34 It is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom.

[0103] R x31 , Rf x32 , Rf x33 , Rf x34 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf x31 When two or more Rf x31 Can be different, there are two or more Rf x32 When two or more Rf x32 Can be different, there are two or more Rf x33 When two or more Rfx33 Can be different, there are two or more Rf x34 When two or more Rf x34 Can be different. x31 , Rf x32 , Rf x33 , Rf x34 Preferably, it is an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom.

[0104] Y 31 is -NH-, -N(CH3)- or -O-, and there are two or more Y 31 When two or more Y 31 Can be different. 31 Preferred is -NH-.

[0105] X 31 , X 32 , X 33 , X 34 Each independently is -OR c (R c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino group C 1-3 Alkyl di-C 1-3 Alkoxysilyl), there are two or more X 31 When two or more X 31 Can be different, there are two or more X 32 When two or more X 32 Can be different, there are two or more X 33 When two or more X 33 Can be different, there are two or more X 34 When two or more X 34 Can be different. 31 , X 32 , X 33 , X 34 Preferably R c -OR is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms c , more preferably R c A hydrogen atom.

[0106] 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 of them 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.

[0107] The organosilicon compound (C3) only needs to satisfy Z 31 and Z 32 At least one of them is amino or Y 31 At least one of them is -NH- or -N(CH3)-, and the terminal is Z 31 - and Z 32 -, -O- is not connected to -O-, then 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 and bonded in any order. p31-{C(R x31 )(R x32 )}-Not required-{C(R x31 )(R x32 )}- are continuously bonded, and may be bonded via other units in the middle, as long as the total number is p31. The same applies to the units bracketed by p32 to p37.

[0108] As the organosilicon compound (C3), the following compounds are preferred: In the above formula (c3), Z 31 and Z 32 is amino, R x31 and R x32 is a hydrogen atom, p31 is 3 to 13 (preferably 5 to 10), R x33 and R x34 All are hydrogen atoms, Rf x31 ~Rf x34 are all alkyl groups with 1 to 10 carbon atoms or fluorine atoms in which one or more hydrogen atoms are replaced by fluorine atoms, p32 to p34 are all 0 to 5, Y 31 is -NH-, p35 is 0 to 5 (preferably 0 to 3), X 31 ~X 34 All are -OH, p36 is 1 to 5 (preferably 1 to 3), and p37 is 1.

[0109] The organosilicon compound (C3) is preferably a compound represented by the following formula (c3-2).

[0110]

[0111] In the above formula (c3-2),

[0112] Z 31 , Z 32 , X 31 , X 32 , X 33 , X 34 , Y 31 and Z in formula (c3) 31 , Z 32 , X 31 , X 32 , X 33 , X 34 , Y 31 have the same meaning; p41 to p44 are each independently an integer of 1 to 6; and p45 and 46 are each independently 0 or 1.

[0113] In formula (c3-2), Z 31 and Z 32 It is preferably an amino group, a mercapto group or a methacryloyl group, and is particularly preferably an amino group. 31 , X 32 , X 33 , X 34 Preferably R c -OR is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms c , more preferably R c Y is a hydrogen atom. 31 It is preferably -NH-. p41 to p44 are preferably 2 or more, and preferably 5 or less, and more preferably 4 or less. p45 and p46 are both preferably 0.

[0114] The organosilicon compound (C) is preferably at least one selected from the group consisting of organosilicon compounds (C1) and organosilicon compounds (C2), more preferably the organosilicon compound (C2), and further preferably the compound represented by formula (c2-2).

[0115] As the organosilicon compound (C), only one kind may be used, or two or more kinds may be used.

[0116] [Steps of process 1]

[0117] Step 1 is a step of forming an intermediate layer (c) on the antireflection layer of the substrate (s) having the antireflection layer by vapor deposition. The intermediate layer (c) is a vapor-deposited layer of an organosilicon compound (C) having silicon atoms and having an amino group and / or an amine skeleton.

[0118] The organosilicon compound (C) used for vapor deposition is as described above.

[0119] As the vapor deposition method, a known method can be used, and for example, a vacuum vapor deposition method can be mentioned. The vacuum vapor 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.

[0120] The vacuum degree in the vacuum deposition method is preferably 1.0×10 -1 Pa or less, more preferably 5.0×10 -2 Pa or less, more preferably 2.0×10 -2 Pa or less. The lower limit is not particularly limited, but is usually 1.0×10 - 4 Pa or above.

[0121] Examples of the evaporation method of the deposition source in the vacuum deposition method include an electron beam method, a resistance heating method, a heater heating method, and an induction heating method. From the viewpoint of energy conversion efficiency, the electron beam method is preferred.

[0122] The output power of the electron beam can be appropriately adjusted according to the raw material and substrate used, the evaporation device, the vacuum degree, the irradiation area and the average evaporation rate. For example, the beam current is preferably 6 to 36 mA.

[0123] The average vapor deposition rate when the organic silicon compound (C) is vapor deposited on the antireflection layer of the substrate (s) having the antireflection layer is 0.2 nm / s or more and less than 1.2 nm / s (0.20 nm / s or more and 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.

[0124] The average vapor deposition rate refers to the value obtained by dividing the thickness of the vapor deposited film by the vapor deposition time required to form the vapor deposited film of the above thickness (average vapor deposition rate (nm / s) = film thickness (nm) / vapor deposition time (s)).

[0125] When the average vapor deposition rate is 1.2 nm / s or more, wear resistance and productivity decrease, and when the average vapor deposition rate is less than 0.2 nm / s, productivity decreases, which is not preferable.

[0126] [Middle layer (c)]

[0127] The intermediate layer (c) is a vapor-deposited layer of the organosilicon compound (C). The vapor deposition method is as described above.

[0128] The intermediate layer (c) is a layer having silicon atoms and an amino group or an amine skeleton (-NR 100 -, R 100The intermediate layer (c) is a vapor-deposited layer of an organosilicon compound (C) having an amino group or an amine skeleton. In a preferred embodiment, a hydrolyzable group or a hydroxyl group is bonded to the silicon atom of the organosilicon compound (C), and the Si-OH groups produced by the hydrolysis of the Si-OH groups of the organosilicon compound (C) and / or the hydrolyzable groups bonded to the silicon atom are dehydrated and condensed with each other, so 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 of the water-repellent layer (r).

[0129] The thickness of the intermediate layer (c) is, for example, about 1 nm to about 1000 nm, preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm, and preferably 100 nm or less, more preferably 80 nm or less, further preferably 50 nm or less.

[0130] [Process 2]

[0131] The present production method comprises a step 2 of forming a water-repellent layer (r) on the intermediate layer (c) obtained in the 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 them, the mixed composition (ca) is preferably a mixed composition of the organosilicon compound (A) and the organosilicon compound (B) described later.

[0132] The materials and procedures used in this process are described below.

[0133] <Organic silicon compound (A)>

[0134] 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 via a linking group, and a hydrolyzable group is bonded to the silicon atom via a linking group or not via a linking group. The water-repellent layer (r) is obtained by applying the mixed composition (ca) and curing it, 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 (or via a linking group), and the -SiOH group (Si and OH can be bonded via a linking group) of the organosilicon compound (A) generated by hydrolysis is dehydrated and condensed with each other, so the water-repellent layer (r) usually has a condensation structure derived from the organosilicon compound (A). As the hydrolyzable group, alkoxy groups, halogen atoms, cyano groups, acetoxy groups, isocyanate groups, etc. can be listed.

[0135] The perfluoropolyether structure may also be referred to as a perfluoroalkylene oxide. The perfluoropolyether structure has liquid repellency such as water repellency or oil repellency. The number of carbon atoms contained in the longest straight chain portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and further more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, about 200. The monovalent group having a perfluoropolyether structure of the organosilicon compound (A) preferably further has a perfluoroalkyl group at the free end.

[0136] The water-repellent layer (r) may also be represented as a layer having a perfluoropolyether structure and a polysiloxane skeleton, preferably further having a perfluoroalkyl group. The water-repellent layer (r) preferably has a structure in which a monovalent group having a perfluoroalkyl group at a free end and a perfluoropolyether structure is bonded to a portion of silicon atoms in the polysiloxane skeleton. The presence of a perfluoroalkyl group at the free end side improves the water repellency of the water-repellent layer (r).

[0137] The number of carbon atoms in the perfluoroalkyl group (particularly the number of carbon atoms in the longest linear chain) is, for example, preferably 3 or more, more preferably 5 or more, and further preferably 7 or more. The upper limit of the number of carbon atoms is not particularly limited, and, for example, even about 20 can exhibit excellent water repellency.

[0138] The perfluoroalkyl group may be bonded to a hydrocarbon group and / or a group in which at least a portion of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms to form a fluorinated group such as a fluoroalkyl group, for example, CF3(CF2) m -(CH2) n -、CF3(CF2) m -C6H4- (m is 1 to 10, preferably 3 to 7, n is 1 to 5, preferably 2 to 4), preferably CF3 (CF2) m -(CH2) n - (m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4) The perfluoroalkyl group is more preferably directly bonded to the perfluoropolyether structure.

[0139] In the organosilicon compound (A), the monovalent group having a perfluoropolyether structure and the silicon atom may be bonded via an appropriate linking group, or the monovalent group having a perfluoropolyether may be directly bonded to the silicon atom without the linking group. As the linking group, for example, hydrocarbon groups such as alkylene groups, aromatic hydrocarbon groups, (poly) alkylene glycol groups, or groups in which some of their hydrogen atoms are substituted with F or substituents, and groups formed by their appropriate connection, etc. may be cited. The number of carbon atoms in the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less.

[0140] The hydrolyzable group has the function of bonding the organosilicon compounds (A) to each other or to the active hydrogen (hydroxyl group, etc.) on the surface of the substrate by hydrolysis / dehydration condensation reaction. Examples of such hydrolyzable groups include alkoxy groups (especially alkoxy groups having 1 to 4 carbon atoms), hydroxyl groups, acetoxy groups, halogen atoms (especially chlorine atoms), etc. Preferred hydrolyzable groups are alkoxy groups and halogen atoms, and methoxy groups, ethoxy groups, and chlorine atoms are particularly preferred.

[0141] The hydrolyzable group may be bonded to the silicon atom via a linking group or directly bonded to the silicon atom without a linking group. The number of hydrolyzable groups bonded to the silicon atom may be 1 or more, may be 2 or 3, preferably 2 or 3, and particularly preferably 3. When 2 or more hydrolyzable groups are bonded to the silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but preferably the same hydrolyzable groups are bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to the silicon atom is usually 4, but may be 2 or 3 (particularly 3). When there are 3 or less, the remaining bonds may be bonded to monovalent groups other than the hydrolyzable groups, for example, alkyl groups (particularly alkyl groups having 1 to 4 carbon atoms), H, NCO, etc.

[0142] The monovalent group having a perfluoropolyether structure of the organosilicon compound (A) may be linear or may have a side chain, but is preferably linear.

[0143] As an example of the organosilicon compound (A), there is mentioned a compound represented by the following formula (a).

[0144]

[0145] In the above formula (a), D 1 is a monovalent group having a perfluoropolyether structure, D 1 in and D 2 The end of the bonding side is -CF2-O-*, -CFD 9 -*(* is D 2 Side key), D 2 is a single bond or a divalent hydrocarbon group not substituted by a fluorine atom, D 3 is a trivalent hydrocarbon group not substituted by fluorine atoms, part of the methylene groups of the hydrocarbon group may be replaced by oxygen atoms, D 4 is a hydrogen atom or a fluorine atom, D 5 is a single bond or a divalent hydrocarbon group, D 6 is a monovalent group other than a hydrolyzable group, D 7 is a divalent group or a single bond, D 8 is a hydrolyzable group, D 9 is a hydrogen atom, a fluorine atom or a hydrocarbon group, n1 is 1 to 30, and n2 is 1 to 3.8 The hydrolyzable group may include the above-mentioned hydrolyzable groups.

[0146] The organosilicon compound (A) is preferably a compound represented by the following formula (a1).

[0147]

[0148] In the above formula (a1),

[0149] R a1 It is a divalent perfluoropolyether structure with oxygen atoms at both ends.

[0150] R 11 , R 12 and R 13 Each independently (i.e., R 11 With R 12 With R 13 may be the same or different) is an alkyl group having 1 to 20 carbon atoms, and there are two or more R 11 When two or more R 11 Can be different, there are two or more R 12 When two or more R 12 Can be different, there are two or more R 13 When two or more R 13 Can be different,

[0151] E 1 、E 2 、E 3 、E 4 and E 5 Each independently is a hydrogen atom or a fluorine atom, and there are two or more E 1 When two or more E 1 Can be different, there are more than two E 2 When two or more E 2 Can be different, there are more than two E 3 When two or more E 3 Can be different, there are more than two E 4 When two or more E 4 Can be different,

[0152] G 1 and G 2 are each independently a divalent to decavalent organosiloxane group having a siloxane bond,

[0153] J 1 , J 2 and J 3 Each is independently a hydrolyzable group or -(CH2) e6 -Si(OR14 )3, e6 is 1 to 5, R 14 is methyl or ethyl, and there are two or more J 1 When two or more J 1 Can be different, there are two or more J 2 When two or more J 2 Can be different, there are two or more J 3 When two or more J 3 Can be different,

[0154] 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, and there are two or more L 1 When two or more L 1 Can be different, there are two or more L 2 When two or more L 2 Can be different,

[0155] d11 is 1 to 9,

[0156] d12 is 0 to 9,

[0157] a10 and a14 are each independently 0 to 10,

[0158] a11 and a15 are each independently 0 or 1,

[0159] a12 and a16 are each independently 0 to 9,

[0160] a13 is 0 or 1,

[0161] a21, a22 and a23 are each independently 0 to 2,

[0162] e1, e2 and e3 are each independently 1 to 3.

[0163] The organosilicon compound (A) is represented by the above formula (a1) and has Rf a1 The perfluoropolyether structure shown in FIG. 2 The hydrolyzable group represented by e6 -Si(OR 14 )3(where R 14 is methyl or ethyl). The perfluoropolyether structure is a structure in which all hydrogen atoms of polyoxyalkylene are replaced by fluorine atoms, also known as perfluorooxyalkylene, and can impart water repellency to the obtained film. In addition, the following compounds are present: 2 The organosilicon compounds (A) can be bonded to each other or to other monomers by a polymerization reaction (particularly a polycondensation reaction) to form a matrix of the obtained film.

[0164] R a1 Preferably -O-(CF2CF2O) e4 -or-O-(CF2CF2CF2O) e5 -. e4 and e5 are both 15 to 80.

[0165] R 11 , R 12 and R 13 Preferably, each independently is an alkyl group having 1 to 10 carbon atoms.

[0166] L 1 and L 2 Preferably, each of them is independently a divalent linking group having 1 to 5 carbon atoms and containing a fluorine atom.

[0167] G 1 and G 2 Preferably, each independently is a divalent to pentavalent organosiloxane group having a siloxane bond.

[0168] J 1 , J 2 and J 3 Preferably, each independently is methoxy, ethoxy or -(CH2) e6 -Si(OR 14 )3.

[0169] 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 preferably all 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 preferably all 3. In addition, a13 is preferably 1.

[0170] As the organosilicon compound (A), the following compounds are preferably used: a1 -O-(CF2CF2CF2O) e5 -, e5 is 35~50, L 1 and L 2 are all perfluoroalkylene groups having 1 to 3 carbon atoms, 1 、E 2 and E 3 are all hydrogen atoms, E 4 and E 5 is a hydrogen atom or a fluorine atom, J 1 , J 2 and J 3are all methoxy or ethoxy (especially methoxy), a10 is 1-3, a11 is 0, a12 is 0-5, a13 is 1, a14 is 2-5, a15 is 0, a16 is 0-6, a21-a23 are each independently 0 or 1 (more preferably, a21-a23 are all 0), d11 is 1, d12 is 0 or 1, and e1-e3 are all 3.

[0171] As the organosilicon compound (A), the following compounds are also preferably used: a1 -O-(CF2CF2CF2O) e5 -, e5 is 25 to 40, L 1 is a divalent linking group having 3 to 6 carbon atoms and containing fluorine atoms and oxygen atoms, 2 is a perfluoroalkylene group having 1 to 3 carbon atoms, E 2 、E 3 are all hydrogen atoms, E 5 is a fluorine atom, J 2 -(CH2) e6 -Si(OCH3)3, 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, all a21 to a23 are 0), d11 is 1, d12 is 0, and e2 is 3.

[0172] Furthermore, the organosilicon compound (A) is also preferably a compound represented by the following formula (a2-1).

[0173]

[0174] In the above formula (a2-1),

[0175] R a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms,

[0176] R a22 , Rf a23 , Rf a24 and Rf a25 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf a22 When two or more Rf a22 Can be different, there are two or more Rf a23 When two or more Rf a23 Can be different, there are two or more Rf a24 When two or more Rf a24 Can be different, there are two or more Rfa25 When two or more Rf a25 Can be different,

[0177] R 20 , R 21 , R 22 and R 23 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R 20 When two or more R 20 Can be different, there are two or more R 21 When two or more R 21 Can be different, there are two or more R 22 When two or more R 22 Can be different, there are two or more R 23 When two or more R 23 Can be different,

[0178] R 24 is an alkyl group having 1 to 20 carbon atoms, and there are two or more R 24 When two or more R 24 Can be different,

[0179] M 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more M 1 When two or more M 1 Can be different,

[0180] M 2 is a hydrogen atom or a halogen atom,

[0181] M 3 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms), and there are two or more M 3 When two or more M 3 Can be different,

[0182] M 4 is a hydrolyzable group, and there are two or more M 4 When two or more M 4 Can be different,

[0183] f11, f12, f13, f14 and f15 are each independently an integer of 0 to 600, and the total value of f11, f12, f13, f14 and f15 is 13 or more,

[0184] f16 is an integer from 1 to 20.

[0185] f17 is an integer from 0 to 2.

[0186] g1 is an integer from 1 to 3,

[0187] R a21 -、M 2 -、f11-{C(R 20 )(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 -[CH2C(M 1 ){(CH2) f17 -Si(M 4 ) g1 (R 24 ) 3-g1}]-As long as Rf a21 -、M 2 - is the terminal, and at least a part of them is arranged in the order of forming a perfluoropolyether structure, and -O- is not connected to -O- or -F, and the bonds are arranged in an arbitrary order. That is, formula (a2-1) does not necessarily mean the following: f11 -{C(R 20 )(R 21 )}-continuous, f12-{C(Rf a22 )(Rf a23 )}-continuous, f13-{Si(R 22 )(R 23 )}-continuous, f14-{Si(Rf a24 )(Rf a25 )}-Continuous, f15-M 3 -Continuous, f16-[CH2C(M 1 ){(CH2) f17 -Si(M 4 ) g1 (R 24 ) 3-g1}]-continuous and sequentially arranged, such as -C(R 20 )(R 21 )-Si(Rf a24 )(Rf a25 )-CH2C(M 1 ){(CH2) f17 -Si(M 4 ) g1 (R 24 )3-g1}-C(Rf a22 )(Rf a23 )-M 3 -Si(R 22 )(R 23 )-C(Rf a22 )(Rf a23 )-etc., and they are arranged in any order.

[0188] R a21 An alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms is preferred, a perfluoroalkyl group having 1 to 10 carbon atoms is more preferred, and a perfluoroalkyl group having 1 to 5 carbon atoms is further preferred.

[0189] R a22 , Rf a23 , Rf a24 and Rf a25 Preferably, each independently represents a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, and more preferably, all of them represent fluorine atoms.

[0190] R 20 , R 21 , R 22 and R 23 Preferably, each independently is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably, all are hydrogen atoms.

[0191] R 24 An alkyl group having 1 to 5 carbon atoms is preferred.

[0192] M 1 Preferably, each independently is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably, all are hydrogen atoms.

[0193] M 2 Preferred is a hydrogen atom.

[0194] M 3 Preferred are -C(=O)-O-, -O-, and -OC(=O)-, and more preferably all are -O-.

[0195] M 4 An alkoxy group or a halogen atom is preferred, and a methoxy group, an ethoxy group or a chlorine atom is more preferred.

[0196] It is preferred that f11, f13 and f14 are each 1 / 2 or less of f12, more preferably 1 / 4 or less, further preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.

[0197] It is preferable that f15 is 1 / 5 or more of the total value of f11, f12, f13, and f14 and is not more than the total value of f11, f12, f13, and f14.

[0198] f12 is preferably 20 to 600, more preferably 20 to 200, further preferably 50 to 200 (further preferably 30 to 150, particularly 50 to 150, most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, further preferably 10 to 200 (further preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20 to 600, more preferably 20 to 200, further preferably 50 to 200.

[0199] f16 is preferably 1-18, more preferably 1-15, and further preferably 1-10.

[0200] f17 is preferably 0-1.

[0201] g1 is preferably 2-3, more preferably 3.

[0202] 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 3 The order of - in the formula is arbitrary as long as at least a part of them forms a perfluoropolyether structure, but the repeating unit marked with f12 and enclosed in brackets on the most fixed end side (the side bonded to the silicon atom) is preferred (i.e., -{C(Rf a22 )(Rf a23 )}-) located at the most free end side of the repeating unit marked f11 and enclosed in brackets (ie, -{C(R 20 )(R 21 )}-) The repeating units enclosed in brackets and labeled f12 and f14 are closer to the free end side, and more preferably the most fixed end side (ie, -{C(Rf a22 )(Rf a23 )}- and -{Si(Rf a24 )(Rf a25 )}-) located on the side of the most free end and enclosed in brackets by the repeating units labeled f11 and f13 (ie, -{C(R 20 )(R 21 )}- and -{Si(R 22 )(R 23 )}-) is closer to the free end side.

[0203] Preferably, in the above formula (a2-1), Rf a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf a22 , Rf a23 , Rf a24 , Rf a25 All are fluorine atoms, M 3 All are -O-,M 4 All are methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M 1 、M 2 All are hydrogen atoms, f11 is 0, f12 is 30-150 (more preferably 80-140), f15 is 30-60, f13 and f14 are 0, f17 is 0-1 (especially 0), g1 is 3, and f16 is 1-10.

[0204] Furthermore, the organosilicon compound (A) is also preferably a compound represented by the following formula (a2-2).

[0205]

[0206] In the above formula (a2-2),

[0207] R a26 , Rf a27 , Rf a28 and Rf a29 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf a26 When two or more Rf a26 Can be different, there are two or more Rf a27 When two or more Rf a27 Can be different, there are two or more Rf a28 When two or more Rf a28 Can be different, there are two or more Rf a29 When two or more Rf a29 Can be different,

[0208] R 25 , R 26 , R 27 and R 28 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R 25 When two or more R 25 Can be different, there are two or more R 26 When two or more R 26 Can be different, there are two or more R 27 When two or more R 27 Can be different, there are two or more R28 When two or more R 28 Can be different,

[0209] R 29 and R 30 Each independently represents an alkyl group having 1 to 20 carbon atoms, and there are two or more R 29 When two or more R 29 Can be different, there are two or more R 30 When two or more R 30 Can be different,

[0210] M 7 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)- or -C(=O)NR-, the above R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, and there are two or more M 7 When two or more M 7 Can be different,

[0211] M 5 、M 9 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more M 5 When two or more M 5 Can be different, there are two or more M 9 When two or more M 9 Can be different,

[0212] M 6 and M 10 are each independently a hydrogen atom or a halogen atom,

[0213] M 8 and M 11 Each independently is a hydrolyzable group, and there are two or more M 8 When two or more M 8 Can be different, there are two or more M 11 When two or more M 11 Can be different,

[0214] f21, f22, f23, f24 and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24 and f25 is 13 or more,

[0215] f26 and f28 are each independently an integer of 1 to 20,

[0216] f27 and f29 are each independently an integer of 0 to 2,

[0217] g2 and g3 are each independently an integer of 1 to 3,

[0218] 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-M 7 -、f26-[CH2C(M 5 ){(CH2) f27 -Si(M 8 ) g2 (R 29 ) 3-g2}] and f28 -[CH2C(M 9 ){(CH2) f29 -Si(M 11 ) g3 (R 30 ) 3-g3}]As long as M 10 -、M 6 - is the terminal, and is arranged in the order that at least a part forms a perfluoropolyether structure, and -O- is not continuous with -O-, and is arranged and bonded in an arbitrary order. Arrangement and bonding in an arbitrary order is the same as the case described in the above formula (a2-1), and is not limited to the meaning that each repeating unit is continuous and arranged in the order described in the above formula (a2-2).

[0219] Preferably, in the above formula (a2-2), Rf a26 , Rf a27 , Rf a28 and Rf a29 All are fluorine atoms, M 7 All are -O-,M 8 and M 11 All are methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M 5 、M 6 、M 9 and M 10 All of them are hydrogen atoms, f21 is 0, f22 is 30-150 (more preferably 80-140), f25 is 30-60, f23 and f24 are 0, f27 and f29 are 0-1 (particularly preferably 0), g2 and g3 are 3, and f26 and f28 are 1-10.

[0220] More specifically, the organosilicon compound (A) includes a compound represented by the following formula (a3).

[0221]

[0222] 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. 30 , R 31 , R 32 , R 33 The number of carbon atoms of each independently is preferably 2 to 4, 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, more preferably 20 to 50, h2 is preferably 1 to 4, more preferably 1 to 3, and h3 is preferably 1 to 8, more preferably 1 to 6.

[0223] Examples of the organosilicon compound (A) include compounds represented by the following formula (a4).

[0224]

[0225] In the above formula (a4), R 40 is a perfluoroalkyl group having 2 to 5 carbon atoms, R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms, R 42 is a fluoroalkylene group in which a part of the hydrogen atoms of an alkylene group having 2 to 5 carbon atoms are replaced by fluorine atoms, and R 43 , R 44 are each independently an alkylene group having 2 to 5 carbon atoms, R 45 k1, k2, and k3 are each independently an integer of 1 to 5.

[0226] The number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, further preferably 6,000 or more, particularly preferably 7,000 or more, and is preferably 40,000 or less, more preferably 20,000 or less, further preferably 15,000 or less.

[0227] Examples of the organosilicon compound (A) include a compound represented by the following formula (1) or a compound having a structure similar to the compound, and examples thereof include OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd.

[0228]

[0229] Examples of the compound represented by the formula (1) include compounds synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609, wherein r is 43, s is an integer of 1 to 6, and the number average molecular weight is about 8,000.

[0230] Examples of similar structures include structures in which the number of carbon atoms of the hydrocarbon group of the above formula (1) or the number of carbon atoms of the hydrocarbon group substituted with fluorine atoms is different, structures in which the perfluoropolyether structure and the silicon atom are not bonded via a connecting group, structures in which other hydrocarbon groups (including hydrocarbon groups in which at least a part of hydrogen atoms are substituted with fluorine atoms) are interposed at any position of the connecting group between the perfluoropolyether structure and the silicon atom, structures in which the silicon atom and the hydrolyzable group are bonded via a connecting group, structures in which the values ​​of r and s are different, etc., but the structure is not limited to these structures.

[0231] As the organosilicon compound (A), the compound represented by the formula (a1) is preferred, the compound represented by the formula (a2-1) is more preferred, and the compound represented by the formula (a3) ​​is further preferred.

[0232] As the organosilicon compound (A), only one kind may be used, or two or more kinds may be used.

[0233] <Organic silicon compound (B)>

[0234] The organosilicon compound (B) is a compound represented by formula (b1).

[0235] As described later, the organosilicon compound (B) represented by the following formula (b1) has A 2 The hydrolyzable group shown is usually a -SiOH group of the organosilicon compound (B) generated by hydrolysis, a -SiOH group of the organosilicon compound (A) generated by hydrolysis and / or a -SiOH group of the organosilicon compound (B) generated by hydrolysis, which undergoes dehydration condensation. Therefore, in a preferred embodiment, the water-repellent layer (r) as the cured layer of the mixed composition (ca) has a condensation structure derived from the organosilicon compound (A) and 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, an isocyanate group, and the like.

[0236]

[0237] In formula (b1),

[0238] R b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms,

[0239] R b11 , R b12 , Rb13 , R b14 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R b11 When two or more R b11 Can be different, there are two or more R b12 When two or more R b12 Can be different, there are two or more R b13 When two or more R b13 Can be different, there are two or more R b14 When two or more R b14 Can be different,

[0240] R b11 , Rf b12 , Rf b13 , Rf b14 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf b11 When two or more Rf b11 Can be different, there are two or more Rf b12 When two or more Rf b12 Can be different, there are two or more Rf b13 When two or more Rf b13 Can be different, there are two or more Rf b14 When two or more Rf b14 Can be different,

[0241] R b15 is an alkyl group having 1 to 20 carbon atoms, and there are two or more R b15 When two or more R b15 Can be different,

[0242] A 1 is -O-, -C(=O)-O-, -OC(=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 fluorinated alkyl group having 1 to 4 carbon atoms, and there are two or more A 1 When two or more A 1 Can be different,

[0243] A 2 is a hydrolyzable group, and there are two or more A 2 When two or more A 2 Can be different,

[0244] b11, b12, b13, b14, and b15 are each independently an integer of 0 to 100,

[0245] c is an integer from 1 to 3,

[0246] R 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 -As long as Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c The -O- is a terminal, a perfluoropolyether structure is not formed, and -O- is not connected to -O- or -F, and the bonds are arranged in an arbitrary order.

[0247] R b10 Preferably, each independently is a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).

[0248] R b11 , R b12 , R b13 and R b14 Preferred is a hydrogen atom.

[0249] R b15 An alkyl group having 1 to 5 carbon atoms is preferred.

[0250] A 1 Preferred is -O-, -C(=O)-O- or -OC(=O)-.

[0251] A 2 An alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred, and a methoxy group, an ethoxy group or a chlorine atom is more preferred.

[0252] b11 is preferably 1-30, more preferably 1-25, further preferably 1-10, particularly preferably 1-5, and most preferably 1-2.

[0253] b12 is preferably 0-15, more preferably 0-10.

[0254] b13 is preferably 0-5, more preferably 0-2.

[0255] b14 is preferably 0-4, more preferably 0-2.

[0256] b15 is preferably 0-4, more preferably 0-2.

[0257] c is preferably 2-3, more preferably 3.

[0258] 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 further preferably 20 or less.

[0259] Rf is particularly preferred b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, R b11 , R b12 are all hydrogen atoms, A 2 is 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.

[0260] It should be noted that in the examples described below, when FAS13E used as compound (B) is represented by the above formula (b1), it is defined as: R b11 , R b12 are all hydrogen atoms, b11 is 2, b13, b14 and b15 are all 0, c is 3, A 2 is ethoxy, Rf b10 -{C(Rf b11 )(Rf b12 )} b12 - is the end and is C6F 13 -.

[0261] Specific examples of the compound represented by the formula (b1) include CF3-Si-(OCH3)3, C j F 2j＋1 -Si-(OC2H5)3 (j is an integer from 1 to 12), among which C4F9-Si-(OC2H5)3 and C6F 13 -Si-(OC2H5)3, C7F 15 -Si-(OC2H5)3, C8F 17 -Si-(OC2H5)3. In addition, CF3CH2O(CH2) can be listed. k SiCl3, CF3CH2O(CH2) k Si(OCH3)3, CF3CH2O(CH2) k Si(OC2H5)3, CF3(CH2)2Si(CH3)2(CH2) kSiCl3, CF3(CH2)2Si(CH3)2(CH2) k Si(OCH3)3, CF3(CH2)2Si(CH3)2(CH2) k Si(OC2H5)3, CF3(CH2)6Si(CH3)2(CH2) k SiCl3, CF3(CH2)6Si(CH3)2(CH2) k Si(OCH3)3, CF3(CH2)6Si(CH3)2(CH2) k Si(OC2H5)3, CF3COO(CH2) k SiCl3, CF3COO(CH2) k Si(OCH3)3, CF3COO(CH2) k Si(OC2H5)3 (k is 5 to 20, preferably 8 to 15). In addition, CF3(CF2) can also be mentioned. m -(CH2) n SiCl3, CF3(CF2) m -(CH2) n Si(OCH3)3, CF3(CF2) m -(CH2) n Si(OC2H5)3 (m is 1 to 10, preferably 3 to 7, n is 1 to 5, preferably 2 to 4). CF3(CF2) can also be mentioned p -(CH2) q -Si-(CH2CH=CH2)3 (p is 2 to 10, preferably 2 to 8, q is 1 to 5, preferably 2 to 4). Further examples include CF3(CF2) p -(CH2) q SiCH3Cl2, CF3(CF2) p -(CH2) q SiCH3(OCH3)2, CF3(CF2) p -(CH2) q SiCH3(OC2H5)2 (p is 2 to 10, preferably 3 to 7, q is 1 to 5, preferably 2 to 4).

[0262] The organosilicon compound (B) is preferably a compound represented by the following formula (b2).

[0263]

[0264] In the above formula (b2), R 60 is a perfluoroalkyl group having 3 to 8 carbon atoms, R 61 is an alkylene group having 1 to 5 carbon atoms, R62 It is an alkyl group having 1 to 3 carbon atoms.

[0265] As the organosilicon compound (B), only one kind may be used, or two or more kinds may be used.

[0266] It should be noted that the mixed composition (ca) is a composition mixed with an organosilicon compound (A), preferably a composition mixed with an organosilicon compound (A) and an organosilicon compound (B), obtained by mixing the organosilicon compound (A) and the organosilicon compound (B) as required, and in the case of mixing components other than the organosilicon compound (A) and the organosilicon compound (B), the composition is obtained by mixing the organosilicon compound (A), the organosilicon compound (B) as required, and other components. The mixed composition (ca) also includes a substance obtained by reacting after mixing, for example, during storage.

[0267] <Solvent (D)>

[0268] The mixed composition (ca) preferably contains a solvent (D).

[0269] As the solvent (D), a fluorinated solvent is preferably used, for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent, etc., and a boiling point of 100°C or more is particularly preferred. As the fluorinated ether solvent, a hydrofluoroether such as a fluoroalkyl (especially a perfluoroalkyl having 2 to 6 carbon atoms)-alkyl (especially a methyl or ethyl) ether is preferred, and examples thereof include ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether. As ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether, for example, Novec (registered trademark) 7200 (manufactured by 3M Company, molecular weight of about 264) can be cited. As the fluorinated amine solvent, an amine in which at least one hydrogen atom in ammonia is substituted with a fluoroalkyl group is preferred, and a tertiary amine in which all hydrogen atoms in ammonia are substituted with a fluoroalkyl group (especially a perfluoroalkyl group) is preferred, and specifically, tris(heptafluoropropyl)amine can be cited, and Fluorinert (registered trademark) FC-3283 (manufactured by 3M Company, molecular weight of about 521) corresponds thereto. Examples of the fluorinated hydrocarbon solvent 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 Solve 55 (manufactured by Solvex).

[0270] As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC Corporation) and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by AGC Corporation) can be used.

[0271] As the solvent (D), it is preferred to use at least a fluorinated amine solvent. In addition, it is preferred to use two or more fluorinated solvents as the solvent (D), and it is preferred to use a fluorinated amine solvent and a fluorinated hydrocarbon solvent (particularly a fluorinated aliphatic hydrocarbon solvent).

[0272] <Other ingredients>

[0273] The mixed composition (ca) may be mixed with various additives such as silanol condensation catalysts, antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, mildew inhibitors, antibacterial agents, biofouling inhibitors, deodorants, pigments, flame retardants, antistatic agents, etc., within the range that does not hinder the effects of the present invention.

[0274] 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 further preferably 0.6% by mass or less, relative to 100% by mass of the entire mixed composition (ca).

[0275] 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, more preferably 0.2 mass % or less, based on 100 mass % of the entire mixed composition (ca).

[0276] The mass ratio of the content of the organosilicon compound (B) to the content of the organosilicon compound (A) is preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.10 or more, and is preferably 2.0 or less, more preferably 1.0 or less, further preferably 0.6 or less.

[0277] The amounts of the organosilicon compounds (A) and (B) can be adjusted during the preparation of the composition or can be calculated from the analysis results of the composition.

[0278] [Steps of process 2]

[0279] 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).

[0280] The method for forming the cured layer is not particularly limited, and examples thereof include a method of applying the mixed composition (ca) on the intermediate layer (c) obtained in step 1 and then curing the applied mixed composition (ca).

[0281] The mixed composition (ca) can be prepared by mixing the respective components, for example.

[0282] There is no particular restriction on the order and / or timing of mixing the above-mentioned components, and for example, a method of sequentially adding the organosilicon compound (A) and optional components as required in a container and then stirring and mixing them can be cited. In addition, when adding each component to the container, it can be added all at once or divided into multiple additions.

[0283] The stirring may be performed using a known stirring device, and examples thereof include a mechanical stirrer, a magnetic stirrer, a homogenizer, and an ultrasonic disperser.

[0284] Examples of a method 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.

[0285] From the viewpoint of productivity, the coating method of the mixed composition (ca) is preferably a dip coating method.

[0286] The immersion time of the dip coating method can be appropriately adjusted according to the mixed composition (ca) and the substrate, preferably 1 to 180 seconds, more preferably 5 to 60 seconds. In addition, the pulling speed of the dip coating method can also be appropriately adjusted according to the mixed composition (ca) and the substrate, preferably 1.0 to 10.0 mm / second, more preferably 2.0 to 6.0 mm / second.

[0287] Examples of a method for curing the mixed composition (ca) applied on the intermediate layer (c) include drying and heat curing.

[0288] 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 on the intermediate layer (c) by wet heating.

[0289] The curing temperature is preferably 5° C. or higher, more preferably 10° C. or higher, and further preferably 15° C. or higher, and is preferably 100° C. or lower, more preferably 80° C. or lower, and further preferably 60° C. or lower.

[0290] The curing humidity is preferably 30% RH or more, more preferably 50% RH or more, further preferably 60% RH or more, and is preferably 90% RH or less, more preferably 85% RH or less.

[0291] The curing time is preferably 5 minutes or more, more preferably 10 minutes or more, further preferably 20 minutes or more, and is preferably 24 hours or less, more preferably 12 hours or less, further preferably 6 hours or less, and particularly preferably 1 hour or less.

[0292] [Water repellent layer (r)]

[0293] The water-repellent layer (r) is a cured layer of the mixed composition (ca) of the organosilicon compound (A).

[0294] As described above, the water-repellent layer (r) is obtained, for example, by applying the mixed composition (ca) and curing it, 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 (which may be Si and OH 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) generally has a condensation structure derived from the organosilicon compound (A).

[0295] The thickness of the water-repellent layer (r) is, for example, 1 to 1000 nm.

[0296] [Process 3]

[0297] The present production method preferably comprises, before step 1, step 3 of subjecting the antireflection layer of the substrate (s) having the antireflection layer to a hydrophilic treatment.

[0298] As the hydrophilic treatment, hydrophilic treatments such as corona treatment, plasma treatment, ultraviolet treatment, and ion cleaning treatment can be listed, and plasma treatment and ion cleaning treatment are more preferred. By performing hydrophilic treatments such as plasma treatment, functional groups such as OH groups and COOH groups can be formed on the surface of the anti-reflection layer. When such functional groups are formed on the surface of the anti-reflection layer, the adhesion between the intermediate layer (c) and the substrate (s) having the anti-reflection layer can be further improved. Therefore, in the case of implementing step 3, step 1 is preferably a step of vapor-depositing an organosilicon compound (C) on the surface to which the above-mentioned hydrophilic treatment has been applied. However, in the case of using the laminate for eyeglass lenses, it is preferred to vapor-deposit the organosilicon compound (C) without performing a hydrophilic treatment on the anti-reflection layer of the substrate (s). Therefore, the hydrophilic treatment is preferably performed when the laminate is used for purposes other than eyeglass lenses.

[0299] [Manufacture of eyeglass lenses]

[0300] The present manufacturing method can be suitably used in the manufacturing process of eyeglass lenses.

[0301] The present manufacturing method may be implemented in combination with or after other steps performed on the laminate for manufacturing the eyeglass lens. Examples of other steps include a ball grinding step, a dyeing step, a shape processing step, and an inspection step of the laminate.

[0302] It should be noted that the laminate can also be used as a spectacle lens as it is.

[0303] [Laminated body]

[0304] The laminated body produced by the present production method will be described.

[0305] [Configuration of Laminated Body]

[0306] The laminate includes a substrate (s) having an antireflection layer, an intermediate layer (c) formed on the antireflection layer by vapor deposition, and a water-repellent layer (r) formed on the intermediate layer.

[0307] The laminate may have other members within the range not inhibiting the effects of the present invention. Examples of the other members include a primer layer, a hard coat layer, a protective film, and a hydrophobic resin film.

[0308] [Physical properties of laminated body]

[0309] The laminate preferably has a water contact angle and a water sliding angle measured on the surface subjected to the wear resistance test after the surface on the water-repellent layer (r) side is subjected to the wear resistance test described below, and satisfies at least one of the following requirements (1) and (2), and more preferably satisfies both requirements (1) and (2).

[0310] (1) The contact angle of water is 110° or more.

[0311] (2) The water sliding angle is less than 10°.

[0312] The contact angle is also preferably 115° or more, and may be 130° or less.

[0313] The above-mentioned slide angle may be greater than 0.5°.

[0314] The wear resistance test is a test in which a load of 200 g is applied to the water-repellent layer (r) side surface of the laminate for every 1.5 cm × 1.5 cm area and rubbed 20,000 times. When wiping, it is preferably wiped with paper made of pulp raw materials, and more preferably wiped with paper made of pulp raw materials installed on an elastomer. As the paper made of pulp raw materials, KimWipe S-200 manufactured by Nippon Paper CRECIA Co., Ltd. is preferably used. For example, it is preferred to use KimWipe S-200, set the stroke distance of the wear resistance test to 30 mm, set the wiping speed to 70 to 90 reciprocating / minute, and measure the contact angle and the sliding angle at the approximate center of the stroke area. When applying a load, it is sufficient to apply a pressure equivalent to a load of 200 g per 1.5 cm × 1.5 cm area, and a laminate having a water-repellent layer (r) of a size less than 1.5 cm × 1.5 cm is also included in the scope of the present invention.

[0315] [Application of laminate]

[0316] The laminate can be used in various applications.

[0317] When a spectacle lens substrate is used as the substrate, it can be suitably used as a spectacle lens.

[0318] In addition, the laminate can preferably be used as a front panel in a flexible display device, and the front panel is sometimes referred to as a window film. The flexible display device is preferably composed of a laminate for a flexible display device and an organic EL display panel, and a flexible display device laminate is configured on the visual side of the organic EL display panel, and is configured to be able to be bent. The laminate for a flexible display device may further contain a polarizer (preferably a circular polarizer), a touch sensor, etc., and their stacking order is arbitrary, preferably from the visual side in the order of a window film (i.e., a laminate obtained by the present manufacturing method), a polarizer, a touch sensor, or a window film, a touch sensor, and a polarizer. If there is a polarizer on the visual side closer to the touch sensor, the pattern of the touch sensor becomes less visible, and the visibility of the displayed image becomes good, and thus it is preferred. Each component can be stacked using an adhesive, an adhesive, etc. In addition, the flexible display device may have a shading pattern formed on at least one surface of any layer of a window film, a polarizer, or a touch sensor.

[0319] Example

[0320] The present invention will be described in more detail below by giving examples. The present invention is not limited to the following examples, and can of course be implemented with appropriate modifications within the scope of the gist, and all of them are included in the technical scope of the present invention.

[0321] [Examples 1 to 4 and Comparative Examples 1 to 2]

[0322] [Production of Laminated Body]

[0323] <Preparation of substrate(s) having antireflection layer>

[0324] The coating liquid was applied to the surface of NL3-SP (size 75 mmφ, center thickness 1.1 mm) manufactured by Nikon Essilor by a dipping method and heated to cure, and a urethane coating (primer) with a thickness of about 1 μm to improve impact resistance and a silicone hard coating (hard coating) with a thickness of about 2 μm to improve scratch resistance were layered in sequence.

[0325] Next, a multilayer anti-reflection coating (anti-reflection layer (ar). A layer formed by alternating stacking of silicon dioxide layers and zirconium oxide layers) with a thickness of about 0.4 μm is formed on the above-mentioned hard coating layer by vacuum evaporation to obtain a substrate (s) with an anti-reflection layer.

[0326] <Process 1>

[0327] As the organosilicon compound (C), a reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330 (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula was used.

[0328]

[0329] A vacuum deposition apparatus (manufactured by Satisloh, model 1200-DLX-2) was used, and the output power of the electron beam was set so that the average deposition rate was the value shown in Table 1. The vacuum was 1.0×10 -2 Pa, the organosilicon compound (C) is deposited on the antireflection layer of the substrate (s) having the antireflection layer to form an intermediate layer (c) having a thickness of 15 to 35 nm.

[0330] The average vapor deposition rate is a value obtained 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)).

[0331] The film thickness is measured using a quartz resonator film thickness meter in which a calibration value is set so as to indicate the film thickness on the substrate.

[0332] <Process 2>

[0333] OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd. was used as the organosilicon compound (A), and FAS13E (C6F 13 -C2H4-Si(OC2H5)3, manufactured by Tokyo Chemical Industry Co., Ltd.), FC-3283 (C9F 21 N, Fluorinert, manufactured by 3M Co.) was mixed and stirred at room temperature for a predetermined time to obtain a mixed composition (ca).

[0334] In the mixed composition (ca), the ratio of the organosilicon compound (A) was 0.425% by mass, and the ratio of the organosilicon compound (B) was 0.05% by mass when the entire mixed composition (ca) was taken as 100% by mass.

[0335] The mixed composition (ca) was applied onto the intermediate layer (c) formed in the above step 1 using a dip coater (DT-0001-S3 manufactured by SDI Co., Ltd.) under the conditions of a liquid immersion time of 10 seconds and a pull-up speed of 3.5 mm / sec. Then, wet heat curing was performed at 50°C and 80% RH for 30 minutes to form a water-repellent layer (r) as a cured layer of the mixed composition (ca).

[0336] [evaluate]

[0337] The laminated bodies obtained in Examples and Comparative Examples were evaluated by the following methods.

[0338] 16 overlapping sheets of KimWipe Wiper S-200 manufactured by Nippon Paper CRECIA were installed on a 15 mm square elastomer (plastic eraser manufactured by Maped (France), model 1156SMTR00), a load of 200 g was applied to the water-repellent layer (r) of the laminate, and an abrasion resistance test was carried out by wiping 20,000 times with a stroke of 30 mm and 90 r / min (90 reciprocating times per minute).

[0339] Then, at the substantially central portion of the worn area, the water contact angle and the water sliding-off angle after the wear resistance test were measured by the following method.

[0340] 1 μL of water was dropped onto the water-repellent layer (r) of the obtained laminate, and the contact angle of water was measured by a drop method (analysis method: ellipse fitting method) using a contact angle measuring device (DM-500 / DM-SA manufactured by Kyowa Interface Science Co., Ltd.).

[0341] A 20 μL drop of water was dripped onto the water-repellent layer (r) of the obtained laminate, and the water sliding angle 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).

[0342] For each of three samples of the laminated bodies produced under the conditions described in Examples 1 to 4 and Comparative Examples 1 and 2, the water contact angle and the water sliding-off angle after the above-mentioned abrasion resistance test were measured.

[0343] After the wear resistance test, samples satisfying all of the following requirements (1) and (2) were judged as good products with excellent wear resistance, and samples not satisfying at least one requirement were judged as defective products.

[0344] (1) The water sliding angle after the wear resistance test is 10° or less.

[0345] (2) The water contact angle after the wear resistance test is 110° or more.

[0346] The ratio of good products among the three samples subjected to evaluation was defined as the good product rate, and the good product rate was calculated (good product rate (%) = number of good product samples / number of measured samples×100).

[0347] The higher the yield rate, the higher the wear resistance and the higher the productivity of the laminated body.

[0348] [result]

[0349] Table 1 shows the results of Examples 1 to 4 and Comparative Examples 1 and 2.

[0350]

[0351] As shown in Table 1, it was confirmed that the method for producing a laminated body of the present invention can produce a laminated body having excellent wear resistance with good productivity.

Claims

1. A method for producing a laminate, comprising: Step 1 of forming an intermediate layer (c) on the 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 organic silicon compound (C) having silicon atoms 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 a linking group or not, and a hydrolyzable group is bonded to the silicon atom via a linking group or not, 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.

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), In the formula (a1), R a1 It is a divalent perfluoropolyether structure with oxygen atoms at both ends. R 11 , R 12 and R 13 Each independently represents an alkyl group having 1 to 20 carbon atoms, and there are two or more R 11 When two or more R 11 Can be different, there are two or more R 12 When two or more R 12 Can be different, there are two or more R 13 When two or more R 13 Can be different, E 1 、E 2 、E 3 、E 4 and E 5 Each independently is a hydrogen atom or a fluorine atom, and there are two or more E 1 When two or more E 1 Can be different, there are two or more E 2 When two or more E 2 Can be different, there are two or more E 3 When two or more E 3 Can be different, there are more than two E 4 When two or more E 4 Can be different, G 1 and G 2 are each independently a divalent to decavalent organosiloxane group having a siloxane bond, J 1 , J 2 and J 3 Each is independently a hydrolyzable group or -(CH2) e6 -Si(OR 14 )3, e6 is 1 to 5, R 14 is methyl or ethyl, and there are two or more J 1 When two or more J 1 Can be different, there are two or more J 2 When two or more J 2 Can be different, there are two or more J 3 When two or more J 3 Can 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, and there are two or more L 1 When two or more L 1 Can be different, there are two or more L 2 When two or more L 2 Can be different, 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, e1, e2 and e3 are each independently 1 to 3.

3. The method for producing a laminate according to claim 1 or 2, wherein: The mixed composition (ca) further comprises at least one organosilicon compound (B) represented by the following formula (b1), In the formula (b1), Rf b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, R b11 , R b12 , R b13 and R b14 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R b11 When two or more R b11 Can be different, there are two or more R b12 When two or more R b12 Can be different, there are two or more R b13 When two or more R b13 Can be different, there are two or more R b14 When two or more R b14 Can be different, R b11 , Rf b12 , Rf b13 and Rf b14 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf b11 When two or more Rf b11 Can be different, there are two or more Rf b12 When two or more Rf b12 Can be different, there are two or more Rf b13 When two or more Rf b13 Can be different, there are two or more Rf b14 When two or more Rf b14 Can be different, R b15 is an alkyl group having 1 to 20 carbon atoms, and there are two or more R b15 When two or more R b15 Can be different, A 1 is -O-, -C(=O)-O-, -OC(=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 fluorinated alkyl group having 1 to 4 carbon atoms, and there are two or more A 1 When two or more A 1 Can be different, A 2 is a hydrolyzable group, and there are two or more A 2 When two or more A 2 Can be different, b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100, c is an integer from 1 to 3, R 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 -As long as Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c If -O- is a terminal, a perfluoropolyether structure is not formed, and -O- is not connected to -O- or -F, the bonds can be arranged in an arbitrary order.

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

0.

5. The method for producing a laminate according to any one of claims 1 to 4, wherein: A hydrolyzable group or a hydroxyl group is bonded to at least one silicon atom in the organic silicon compound (C).

6. The method for producing a laminate according to any one of claims 1 to 5, wherein: The organosilicon compound (C) is an organosilicon compound represented by the following formula (c2): In the formula (c2), R x20 and R x21 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are two or more R x20 When two or more R x20 Can be different, there are two or more R x21 When two or more R x21 Can be different, R x20 and Rf x21 Each independently represents an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and there are two or more Rf x20 When two or more Rf x20 Can be different, there are two or more Rf x21 When two or more Rf x21 Can be different, R x22 and R x23 Each independently represents an alkyl group having 1 to 20 carbon atoms, and there are two or more R x22 and R x23 When two or more R x22 and R x23 Can be different, X 20 and X 21 Each independently is a hydrolyzable group, and there are two or more X 20 and X 21 When two or more X 20 and X 21 Can 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 indicated by p20 or p21 and enclosed in parentheses is replaced by an amine skeleton -NR 100 -, R in the amine skeleton 100 is a hydrogen atom or an alkyl group, p22 and p23 are each independently an integer of 1 to 3, p20-{C(R x20 )(R x21 )}-、p21-{C(Rf x20 )(Rf x21 )}-bond in any order without requiring p20 or p21 to be continuous, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 .

7. The method for producing a laminate according to any one of claims 1 to 6, 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), In the 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, In the formula (c2-2), X 22 and X 23 Each independently is a hydrolyzable group, and there are two or more X 22 and X 23 When two or more X 22 and X 23 Can be different, R x24 and R x25 Each independently represents an alkyl group having 1 to 20 carbon atoms, and there are two or more R x24 and R x25 When two or more R x24 and R x25 Can be different, -C w H 2w -At least one of the methylene groups of a part of - is replaced by an amine skeleton -NR 100 -, R 100 is a hydrogen atom or an alkyl group, w is an integer of 1 to 30, excluding the number of methylene groups replaced by the amine skeleton, and p24 and p25 are each independently an integer of 1 to 3.

8. The method for producing a laminate according to any one of claims 1 to 7, wherein: After an abrasion resistance test in which a load of 200 g is applied to the surface of the water-repellent layer (r) side of the laminate per an area of ​​1.5 cm×1.5 cm and the laminate is rubbed 20,000 times, the properties measured on the surface of the water-repellent layer (r) side of the laminate satisfy at least one of the following requirements (1) and (2), (1) The water sliding angle is less than 10°; (2) The contact angle of water is 110° or more.

9. The method for producing a laminate according to any one of claims 1 to 8, 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 any one of claims 1 to 9, wherein: The step 2 is a step of forming the water-repellent layer (r) by applying the mixed composition (ca) on the intermediate layer (c) and curing the mixed composition (ca).

11. The method for producing a laminate according to any one of claims 1 to 10, wherein: Prior to step 1, step 3 is provided of subjecting the antireflection layer of the substrate (s) having the antireflection layer to a hydrophilic treatment. The step 1 is a step of forming the intermediate layer (c) by vapor deposition on the surface of the antireflection layer subjected to the hydrophilization treatment. 12 . A method for producing an eyeglass lens, comprising the method for producing a laminate according to claim 1 .

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