Laminate and method for producing same

Abstract

The present invention provides a laminate which is provided with a substrate (s) having an anti-reflection layer, an intermediate layer (c) provided on the anti-reflection layer side of the substrate, and a water-repellent layer (r) in this order, the intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) having a silicon atom and an amino group and / or an amine skeleton or a vapor-deposited layer of the organosilicon compound (C), and the water-repellent layer (r) is formed by bonding a monovalent group having a perfluoropolyether structure to a silicon atom via a linking group or without a linking group. And a cured layer of a mixed composition (ca) of an organosilicon compound (A) in which a hydrolyzable group is bonded to the silicon atom via a linking group or without a linking group. The laminate satisfies the following requirements (1). (1) The slip angle of water after a wear resistance test in which a 200 g load is applied to the water-repellent layer (r)-side surface of the laminate per 1.5 cm * 1.5 cm area and the laminate is wiped for 20000 times is 50 DEG or less.

Description

[0001] This application is a divisional application of the invention patent application with Chinese application number 202080030045.7 (the invention name of the original application is "Laminate and its manufacturing method", and the application date of the original application is April 22, 2020). Technical Field

[0002] The present invention relates to a laminate and a method for producing the same. Background Art

[0003] Fluorine-based water-repellent films, represented by films formed from compositions containing compounds having a perfluoropolyether structure, have very low surface free energy and are therefore used as antifouling coatings or water- and oil-repellent coatings in various fields, such as display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobiles, and window glass in buildings.

[0004] A water-repellent film is usually formed on a substrate for use. When applying a water-repellent film-forming composition to a substrate, another layer such as a primer layer may be formed on the substrate in advance, and then the composition is applied to form an antifouling coating film or a water- and oil-repellent coating film.

[0005] For example, Patent Document 1 discloses a hard coat film comprising a hard coat layer (X), a primer layer (Y), and a surface layer (Z) laminated in this order on at least one surface of a substrate, wherein the surface layer (Z) has a water contact angle of 110° or greater. Patent Document 1 discloses that a fluorine-based compound having a polyperfluoropolyether chain is preferably used to form the surface layer (Z), while a silane compound such as 3-acryloxypropyltrimethoxysilane is preferably used to form the primer layer (Y).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-120253 Summary of the Invention

[0009] In order to maintain good water repellency in a laminate having a water-repellent layer on a substrate, it is required to have good abrasion resistance when evaluated from the side of the water-repellent layer exposed to the surface. Therefore, an object of the present invention is to provide a laminate having excellent abrasion resistance, comprising a substrate, an intermediate layer, and a water-repellent layer laminated in this order.

[0010] The present invention for achieving the above-mentioned objects is as follows.

[0011] [1] A laminate comprising, in this order, a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r);

[0012] The intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) having silicon atoms and an amino group and / or an amine skeleton, or a vapor-deposited layer of the organosilicon compound (C).

[0013] 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.

[0014] The laminated body satisfies the following requirement (1).

[0015] (1) After an abrasion resistance test in which a load of 200 g is applied to the water-repellent layer (r) side surface of the laminate per an area of 1.5 cm×1.5 cm and the laminate is rubbed 20,000 times, the water sliding-off angle is 50° or less.

[0016] [2] The laminate according to [1], wherein the organosilicon compound (A) is at least one organosilicon compound represented by the following formula (a1).

[0017]

[0018] In the above formula (a1),

[0019] Rf a1 It is a divalent perfluoropolyether structure with oxygen atoms at both ends.

[0020] R 11 、R 12 and R 13 are each independently an alkyl group having 1 to 20 carbon atoms, R 11 When there are multiple, multiple R 11 Can be different, R 12 When there are multiple, multiple R 12 Can be different, R 13 When there are multiple, multiple R 13 Can be different,

[0021] E 1 、E 2 、E 3 、E 4 and E 5 are each independently a hydrogen atom or a fluorine atom, E 1 When there are multiple, multiple E 1 Can be different, E 2 When there are multiple, multiple E 2 Can be different, E 3 When there are multiple, multiple E 3Can be different, E 4 When there are multiple, multiple E 4 Can be different,

[0022] G 1 and G 2 are each independently a di- to decavalent organosiloxane group having a siloxane bond,

[0023] J 1 、J 2 and J 3 Each independently a hydrolyzable group or -(CH2) e6 -Si(OR 14 )3, e6 is 1 to 5, R 14 is methyl or ethyl, J 1 When there are multiple, multiple J 1 Can be different, J 2 When there are multiple, multiple J 2 Can be different, J 3 When there are multiple, multiple J 3 Can be different,

[0024] L 1 and L 2 Each independently represents a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom or a fluorine atom, L 1 When there are multiple L 1 Can be different, L 2 When there are multiple L 2 Can be different,

[0025] d11 is 1 to 9,

[0026] d12 is 0 to 9,

[0027] a10 and a14 are each independently 0 to 10,

[0028] a11 and a15 are each independently 0 or 1,

[0029] a12 and a16 are each independently 0 to 9,

[0030] a13 is 0 or 1,

[0031] a21, a22 and a23 are each independently 0 to 2,

[0032] e1, e2 and e3 are each independently 1 to 3.

[0033] [3] The laminate according to [1] or [2], wherein the mixed composition (ca) further contains at least one organosilicon compound (B) represented by the following formula (b1).

[0034]

[0035] In the above formula (b1),

[0036] Rf b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, or a fluorine atom,

[0037] R b11 、R b12 、R b13 and R b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R b11 When there are multiple, multiple R b11 Can be different, R b12 When there are multiple, multiple R b12 Can be different, R b13 When there are multiple, multiple R b13 Can be different, R b14 When there are multiple, multiple R b14 Can be different,

[0038] Rf 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, Rf b11 When there are multiple, multiple Rf b11 Can be different, Rf b12 When there are multiple, multiple Rf b12 Can be different, Rf b13 When there are multiple, multiple Rf b13 Can be different, Rf b14 When there are multiple, multiple Rf b14 Can be different,

[0039] R b15 is an alkyl group with 1 to 20 carbon atoms, R b15 When there are multiple, multiple R b15 Can be different,

[0040] A 1 is -O-, -C(=O)-O-, -O-C(=O)-, -NR-, -NRC(=O)- or -C(=O)NR-, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, and A 1 When there are multiple A 1 Can be different,

[0041] A 2 A is a hydrolyzable group. 2 When there are multiple A 2 Can be different,

[0042] b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100,

[0043] c is an integer from 1 to 3,

[0044] Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c 、b11-{C(R b11 )(R b12 )}-、b12 -{C(Rf b11 )(Rf b12 )}-、b13-{Si(R b13 )(R b14 )}-、b14-{Si(Rf b13 )(Rf b14 )}-、b15 -A 1 -As long as Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c The -O- radicals are not connected to -O- or -F, and the radicals are arranged and bonded in any order.

[0045] [4] The laminate according to [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.

[0046] [5] The laminate according to any one of [1] to [4], wherein a hydrolyzable group or a hydroxyl group is bonded to at least one silicon atom in the organosilicon compound (C).

[0047] [6] The laminate according to any one of [1] to [5], wherein the organosilicon compound (C) is an organosilicon compound represented by any one of the following formulae (c1) to (c3).

[0048]

[0049] In the above formula (c1),

[0050] R x11 、R x12、R x13 、R x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x11 When there are multiple, multiple R x11 Can be different, R x12 When there are multiple, multiple R x12 Can be different, R x13 When there are multiple, multiple R x13 Can be different, R x14 When there are multiple, multiple R x14 Can be different,

[0051] Rf 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, Rf x11 When there are multiple, multiple Rf x11 Can be different, Rf x12 When there are multiple, multiple Rf x12 Can be different, Rf x13 When there are multiple, multiple Rf x13 Can be different, Rf x14 When there are multiple, multiple Rf x14 Can be different,

[0052] R x15 is an alkyl group with 1 to 20 carbon atoms, R x15 When there are multiple, multiple R x15 Can be different,

[0053] X 11 is a hydrolyzable group, X 11 When there are multiple, multiple X 11 Can be different,

[0054] Y 11 is -NH- or -S-, Y 11 When there are multiple, multiple Y 11 Can be different,

[0055] 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,

[0056] 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.

[0057] p6 is an integer from 1 to 3,

[0058] 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,

[0059] 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 not connected to -O-, the bonds can be arranged in any order.

[0060]

[0061] In the above formula (c2),

[0062] R x20 and R x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x20 When there are multiple, multiple R x20 Can be different, R x21 When there are multiple, multiple R x21 Can be different,

[0063] Rf 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, Rf x20 When there are multiple, multiple Rf x20 Can be different, Rf x21 When there are multiple, multiple Rf x21 Can be different,

[0064] R x22 and R x23are each independently an alkyl group having 1 to 20 carbon atoms, R x22 and R x23 When there are multiple, multiple R x22 and R x23 Can be different,

[0065] X 20 and X 21 are each independently a hydrolyzable group, X 20 and X 21 When there are multiple, multiple X 20 and X 21 Can be different,

[0066] p20 is an integer of 1 to 30, and p21 is an integer of 0 to 30, and at least one of the repeating units enclosed in parentheses and labeled with p20 or p21 is substituted with an amine skeleton -NR 100 -, R in the above amine skeleton 100 is a hydrogen atom or an alkyl group,

[0067] p22 and p23 are each independently an integer of 1 to 3,

[0068] p20-{C(R x20 )(R x21 )}-、p21 -{C(Rf x20 )(Rf x21 )}- does not need p20 or p21 to be continuous, and can be bonded in any order, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 .

[0069]

[0070] In the above formula (c3),

[0071] Z 31 , Z 32 are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group,

[0072] R x31 、R x32 、R x33 、R x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x31 When there are multiple, multiple R x31 Can be different, R x32When there are multiple, multiple R x32 Can be different, R x33 When there are multiple, multiple R x33 Can be different, R x34 When there are multiple, multiple R x34 Can be different,

[0073] Rf 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, Rf x31 When there are multiple, multiple Rf x31 Can be different, Rf x32 When there are multiple, multiple Rf x32 Can be different, Rf x33 When there are multiple, multiple Rf x33 Can be different, Rf x34 When there are multiple, multiple Rf x34 Can be different,

[0074] Y 31 is -NH-, -N(CH3)- or -O-, Y 31 When there are multiple, multiple Y 31 Can be different,

[0075] X 31 、X 32 、X 33 、X 34 Each independently is -OR c (R c A hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an amino group C 1-3 Alkyl di-C 1-3 Alkoxysilyl), X 31 When there are multiple, multiple X 31 Can be different, X 32 When there are multiple, multiple X 32 Can be different, X 33 When there are multiple, multiple X 33 Can be different, X 34 When there are multiple, multiple X 34 Can be different,

[0076] 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.

[0077] As long as Z 31 and Z 32 At least one of Y is amino, or 31 At least one of them is -NH- or -N(CH3)-, and the terminal is Z 31 - and Z 32 -, -O- is not connected with -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 composed by arranging bonds in any order.

[0078] [7] The laminate according to any one of [1] to [6], wherein the organosilicon compound (A) is a compound represented by the following formula (a3) or (a4), and the organosilicon compound (C) is a compound represented by the following formula (c1-2) or (c2-2).

[0079]

[0080] In the above formula (a3), R 30 is a perfluoroalkyl group with 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 It is an alkyl group having 1 to 3 carbon atoms.

[0081]

[0082] In the above formula (a4), R 40 is a perfluoroalkyl group with 2 to 5 carbon atoms, R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms, R 42 It is a fluoroalkylene group in which a part of the hydrogen atoms of an alkylene group having 2 to 5 carbon atoms is substituted with fluorine, and R 43 、R 44 are each independently an alkylene group having 2 to 5 carbon atoms, R 45k1, k2, and k3 are each independently an integer of 1 to 5.

[0083] Z 12 -C q H 2q -Y 12 -C r H 2r -si(x 12 ) p (R x16 ) 3-p …(c1-2)

[0084] In the above formula (c1-2), X 12 is a hydrolyzable group, X 12 When there are multiple, multiple X 12 Can be different, Y 12 is -NH-, Z 12 is amino or thiol, R x16 is an alkyl group with 1 to 20 carbon atoms, R x16 When there are multiple, multiple R x16 They may be different from each other, p is an integer of 1 to 3, q is an integer of 2 to 5, and r is an integer of 0 to 5.

[0085] (R x25 ) 3-p25 (X 23 ) p25 Si-C w H 2w -Si(X 22 ) p24 (R x24 ) 3-p24 (c2-2)

[0086] In the above formula (c2-2), X 22 and X 23 are each independently a hydrolyzable group, X 22 and X 23 When there are multiple, multiple X 22 and X 23 Can be different, R x24 and R x25 are each independently an alkyl group having 1 to 20 carbon atoms, R x24 and R x25 When there are multiple, multiple R x24 and R x25 Can be different, for -C w H 2w -, at least one of the methylene groups in a part thereof is substituted with an amine skeleton -NR 100 -, R 100is a hydrogen atom or an alkyl group, w is an integer of 1 to 30 (excluding the number of methylene groups substituted with the amine skeleton), and p24 and p25 are each independently an integer of 1 to 3)

[0087] [8] The laminate according to any one of [1] to [7], wherein the properties measured on the surface of the water-repellent layer further satisfy at least one of the following requirements (1') and (3).

[0088] (1′) The contact angle of water after the abrasion resistance test is 90° or greater.

[0089] (3) The initial sliding angle of water is less than 21°.

[0090] [9] The laminate according to any one of [1] to [8], wherein the characteristics measured on the surface of the water-repellent layer further satisfy the requirement of the following (4).

[0091] (4) The coefficient of dynamic friction after the wear resistance test is 0.40 or less.

[0092]

[10] The laminate according to any one of [1] to [9], wherein the surface F content of the water-repellent layer (r) side surface of the laminate measured by XPS is 5 atomic % or more, and the N content is 0.15 atomic % or more.

[0093]

[11] A laminate according to any one of [1] to

[10] , wherein the ratio of the absolute value of the arithmetic mean height Sa(c) of the above-mentioned intermediate layer (c) before laminating the above-mentioned water-repellent layer (r) to the absolute value of the arithmetic mean height Sa(s) of the above-mentioned substrate (s) before laminating the above-mentioned intermediate layer (c) (absolute value of Sa(c) / absolute value of Sa(s)) is less than 100%.

[0094]

[12] The laminate according to any one of [1] to

[11] , wherein the substrate (s) has an antireflection layer formed on a glass layer or a resin layer.

[0095]

[13] A spectacle lens comprising the laminate according to any one of [1] to

[12] .

[0096]

[14] A method for producing a laminate comprising, in order: a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r);

[0097] The above manufacturing method includes the following steps:

[0098] a step of applying a mixed composition (cc) of an organosilicon compound (C) represented by any one of the formulae (c1) to (c3) on the antireflection layer of the substrate (s) having the antireflection layer,

[0099] a step of applying a mixed composition (ca) of the organosilicon compound (A) represented by the formula (a1) onto the coating surface of the mixed composition (cc); and

[0100] The mixed composition (cc) and the mixed composition (ca) are cured to form the intermediate layer (c) from the coating layer of the mixed composition (cc), and the water-repellent layer (r) from the coating layer of the mixed composition (ca).

[0101]

[15] A method for producing a laminated body, characterized in that the laminated body comprises, in order: a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r);

[0102] The above manufacturing method includes the following steps:

[0103] a step of forming the intermediate layer (c) by vapor-depositing the organosilicon compound (C) represented by any one of the formulae (c1) to (c3) on the anti-reflection layer of the substrate (s) having the anti-reflection layer,

[0104] A step of applying a mixed composition (ca) of the organosilicon compound (A) represented by the formula (a1) on the intermediate layer (c) and curing the mixed composition (ca) to form the water-repellent layer (r) from the coating layer of the mixed composition (ca).

[0105]

[16] A method for producing a laminate according to

[14] or

[15] , wherein the anti-reflection layer of the substrate (s) is subjected to a hydrophilic treatment before the application of the mixed composition (cc) or before the vapor deposition of the organosilicon compound (C), and the mixed composition (cc) is applied to the hydrophilicized surface or the organosilicon compound (C) is vapor deposited.

[0106] The laminate of the present invention comprising a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r) in this order has excellent abrasion resistance. DETAILED DESCRIPTION

[0107] The laminate of the present invention is a laminate comprising, in this order, a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r).

[0108] The intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) having an amino group and / or an amine skeleton or a vapor-deposited layer of the organosilicon compound (C).

[0109] 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, and the laminate satisfies the following requirement (1).

[0110] (1) After an abrasion resistance test in which a load of 200 g is applied to the water-repellent layer (r) side surface of the laminate per an area of 1.5 cm×1.5 cm and the laminate is rubbed 20,000 times, the water sliding-off angle is 50° or less.

[0111] The laminate of the present invention that satisfies the above requirements can achieve excellent wear resistance.

[0112] In the above requirement (1), the water drop angle is preferably 40° or less, more preferably 30° or less, further preferably 20° or less, and further preferably 10° or less. Alternatively, the water drop angle may be 1° or more.

[0113] 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 the laminate is wiped 20,000 times. When wiping, it is preferably wiped with paper made of pulp raw material, and more preferably wiped with paper made of pulp raw material attached to an elastomer. As the paper made of pulp raw material, 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 back and forth / minute, and measure the slip 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. Laminates having a water-repellent layer (r) of a size less than 1.5 cm × 1.5 cm are also included in the scope of the present invention.

[0114] The laminate of the present invention preferably further satisfies the following requirement (2).

[0115] (2) The reflectivity measured on the surface of the water-repellent layer (r) side is: (2-i) a reflectivity obtained by subtracting the surface reflection loss and the back reflection loss from the reflectivity obtained by calculating the spectral reflectivity at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° according to JIS Z8701 with a 2-degree field of view (light source C) of 5.0% or less, or (2-ii) a reflectivity at a wavelength of 530 nm converted to D65 light source and a 10° field of view using a halogen lamp with a 10x objective lens is 5.0% or less.

[0116] In the above requirement (2), the reflectivity (including both the reflectivities defined in (2-i) and (2-ii) above) is preferably 4.0% or less, more preferably 3.5% or less, further preferably 3.0% or less, and further preferably 2.5% or less. For example, the reflectivity may be 1.0% or more.

[0117] In addition, the laminate of the present invention preferably further satisfies at least any one of the following requirements (1′), (3) and (4) when measured on the surface of the water-repellent layer side, more preferably satisfies (1′) and (3), and even more preferably satisfies (1′), (3) and (4).

[0118] (1′) The contact angle of water after the abrasion resistance test is 90° or greater.

[0119] The water contact angle after the abrasion resistance test is more preferably 95° or greater, further preferably 100° or greater, and further preferably 110° or greater. The water contact angle may be, for example, 130° or less.

[0120] (3) The initial sliding angle of water is less than 21°.

[0121] The initial water sliding angle in requirement (3) refers to the water sliding angle measured before the wear resistance test. The initial water sliding angle is more preferably 20° or less, further preferably 15° or less, and further preferably 10° or less. The initial water sliding angle may be 0.5° or more.

[0122] (4) The coefficient of dynamic friction after the wear resistance test is 0.40 or less.

[0123] The dynamic friction coefficient after the wear resistance test is more preferably 0.35 or less, further preferably 0.30 or less, and further preferably 0.25 or less. The dynamic friction coefficient may be 0.10 or more.

[0124] The initial dynamic friction coefficient (ie, before the wear resistance test) is preferably 0.35 or less, more preferably 0.30 or less, further preferably 0.25 or less, and may be 0.10 or more.

[0125] In addition, it is preferred that the amount of F on the surface of the water-repellent layer (r) side of the above-mentioned laminate measured by XPS is 5 atomic % or more, and the amount of N is 0.15 atomic % or more. By satisfying such requirements, at least one of the initial water repellency, initial water sliding properties, and wear resistance (water repellency, water sliding properties, and reduction in dynamic friction coefficient after the wear resistance test) of the water-repellent layer (r) side surface can be made good. The amount of F is more preferably 10 atomic % or more, further preferably 25 atomic % or more, further preferably 40 atomic % or more, and can be 70 atomic % or less. The amount of N is more preferably 0.5 atomic % or more, further preferably 1.0 atomic % or more, further preferably 2.0 atomic % or more, and can be 10 atomic % or less.

[0126] Hereinafter, the substrate (s) having an antireflection layer, the intermediate layer (c), and the water-repellent layer (r) constituting the laminate of the present invention will be described in order.

[0127] 1. Substrate(s)

[0128] The material of the substrate (s) other than the antireflection layer (ar) is not particularly limited and may be any of organic and inorganic materials, as long as the antireflection layer (ar) is provided on at least one side. Examples of organic materials include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, and vinyl resins (polyethylene, polyvinyl chloride, polystyrene, vinylbenzyl chloride resins, polyvinyl alcohol, etc.); and thermosetting resins such as phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, or alloys containing these metals, ceramics, and glass.

[0129] The laminate of the present invention can be used, for example, in eyeglass lenses. In this case, the substrate (s) preferably has an antireflection layer (ar) formed on a glass layer (sg) or a resin layer (sp). The antireflection layer (ar) is preferably formed at least on the side of the intermediate layer (c). As the resin layer (sp), allyl diglycol carbonate resin, polycarbonate resin, thiourethane resin, episulfide resin, etc. can be used. A primer layer and / or a hard coat layer may be formed between the glass layer (sg) or the resin layer (sp) and the antireflection layer (ar).

[0130] The primer layer is a layer that improves the adhesion between two layers stacked via the primer layer, and a known material can be used.

[0131] The hard coating layer imparts scratch resistance to the glass layer (sp) or the resin layer (sg), and exhibits a hardness of H or higher using a pencil hardness tester according to the test method specified in JIS K5600. As the hard coating layer, known hard coatings can be used, for example, organic hard coatings, inorganic hard coatings, and organic-inorganic hybrid hard coatings.

[0132] The anti-reflection layer (ar) is a layer having the function of preventing the reflection of incident light, and is a layer showing a reflective characteristic of reducing the reflectivity to about 5.0% or less in the visible light region of 530nm. The reflectivity of the anti-reflection layer (ar) can also be measured by the above-mentioned method (2-i) or (2-ii) which is the same as the reflectivity measured on the side surface of the water-repellent layer (r). The structure of the anti-reflection layer (ar) is not particularly limited, and it can be a single-layer structure or a multi-layer structure. In the case of a multi-layer structure, a structure in which a low refractive index layer and a high refractive index layer are alternately stacked is preferred. As materials constituting the high refractive index layer, oxides of titanium, zirconium, aluminum, tantalum or lanthanum can be mentioned, and as materials constituting the low refractive index layer, silicon dioxide can be mentioned. As an anti-reflection layer (ar) of a multi-layer structure, a structure in which 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 SiO2 is preferred. The anti-reflection layer (ar) can be formed, for example, by a vapor deposition method.

[0133] 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.

[0134] 2. Middle layer (c)

[0135] The intermediate layer (c) is a layer having silicon atoms and an amino group or an amine skeleton (is -NR 100 -, R 100The intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) containing a hydrogen atom or an alkyl group, or a vapor-deposited layer of the organosilicon compound (C), wherein the intermediate layer (c) has 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 of the organosilicon compound (C) or the -SiOH groups of the organosilicon compound (C) generated by hydrolysis of the hydrolyzable groups bonded to the silicon atom are dehydrated and condensed with each other. Therefore, the intermediate layer (c) preferably has a condensation structure derived from the organosilicon compound (C). The intermediate layer (c) can function as a primer layer for the water-repellent layer (r). Examples of the hydrolyzable group bonded to the silicon atom of the organosilicon compound (C) include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group. Preferably, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group is bonded to the silicon atom of the organosilicon compound (C).

[0136] 2-1. Organosilicon compound (C) represented by formula (c1) (hereinafter referred to as organosilicon compound (C1))

[0137]

[0138] In the above formula (c1),

[0139] R x11 、R x12 、R x13 、R x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x11 When there are multiple, multiple R x11 Can be different, R x12 When there are multiple, multiple R x12 Can be different, R x13 When there are multiple, multiple R x13 Can be different, R x14 When there are multiple, multiple R x14 Can be different,

[0140] Rf 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, Rf x11 When there are multiple, multiple Rf x11 Can be different, Rf x12 When there are multiple, multiple Rf x12 Can be different, Rf x13 When there are multiple, multiple Rf x13 Can be different, Rfx14 When there are multiple, multiple Rf x14 Can be different,

[0141] R x15 is an alkyl group with 1 to 20 carbon atoms, R x15 When there are multiple, multiple R x15 Can be different,

[0142] X 11 is a hydrolyzable group, X 11 When there are multiple, multiple X 11 Can be different,

[0143] Y 11 is -NH- or -S-, Y 11 When there are multiple, multiple Y 11 Can be different,

[0144] 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,

[0145] 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.

[0146] p6 is an integer from 1 to 3,

[0147] 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,

[0148] 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 not connected to -O-, the bonds can be arranged in any order.

[0149] R x11 、R x12 、R x13 and R x14 Preferred is a hydrogen atom.

[0150] Rf x11 、Rf x12 、Rf x13 and Rf x14 Preferably, each independently represents 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.

[0151] R x15 An alkyl group having 1 to 5 carbon atoms is preferred.

[0152] 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.

[0153] Y 11 Preferred is -NH-.

[0154] 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.

[0155] 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.

[0156] As the organosilicon compound (C), the following compounds are preferably used: x11 and R x12 are all hydrogen atoms, Y 11 is -NH-, X 11 is an alkoxy group (especially a methoxy group or an ethoxy group), 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.

[0157] The organosilicon compound (C1) is preferably represented by the following formula (c1-2).

[0158] Z 12 -C q H 2q -Y 12 -C r H 2r-Si(X 12 ) p (R x16 ) 3-p …(c1-2)

[0159] In the above formula (c1-2),

[0160] X 12 is a hydrolyzable group, X 12 When there are multiple, multiple X 12 Can be different,

[0161] Y 12 is -NH-,

[0162] Z 12 is an amino group or a thiol group,

[0163] R x16 is an alkyl group with 1 to 20 carbon atoms, R x16 When there are multiple, multiple R x16 Can be different,

[0164] p is an integer of 1-3, q is an integer of 2-5, and r is an integer of 0-5.

[0165] X 12 An alkoxy group, a halogen atom, a cyano group or an isocyanate group is preferred, and an alkoxy group is more preferred.

[0166] Z 12 An amino group is preferred.

[0167] 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.

[0168] p is preferably an integer of 2 to 3, more preferably 3.

[0169] q is preferably an integer of 2-3, and r is preferably an integer of 2-4.

[0170] 2-2. Organosilicon compound (C) represented by formula (c2) (hereinafter referred to as organosilicon compound (C2))

[0171]

[0172] In the above formula (c2),

[0173] R x20 and R x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x20 When there are multiple, multiple R x20 Can be different, R x21 When there are multiple, multiple Rx21 Can be different,

[0174] Rf 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, Rf x20 When there are multiple, multiple Rf x20 Can be different, Rf x21 When there are multiple, multiple Rf x21 Can be different,

[0175] R x22 and R x23 are each independently an alkyl group having 1 to 20 carbon atoms, R x22 and R x23 When there are multiple, multiple R x22 and R x23 Can be different,

[0176] X 20 and X 21 are each independently a hydrolyzable group, X 20 and X 21 When there are multiple, multiple X 20 and X 21 Can be different,

[0177] p20 is an integer of 1 to 30, and p21 is an integer of 0 to 30, and at least one of the repeating units enclosed in parentheses and labeled with p20 or p21 is substituted with an amine skeleton -NR 100 -, R in the above amine skeleton 100 is a hydrogen atom or an alkyl group,

[0178] p22 and p23 are each independently an integer of 1 to 3,

[0179] p20-{C(R x20 )(R x21 )}-、p21 -{C(Rf x20 )(Rf x21 )}-does not require p20 or p21 to be continuous, and can be bonded in any order, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 .

[0180] R x20 and R x21 Preferred is a hydrogen atom.

[0181] Rf x20 and Rf x21 Preferably, each independently represents 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.

[0182] R x22 and R x23 An alkyl group having 1 to 5 carbon atoms is preferred.

[0183] 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.

[0184] Amine skeleton-NR 100 As described above, as long as at least one is present in the molecule, any of the parenthesized repeating units labeled p20 or p21 may be substituted with the above-mentioned amine backbone, preferably a portion of the parenthesized repeating unit labeled p20. Multiple amine backbones may be present, and the number of amine backbones in this case is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. Furthermore, in this case, an alkylene group preferably exists between adjacent amine backbones, and the number of carbon atoms in such alkylene group is preferably 1 to 10, more preferably 1 to 5. The number of carbon atoms in the alkylene group between adjacent amine backbones is included in the total number of p20 or p21.

[0185] 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).

[0186] p20 is preferably 1-15, more preferably 1-10, excluding the number of repeating units substituted with an amine skeleton.

[0187] p21, excluding the number of repeating units substituted with an amine skeleton, is preferably 0 to 5, and more preferably all of them are 0 to 2.

[0188] p22 and p23 are preferably 2 to 3, more preferably 3.

[0189] 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 (especially a methoxy group or an ethoxy group), and at least one of the repeating units enclosed in parentheses and marked with p20 is substituted with an amine skeleton -NR100 -, R 100 is a hydrogen atom, p20 is 1 to 10 (excluding the number of repeating units substituted with an amine skeleton), p21 is 0, and p22 and p23 are 3.

[0190] In addition, the reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in Japanese Patent Application Laid-Open No. 2012-197330 (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) used as compound (C) in the examples described below is represented by the above formula (c2), then R x20 and R x21 are all hydrogen atoms, p20 is 8, p21 is 0, and the amine skeleton is 2 (R 100 are hydrogen atoms), the two ends are identical, p22 and p23 are 3 and X 20 and X 21 It is a methoxy group.

[0191] The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

[0192] (R x25 ) 3-p25 (X 23 ) p25 Si-C w H 2w -Si(X 22 ) p24 (R x24 ) 3-p24 (c2-2)

[0193] In the above formula (c2-2),

[0194] X 22 and X 23 are each independently a hydrolyzable group, X 22 and X 23 When there are multiple, multiple X 22 and X 23 Can be different,

[0195] R x24 and R x25 are each independently an alkyl group having 1 to 20 carbon atoms, R x24 and R x25 When there are multiple, multiple R x24 and R x25 Can be different,

[0196] For -C w H 2w -, at least one of the methylene groups in a part thereof is substituted with an amine skeleton -NR100 -, R 100 is a hydrogen atom or an alkyl group,

[0197] w is an integer of 1 to 30 (excluding the number of methylene groups substituted with the amine skeleton), and p24 and p25 are each independently an integer of 1 to 3.

[0198] 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.

[0199] Amine skeleton-NR 100 - may be present in multiple groups. In this case, the number of amine backbones is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. Furthermore, in this case, an alkylene group is preferably present between adjacent amine backbones. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5. The number of carbon atoms in the alkylene group between adjacent amine backbones is included in the total number of w.

[0200] 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).

[0201] 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.

[0202] p24 and p25 are preferably integers of 2 to 3, and more preferably 3.

[0203] w is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.

[0204] 2-3. Organosilicon compound (C) represented by formula (c3) (hereinafter referred to as organosilicon compound (C3))

[0205]

[0206] In the above formula (c3),

[0207] 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.

[0208] R x31 、R x32 、R x33 、R x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x31 When there are multiple, multiple R x31 Can be different, R x32 When there are multiple, multiple R x32 Can be different, R x33 When there are multiple, multiple R x33 Can be different, R x34 When there are multiple, multiple 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.

[0209] Rf 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, Rf x31 When there are multiple, multiple Rf x31 Can be different, Rf x32 When there are multiple, multiple Rf x32 Can be different, Rf x33 When there are multiple, multiple Rf x33 Can be different, Rf x34 When there are multiple, multiple Rf x34 Can be different. x31 、Rf x32 、Rf x33 、Rf x34 An alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom is preferred.

[0210] Y 31 is -NH-, -N(CH3)- or -O-, Y 31 When there are multiple, multiple Y 31 Can be different. 31 Preferred is -NH-.

[0211] X 31 、X 32 、X33 、X 34 Each independently is -OR c (R c A hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an amino group C 1-3 Alkyl di-C 1-3 Alkoxysilyl), X 31 When there are multiple, multiple X 31 Can be different, X 32 When there are multiple, multiple X 32 Can be different, X 33 When there are multiple, multiple X 33 Can be different, X 34 When there are multiple, multiple X 34 Can be different. X 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 , R c A hydrogen atom is more preferred.

[0212] p31 is an integer from 0 to 20, p32, p33, and p34 are each independently an integer from 0 to 10, p35 is an integer from 0 to 5, p36 is an integer from 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 0 to 2. p35 is preferably 1 to 5, more preferably 1 to 3. p36 is preferably 1 to 5, more preferably 1 to 3. p37 is preferably 1.

[0213] As long as the organosilicon compound (C3) satisfies Z 31 and Z 32 At least one of Y is amino, or 31 At least one of them is -NH- or -N(CH3)-, and the terminal is Z 31 - and Z 32 -, -O- is not connected with -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(X31 )(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 )}- continuous bonding may be carried out through other units in the middle, as long as the total number is p31. The same applies to the units bracketed by p32 to p37.

[0214] As the organosilicon compound (C3), the following compounds are preferred: 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 are all hydrogen atoms, Rf x31 ~Rf x34 are all alkyl groups having 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, and 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.

[0215] The organosilicon compound (C3) is preferably represented by the following formula (c3-2).

[0216]

[0217] In the above formula (c3-2), 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 meanings, p41 to p44 are each independently an integer of 1 to 6, and p45 and 46 are each independently 0 or 1.

[0218] In formula (c3-2), Z 31 and Z32 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 , R c More preferably, it is a hydrogen atom. 31 p41 to p44 are preferably 2 or more, and preferably 5 or less, more preferably 4 or less. p45 and p46 are both preferably 0.

[0219] The mixed composition (cc) is a composition mixed with an organosilicon compound (C). The mixed composition (cc) is obtained by mixing the organosilicon compound (C). When components other than the organosilicon compound (C) are mixed, the mixed composition (cc) is obtained by mixing the other components with the organosilicon compound (C). The mixed composition (cc) also includes products obtained by reacting after mixing, for example, during storage.

[0220] As an example of the reaction during storage of the mixed composition (cc), the mixed composition (cc) includes a condensate of the organosilicon compound (C), and more specifically, the mixed composition (cc) includes the organosilicon compound (C3) in the above X. 31 ~X 34 An organosilicon compound (C3′) obtained by condensing and bonding at least any one of

[0221] The organosilicon compound (C3') is a compound having two or more structures (c31-1) represented by the following formula (c31-1), wherein the structures (c31-1) are bonded to each other at *3 or *4 to form a chain or ring, and the bond at *3 or *4 is based on the above X of the two or more organosilicon compounds (C3). 31 or X 32 The condensation of

[0222] In the following formula (c31-1), *1 and *2 are each bonded to at least one of the units enclosed by p31, p32, p33, p34, p35, (p36)-1, and p37 of the following formula (c31-2), which are bonded in any order and terminate in a Z-group. In a plurality of structures (c31-1), the groups bonded to *1 and *2 may be different.

[0223] When a plurality of the above structures (c31-1) are linked to form a chain, *3 serving as a terminal is a hydrogen atom, and *4 is a hydroxyl group.

[0224]

[0225] In the above formula (c31-2),

[0226] Z is a reactive functional group other than a hydrolyzable group and a hydroxyl group,

[0227] R x31 、R x32 、R x33 、R x34 、Rf x31 、Rf x32 、Rf x33 、Rf 34 、Y 31 、X 31 、X 32 、X 33 、X 34 , p31 to p37 have the same meanings as those in the above formula (c3).

[0228] When the organosilicon compound (C3) is a compound represented by the above formula (c3-2), examples of the organosilicon compound (C3') include compounds having a structure represented by the following formula (c31-3) in which the following *3 or *4 are bonded to form a chain or ring. When the structure represented by the following formula (c31-3) is bonded to form a chain, the terminal *3 is a hydrogen atom, and the terminal *4 is a hydroxyl group.

[0229]

[0230] All the symbols in the above formula (c31-3) have the same meanings as those in the above formula (c3-2).

[0231] The organosilicon compound (C3′) is preferably a compound in which 2 to 10 (preferably 3 to 8) structures represented by the above formula (c31-3) are bonded.

[0232] As the organosilicon compound (C), only one type may be used, or two or more types may be used. As the organosilicon compound (C), it is preferred to use at least the organosilicon compound (C1) and / or the organosilicon compound (C2), and it is more preferred to use at least the organosilicon compound (C2).

[0233] The mixed composition (cc) is preferably mixed with a solvent (E). The solvent (E) is not particularly limited, and examples thereof include water, alcoholic solvents, ketone solvents, etheric solvents, hydrocarbon solvents, and ester solvents. Water, alcoholic solvents, ketone solvents, and hydrocarbon solvents are particularly preferred.

[0234] Examples of the alcoholic solvent include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), and 1-butanol.

[0235] Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0236] Examples of the ether solvent include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dihydrofuran, Alkane, etc.

[0237] Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as pentane and hexane, alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0238] Examples of the ester solvent include ethyl acetate, propyl acetate, and butyl acetate.

[0239] The total amount of the organosilicon compound (C) when the composition (cc) as a whole is set to 100% by mass is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, further preferably 0.02% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less. The amount of the organosilicon compound (C) can be adjusted when preparing the composition. The amount of the organosilicon compound (C) can be calculated from the analysis results of the composition. It should be noted that in this specification, when the range of the amount, mass ratio or molar ratio of each component is recorded, the range can be adjusted when preparing the composition, as described above.

[0240] The thickness of the intermediate layer (c) is, for example, approximately 1 to 1000 nm.

[0241] 3. Water repellent layer (r)

[0242] The water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A). The mixed composition (ca) is more preferably a mixed composition of the organosilicon compound (A) and the organosilicon compound (B).

[0243] 3-1. Organic silicon compound (A)

[0244] The organosilicon compound (A) is a compound 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. The water-repellent layer (r) is obtained by applying and curing the composition (ca) and has a structure derived from the organosilicon compound (A). As described above, the organosilicon compound (A) has a hydrolyzable group bonded to a silicon atom (possibly bonded via a linking group). The -SiOH groups (Si and OH groups may be bonded via a linking group) of the organosilicon compound (A) generated by hydrolysis undergo dehydration condensation, resulting in the water-repellent layer (r) typically having a condensed structure derived from the organosilicon compound (A). Examples of the hydrolyzable group include alkoxy groups, halogen atoms, cyano groups, acetoxy groups, and isocyanate groups.

[0245] The above-mentioned perfluoropolyether structure can also be called perfluorooxyalkylene. The perfluoropolyether structure has liquid repellency such as water repellency or oil repellency. The number of carbon atoms contained in the longest straight chain part of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the above-mentioned number of carbon atoms is not particularly limited, for example, it can be about 200. The monovalent group having a perfluoropolyether structure of the above-mentioned organosilicon compound (A) preferably further has a perfluoroalkyl group at the free end.

[0246] The water-repellent layer (r) may also be a layer having a perfluoropolyether structure and a polysiloxane backbone, preferably further comprising a perfluoroalkyl group. The water-repellent layer (r) preferably comprises a structure in which a monovalent group having a perfluoroalkyl group and a perfluoropolyether structure is bonded to a portion of the silicon atoms of the polysiloxane backbone. The presence of the perfluoroalkyl group on the free end side improves water repellency.

[0247] The number of carbon atoms in the perfluoroalkyl group (particularly the number of carbon atoms in the longest linear chain) is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The upper limit of the number of carbon atoms is not particularly limited, and excellent water repellency is exhibited even when the number is approximately 20.

[0248] 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.

[0249] In the organosilicon compound (A), the monovalent group having a perfluoropolyether structure may be bonded to the silicon atom via an appropriate linking group, or the monovalent group having the perfluoropolyether structure may be directly bonded to the silicon atom without the linking group. Examples of the linking group include hydrocarbon groups such as alkylene groups and aromatic hydrocarbon groups, (poly)alkylene glycol groups, or groups in which a portion of their hydrogen atoms are substituted with F or a substituent, and groups formed by appropriately linking these groups. The number of carbon atoms in the linking group is, for example, 1 to 20, preferably 2 to 15.

[0250] The hydrolyzable group has the function of bonding the organosilicon compounds (A) to each other or to active hydrogen (hydroxyl groups, etc.) on the substrate surface through a hydrolysis-dehydration condensation reaction. Examples of such hydrolyzable groups include alkoxy groups (particularly alkoxy groups having 1 to 4 carbon atoms), hydroxyl groups, acetoxy groups, and halogen atoms (particularly chlorine atoms). Preferred hydrolyzable groups are alkoxy groups and halogen atoms, with methoxy groups, ethoxy groups, and chlorine atoms being particularly preferred.

[0251] The above-mentioned hydrolyzable group may be bonded to the silicon atom via a linking group, or may be 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, or 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 group is bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to the silicon atom is usually 4, or 2 or 3 (particularly 3). In the case of 3 or less, the remaining bonding sites 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. may be bonded.

[0252] The monovalent group having a perfluoropolyether structure in the organosilicon compound (A) may be linear or may have a side chain, but is preferably linear.

[0253] The organosilicon compound (A) can be represented by, for example, the following formula (a).

[0254]

[0255] 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-*, -CFD9 -*(* is D 2 side bonding site), D 2 is a single bond or a divalent hydrocarbon group not substituted with a fluorine atom, D 3 is a trivalent hydrocarbon group not substituted with a fluorine atom, a portion of the methylene group of the hydrocarbon group may be substituted with an oxygen atom, 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 includes the above-mentioned hydrolyzable groups.

[0256] The organosilicon compound (A) is preferably represented by the following formula (a1).

[0257]

[0258] In the above formula (a1),

[0259] Rf a1 It is a divalent perfluoropolyether structure with oxygen atoms at both ends.

[0260] R 11 、R 12 and R 13 Each independently (ie, R 11 With R 12 With R 13 may be the same or different) is an alkyl group having 1 to 20 carbon atoms, R 11 When there are multiple, multiple R 11 Can be different, R 12 When there are multiple, multiple R 12 Can be different, R 13 When there are multiple, multiple R 13 Can be different,

[0261] E 1 、E 2 、E 3 、E 4 and E 5 are each independently a hydrogen atom or a fluorine atom, E 1 When there are multiple, multiple E 1 Can be different, E 2 When there are multiple, multiple E 2 Can be different, E 3 When there are multiple, multiple E3 Can be different, E 4 When there are multiple, multiple E 4 Can be different,

[0262] G 1 and G 2 are each independently a di- to decavalent organosiloxane group having a siloxane bond,

[0263] J 1 、J 2 and J 3 Each independently a hydrolyzable group or -(CH2) e6 -Si(OR 14 )3, e6 is 1 to 5, R 14 is methyl or ethyl, J 1 When there are multiple, multiple J 1 Can be different, J 2 When there are multiple, multiple J 2 Can be different, J 3 When there are multiple, multiple J 3 Can be different,

[0264] L 1 and L 2 Each independently represents a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom or a fluorine atom, L 1 When there are multiple L 1 Can be different, L 2 When there are multiple L 2 Can be different,

[0265] d11 is 1 to 9,

[0266] d12 is 0 to 9,

[0267] a10 and a14 are each independently 0 to 10,

[0268] a11 and a15 are each independently 0 or 1,

[0269] a12 and a16 are each independently 0 to 9,

[0270] a13 is 0 or 1,

[0271] a21, a22 and a23 are each independently 0 to 2,

[0272] e1, e2 and e3 are each independently 1 to 3.

[0273] The organosilicon compound (A) is represented by the above formula (a1) and has Rf a1The perfluoropolyether structure represented by 2 Represents a hydrolyzable group or -(CH2) e6 -Si(OR 14 )3(where R 14 is methyl or ethyl). The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are replaced by fluorine atoms, also known as perfluorooxyalkylene, which can impart water repellency to the resulting film. In addition, the following compounds are present: 2 The organosilicon compounds (A) mentioned above can form a matrix of the obtained film by bonding with each other or with other monomers through a polymerization reaction (particularly a polycondensation reaction).

[0274] Rf a1 Preferred -O-(CF2CF2O) e4 -or-O-(CF2CF2CF2O) e5 -. e4 and e5 are both 15 to 80.

[0275] R 11 、R 12 and R 13 Preferably, each independently is an alkyl group having 1 to 10 carbon atoms.

[0276] L 1 and L 2 Preferably, each independently is a divalent linking group having 1 to 5 carbon atoms and containing a fluorine atom.

[0277] G 1 and G 2 Preferably, each independently is a di- to pentavalent organosiloxane group having a siloxane bond.

[0278] J 1 、J 2 and J 3 Preferably, each independently is methoxy, ethoxy or -(CH2) e6 -Si(OR 14 )3.

[0279] 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. Furthermore, a13 is preferably 1.

[0280] 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 with 1 to 3 carbon atoms, E 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 3 are all methoxy or ethoxy (especially methoxy), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 2 to 5, a15 is 0, a16 is 0 to 6, a21 to a23 are each independently 0 or 1 (more preferably, all a21 to a23 are 0), d11 is 1, d12 is 0 or 1, and e1 to e3 are all 3.

[0281] As the organosilicon compound (A), the following compounds are also preferably used: Rf 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.

[0282] Furthermore, the organosilicon compound (A) is preferably a compound represented by the following formula (a2-1).

[0283]

[0284] In the above formula (a2-1),

[0285] Rf a21 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, or a fluorine atom,

[0286] Rf a22 、Rf a23 、Rfa24 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, Rf a22 When there are multiple, multiple Rf a22 Can be different, Rf a23 When there are multiple, multiple Rf a23 Can be different, Rf a24 When there are multiple, multiple Rf a24 Can be different, Rf a25 When there are multiple, multiple Rf a25 Can be different,

[0287] R 20 、R 21 、R 22 and R 23 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 20 When there are multiple, multiple R 20 Can be different, R 21 When there are multiple, multiple R 21 Can be different, R 22 When there are multiple, multiple R 22 Can be different, R 23 When there are multiple, multiple R 23 Can be different,

[0288] R 24 is an alkyl group with 1 to 20 carbon atoms, R 24 When there are multiple, multiple R 24 Can be different,

[0289] M 1 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, M 1 When there are multiple, multiple M 1 Can be different,

[0290] M 2 is a hydrogen atom or a halogen atom,

[0291] M 3 are -O-, -C(=O)-O-, -O-C(=O)-, -NR-, -

[0292] 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), M 3 When there are multiple, multiple M 3 Can be different, M 4 is a hydrolyzable group, M 4When there are multiple, multiple M 4 Can be different,

[0293] 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.

[0294] f16 is an integer from 1 to 20.

[0295] f17 is an integer from 0 to 2,

[0296] g1 is an integer from 1 to 3,

[0297] Rf 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 a terminal, and is arranged in the order that at least a portion forms a perfluoropolyether structure, and -O- is not connected to -O- or -F, and is arranged in any 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 sequential arrangement, 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 arrange them in any order.

[0298] Rf 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.

[0299] Rf a22 、Rf a23 、Rf a24 and Rf a25 Preferably, each of the groups 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 the groups represent fluorine atoms.

[0300] R 20 、R 21 、R 22 and R 23 Preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably, all of them represent hydrogen atoms.

[0301] R 24 An alkyl group having 1 to 5 carbon atoms is preferred.

[0302] M 1 Preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably, all of them represent hydrogen atoms.

[0303] M 2 Preferred is a hydrogen atom.

[0304] M 3 Preferred are -C(=O)-O-, -O-, and -O-C(=O)-, and all are -O-.

[0305] M 4An alkoxy group or a halogen atom is preferred, and a methoxy group, an ethoxy group or a chlorine atom is more preferred.

[0306] Preferably, 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.

[0307] 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.

[0308] f12 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200 (even more preferably 30 to 150, particularly 50 to 150, and most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, and even more preferably 10 to 200 (even more preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200.

[0309] f16 is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 10.

[0310] f17 is preferably 0-1.

[0311] g1 is preferably 2 to 3, more preferably 3.

[0312] 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 - is arbitrary as long as at least a part of the perfluoropolyether structure is formed, but the repeating unit marked with f12 and enclosed in parentheses (i.e., -{C(Rf a22 )(Rf a23 )}-) the repeating unit enclosed in parentheses and marked f11 located on the side of the most free end (ie, -{C(R 20 )(R 21 )}-) the repeating units enclosed in parentheses and labeled f12 and f14, which are closer to the free end, and more preferably the most fixed end (ie, -{C(Rf a22 )(Rfa23 )}- and -{Si(Rf a24 )(Rf a25 )}-) is located on the free - end side of the marked f11 and f13 and the repeating units enclosed in parentheses (i.e., -{C(R 20 )(R 21 )}- and -{Si(R 22 )(R 23 )}-) is closer to the free - end side.

[0313] In the above formula (a2 - 1), preferably, Rf a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf a22 , Rf a23 , Rf a24 , Rf a25 are all fluorine atoms, M 3 are all -O-, M 4 are all methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M 1 , M 2 are both hydrogen atoms, f11 is 0, f12 is 30 to 150 (more preferably 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (especially 0), g1 is 3, and f16 is 1 to 10.

[0314] In addition, the organosilicon compound (A) is also preferably a compound represented by the following formula (a2 - 2).

[0315]

[0316] In the above formula (a2 - 2),

[0317] Rf a26 , Rf a27 , Rf a28 and Rf a29 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom. When there are multiple Rf a26 , the multiple Rf a26 can be different from each other. When there are multiple Rf a27 , the multiple Rf a27 can be different from each other. When there are multiple Rf a28 , the multiple Rf a28 can be different from each other. When there are multiple Rf a29 , the multiple Rf a29 can be different from each other.

[0318] R 25 , R 26 , R 27 and R28 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 25 When there are multiple, multiple R 25 Can be different, R 26 When there are multiple, multiple R 26 Can be different, R 27 When there are multiple, multiple R 27 Can be different, R 28 When there are multiple, multiple R 28 Can be different,

[0319] R 29 and R 30 are each independently an alkyl group having 1 to 20 carbon atoms, R 29 When there are multiple, multiple R 29 Can be different, R 30 When there are multiple, multiple R 30 Can be different,

[0320] M 7 are -O-, -C(=O)-O-, -O-C(=O)-, -NR-, -

[0321] 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 M 7 When there are multiple, multiple M 7 Can be different,

[0322] M 5 、M 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M 5 When there are multiple, multiple M 5 Can be different, M 9 When there are multiple, multiple M 9 Can be different,

[0323] M 6 and M 10 each independently a hydrogen atom or a halogen atom,

[0324] M 8 and M 11 are each independently a hydrolyzable group, M 8 When there are multiple, multiple M 8 Can be different, M 11 When there are multiple, multiple M 11 Can be different,

[0325] 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.

[0326] f26 and f28 are each independently an integer from 1 to 20,

[0327] f27 and f29 are each independently an integer from 0 to 2,

[0328] g2 and g3 are each independently an integer of 1 to 3,

[0329] 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 a terminal, and the perfluoropolyether structure is formed in at least a portion thereof. If -O- is not consecutive to -O-, the bonds are arranged in any order. The term "arranged in any order" is the same as that described in formula (a2-1) above and is not limited to the meaning that the repeating units are consecutive and arranged in the order shown in formula (a2-2) above.

[0330] In the above formula (a2-2), Rf is preferably 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), M5 、M 6 、M 9 and M 10 All 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.

[0331] More specifically, the organosilicon compound (A) includes a compound represented by the following formula (a3).

[0332]

[0333] In the above formula (a3), R 30 is a perfluoroalkyl group with 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 It is an alkyl group having 1 to 3 carbon atoms. 30 、R 31 、R 32 、R 33 The number of carbon atoms in each of the groups is preferably 2 to 4, 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.

[0334] Examples of the organosilicon compound (A) include compounds represented by the following formula (a4).

[0335]

[0336] In the above formula (a4), R 40 is a perfluoroalkyl group with 2 to 5 carbon atoms, R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms, R 42 It is a fluoroalkylene group in which a part of the hydrogen atoms of an alkylene group having 2 to 5 carbon atoms is substituted with fluorine, 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.

[0337] 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, and further preferably 15,000 or less.

[0338] Examples of the organosilicon compound (A) include compounds represented by the following formula (1) or compounds having a structure similar to the compound, and examples thereof include OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd.

[0339]

[0340] Examples of the compound represented by the formula (1) include compounds synthesized by the methods 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 approximately 8,000.

[0341] Examples of the similar structure include a structure 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 a fluorine atom is different, a structure in which the perfluoropolyether structure and the silicon atom are not bonded via a linking group, a structure in which another hydrocarbon group (including a hydrocarbon group in which at least a part of the hydrogen atoms are substituted with a fluorine atom) is interposed at any position of the linking group between the perfluoropolyether structure and the silicon atom, a structure in which the silicon atom and the hydrolyzable group are bonded via a linking group, and a structure in which the values of r and s are different. However, the structure is not limited to these structures.

[0342] As the organosilicon compound (A), only one type may be used, or two or more types may be used.

[0343] 3-2. Organic silicon compound (B)

[0344] The organosilicon compound (B) represented by the following formula (b1) has A as described below. 2 The hydrolyzable group represented by is generally a -SiOH group of the organosilicon compound (B) generated by hydrolysis, which undergoes dehydration condensation with the -SiOH group of the organosilicon compound (A) generated by hydrolysis and / or the -SiOH group of the organosilicon compound (B) generated by hydrolysis. 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, and an isocyanate group.

[0345]

[0346] In the above formula (b1),

[0347] Rf b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, or a fluorine atom,

[0348] R b11 、R b12 、R b13 、R b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R b11 When there are multiple, multiple R b11 Can be different, R b12 When there are multiple, multiple R b12 Can be different, R b13 When there are multiple, multiple R b13 Can be different, R b14 When there are multiple, multiple R b14 Can be different,

[0349] Rf 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, Rf b11 When there are multiple, multiple Rf b11 Can be different, Rf b12 When there are multiple, multiple Rf b12 Can be different, Rf b13 When there are multiple, multiple Rf b13 Can be different, Rf b14 When there are multiple, multiple Rf b14 Can be different,

[0350] R b15 is an alkyl group with 1 to 20 carbon atoms, R b15 When there are multiple, multiple R b15 Can be different,

[0351] A 1 are -O-, -C(=O)-O-, -O-C(=O)-, -NR-, -

[0352] 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 A 1 When there are multiple A 1 Can be different,

[0353] A 2 A is a hydrolyzable group.2 When there are multiple A 2 Can be different,

[0354] b11, b12, b13, b14, and b15 are each independently an integer of 0 to 100,

[0355] c is an integer from 1 to 3,

[0356] Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c 、b11-{C(R b11 )(R b12 )}-、b12 -{C(Rf b11 )(Rf b12 )}-、b13-{Si(R b13 )(R b14 )}-、b14-{Si(Rf b13 )(Rf b14 )}-、b15 -A 1 -As long as Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c The -O- radicals are not connected to -O- or -F, and the radicals are arranged and bonded in any order.

[0357] Rf b10 Each independently represents preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).

[0358] R b11 、R b12 、R b13 and R b14 A hydrogen atom is preferred.

[0359] R b15 An alkyl group having 1 to 5 carbon atoms is preferred.

[0360] A 1 Preferred is -O-, -C(=O)-O- or -O-C(=O)-.

[0361] 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.

[0362] b11 is preferably 1-30, more preferably 1-25, further preferably 1-10, particularly preferably 1-5, and most preferably 1-2.

[0363] b12 is preferably 0-15, more preferably 0-10.

[0364] b13 is preferably 0-5, more preferably 0-2.

[0365] b14 is preferably 0-4, more preferably 0-2.

[0366] b15 is preferably 0-4, more preferably 0-2.

[0367] c is preferably 2 to 3, more preferably 3.

[0368] 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.

[0369] 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.

[0370] In the examples described below, when FAS13E used as compound (B) is represented by the above formula (b1), it is defined as follows: 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 -.

[0371] 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 mentioned. k SiCl3、CF3CH2O(CH2) kSi(OCH3)3, CF3CH2O(CH2) k Si(OC2H5)3, CF3(CH2)2Si(CH3)2(CH2) k SiCl3, 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, and 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).

[0372] Among the compounds represented by the above formula (b1), compounds represented by the following formula (b2) are preferred.

[0373] R 60 -R61 -Si(OR 62 )3…(b2)

[0374] In the above formula (b2), R 60 is a perfluoroalkyl group with 3 to 8 carbon atoms, R 61 is an alkylene group having 1 to 5 carbon atoms, R 62 It is an alkyl group having 1 to 3 carbon atoms.

[0375] As the organosilicon compound (B), only one type may be used, or two or more types may be used.

[0376] The mixed composition (ca) is a composition containing the organosilicon compound (A), preferably a composition containing the organosilicon compound (A) and the organosilicon compound (B), and is obtained by mixing the organosilicon compound (A) and, if necessary, the organosilicon compound (B). Alternatively, when components other than the organosilicon compound (A) and the organosilicon compound (B) are mixed, the composition is obtained by mixing the organosilicon compound (A), the organosilicon compound (B) if necessary, and other components. The mixed composition (ca) also includes compositions obtained by reacting after mixing, for example, during storage.

[0377] 3-3. Solvent (D)

[0378] The mixed composition (ca) is usually mixed with a solvent (D). 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 above 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 methyl or ethyl) ether is preferred, and examples thereof include ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether. As ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether, for example, Novec (registered trademark) 7200 (manufactured by 3M, molecular weight of about 264) can be mentioned. As the fluorinated amine solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferred, and a tertiary amine in which all hydrogen atoms of ammonia are substituted with fluoroalkyl groups (especially perfluoroalkyl groups) is preferred. Specifically, tris(heptafluoropropyl)amine can be mentioned, and Fluorinert (registered trademark) FC-3283 (manufactured by 3M, molecular weight of about 521) corresponds thereto. Examples of fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane and fluorinated aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethylbenzene). Examples of 1,1,1,3,3-pentafluorobutane include Solve 55 (manufactured by Solvex).

[0379] As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.) and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.) can be used.

[0380] 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), preferably a fluorinated amine solvent and a fluorinated hydrocarbon solvent (particularly a fluorinated aliphatic hydrocarbon solvent).

[0381] The amount of the organosilicon compound (A) in the mixed composition (ca) is, for example, 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less, relative to 100% by mass of the entire composition.

[0382] The amount 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, relative to 100 mass % of the entire composition.

[0383] The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) is preferably 0.05 or more, more preferably 0.08 or more, and even more preferably 0.10 or more, and is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.6 or less.

[0384] The amounts of the organosilicon compounds (A) and (B) can be adjusted during the preparation of the composition. The amounts of the organosilicon compounds (A) and (B) can be calculated from the analysis results of the composition.

[0385] In addition, the above-mentioned mixed composition (ca) for forming the water-repellent layer (r) can 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 a range that does not hinder the effects of the present invention.

[0386] The thickness of the water-repellent layer (r) is, for example, approximately 1 to 1000 nm.

[0387] The laminate of the present invention preferably has a ratio of the absolute value of the arithmetic mean height Sa(c) of the above-mentioned intermediate layer (c) before laminating the above-mentioned water-repellent layer (r) to the absolute value of the arithmetic mean height Sa(s) of the above-mentioned substrate (s) before laminating the above-mentioned intermediate layer (c) (absolute value of Sa(c) / absolute value of Sa(s)) less than 100%.

[0388] The hard coating disclosed in Patent Document 1 above generally has a sufficiently low surface roughness (in the present invention, the surface roughness is evaluated by the arithmetic mean height). Therefore, when other layers are laminated on the hard coating, the surface roughness of the other layers is generally equal to or greater than the surface roughness of the hard coating before the other layers are laminated. Therefore, in a preferred embodiment of the present invention, the ratio of the absolute value of the arithmetic mean height Sa(c) of the intermediate layer (c) before laminating the water-repellent layer (r) to the absolute value of the arithmetic mean height Sa(s) of the substrate (s) before laminating the layer (c) (absolute value of Sa(c) / absolute value of Sa(s)) is less than 100%, indicating that the substrate (s) of the present invention has a surface roughness coarser than that of the hard coating disclosed in Patent Document 1, etc., and is also a preferred requirement for improving the wear resistance of a laminate having a water-repellent layer laminated on a substrate having a surface roughness coarser than that of the hard coating.

[0389] The absolute value of Sa(c) / the absolute value of Sa(s) is preferably 80% or less, more preferably 60% or less, even more preferably 40% or less, and particularly preferably 20% or less. The lower limit of the absolute value of Sa(c) / the absolute value of Sa(s) is not particularly limited, but may be 1%, for example.

[0390] In the preferred embodiment of the present invention in which the substrate (s) is a layer having an absolute value of an arithmetic mean height Sa(s) greater than the absolute value of the arithmetic mean height of the hard coat layer as described above, the absolute value of the arithmetic mean height Sa(s) of the substrate (s) before laminating the above-mentioned layer (c) is not limited as long as the condition of the absolute value of Sa(c) / the absolute value of Sa(s) being less than 100% is satisfied as described above, and is, for example, 0.01 μm or more. In addition, the absolute value of Sa(s) is preferably 5 μm or less, more preferably 3 μm or less, further preferably 1 μm or less, further preferably 0.8 μm or less, and particularly preferably 0.5 μm or less. The value (not the absolute value) of the arithmetic mean height Sa(s) of the substrate (s) before laminating the above-mentioned layer (c) is preferably negative, that is, it preferably has a concave portion. It should be noted that the arithmetic mean height Sa is calculated in accordance with ISO 25178.

[0391] The water contact angle (initial contact angle) of the laminate of the present invention when evaluated according to the method described in the Examples below is, for example, 105° or greater, more preferably 110° or greater, and, for example, 125° or less. Furthermore, the water contact angle after the abrasion resistance test performed in the Examples below (contact angle after abrasion resistance test) is preferably 85% or greater, more preferably 90% or greater, and typically 110% or less of the contact angle before the abrasion resistance test.

[0392] Furthermore, when the laminate of the present invention is evaluated according to the method described in the Examples below, the slip angle is 25° or less, preferably 20° or less, more preferably 15° or less, and for example, 2° or more. Furthermore, the slip angle after the wear resistance test performed in the Examples below is preferably 200% or less, more preferably 150% or less, and typically 15% or more of the slip angle before the wear resistance test.

[0393] Next, the method for producing the laminate of the present invention will be described.

[0394] The first method for producing the laminate of the present invention includes: (i) a step of coating the mixed composition (cc) on the anti-reflection layer surface of the substrate (s) having the anti-reflection layer, (ii) a step of coating the mixed composition (ca) on the coated surface of the mixed composition (cc), and (iii) a step of curing the mixed composition (cc) and the mixed composition (ca), forming the intermediate layer (c) from the coated layer of the mixed composition (cc), and forming the water-repellent layer (r) from the coated layer of the mixed composition (ca).

[0395] The mixed composition (cc) can be applied by a known method, and a dip coating method is preferred.

[0396] Next, the above-mentioned mixed composition (ca) for forming a water-repellent layer (r) is applied to the coating surface of the above-mentioned mixed composition (cc) and dried, thereby forming the above-mentioned intermediate layer (c) from the coating layer of the above-mentioned mixed composition (cc), and forming the above-mentioned water-repellent layer (r) from the coating layer of the above-mentioned mixed composition (ca). The above-mentioned intermediate layer (c) can be formed during the coating of the above-mentioned mixed composition (cc), or it can be formed after coating, or the formation of the above-mentioned intermediate layer (c) and the above-mentioned water-repellent layer (r) can be carried out simultaneously. As a method for coating the composition for forming the above-mentioned water-repellent layer (r), for example, dip coating, roller coating, rod coating, spin coating, spray coating, die coating, gravure coating, etc. can be mentioned.

[0397] After applying the composition for forming the water-repellent layer (r), the laminate of the present invention can be produced by allowing the laminate to stand in the atmosphere at room temperature for, for example, 1 hour or longer (usually 24 hours or less). In the present invention, room temperature refers to a temperature range of 5 to 60°C, preferably 15 to 40°C. The humidity during standing at room temperature can be 50 to 90% RH.

[0398] In a second method for producing a laminate of the present invention, the organosilicon compound (C) is deposited onto the anti-reflection layer of the substrate (s) having the anti-reflection layer to form a layer (c), the mixed composition (ca) is applied onto the intermediate layer (c) and cured, and the water-repellent layer (r) is formed from the applied layer of the mixed composition (ca). When the organosilicon compound (C) is deposited to form the intermediate layer (c), the organosilicon compound (C) may be deposited onto the substrate (s) as a single substance, or a solid substance (i.e., the organosilicon compound (C)) obtained by removing the solvent from a mixed composition of the organosilicon compound (C) and a solvent may be deposited onto the substrate (s). After applying the composition for forming the water-repellent layer (r), the same procedures as those of the first method may be employed.

[0399] It is preferred that the anti-reflection layer of the substrate (s) is subjected to a hydrophilic treatment in advance before applying the composition (cc) or before vapor-depositing the organosilicon compound (C). As the hydrophilic treatment, hydrophilic treatments such as corona treatment, plasma treatment, ultraviolet treatment, and ion cleaning treatment can be cited, and plasma treatment and ion cleaning treatment are more preferred. By performing a hydrophilic treatment such as plasma treatment, functional groups such as OH groups and COOH groups can be formed on the surface of the substrate. When such functional groups are formed on the surface of the substrate, the adhesion between the intermediate layer (c) and the substrate (s) can be further improved. However, when the laminate is used for eyeglass lenses, it is preferred that the anti-reflection layer of the substrate (s) is not subjected to a hydrophilic treatment and the mixed composition (cc) is applied or the organosilicon compound (C) is vapor-deposited. Therefore, the hydrophilic treatment is preferably performed when the laminate is used for purposes other than eyeglass lenses.

[0400] The laminate of the present invention 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 flexible display device laminate and an organic EL display panel, and the flexible display device laminate is configured on the visual side relative to the organic EL display panel, and is configured to be bendable. The flexible display device laminate 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 window film (that is, the laminate of the present invention), polarizer, touch sensor, or window film, touch sensor, polarizer. If there is a polarizer on the visual side closer to the touch sensor, the pattern of the touch sensor becomes less likely to be visually recognized, and the visibility of the displayed image becomes good, thus preferably. Each component can be stacked using an adhesive, an adhesive, etc. In addition, the flexible display device can have a light-shielding pattern formed on at least one surface of any layer of the above-mentioned window film, polarizer, and touch sensor.

[0401] This application claims the benefit of priority based on Japanese Patent Application No. 2019-086595, filed on April 26, 2019. The entire contents of the specification of Japanese Patent Application No. 2019-086595, filed on April 26, 2019, are incorporated herein by reference.

[0402] Example

[0403] The present invention is not limited to the following examples, and can be implemented by appropriately modifying the above and below-mentioned embodiments, which are all included in the technical scope of the present invention.

[0404] [Example 1-1]

[0405] Preparation of solution for forming intermediate layer (c)

[0406] 0.5% by mass of a reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) described in JP-A-2012-197330 and represented by the following formula as an organosilicon compound (C) and 99.5% by mass of isopropyl alcohol as a solvent (E) were mixed, and the resulting solution was stirred at room temperature to obtain a solution for forming an intermediate layer (c).

[0407]

[0408] Preparation of substrate(s)

[0409] A glass substrate (8 cm × 8 cm, "EAGLE XG" manufactured by Corning) was subjected to a hydrophilic treatment using ion cleaning. A multilayer antireflective coating (antireflection layer (ar)) composed of inorganic oxides (silicon dioxide and zirconium oxide) having a thickness of approximately 0.4 μm was formed on the hydrophilicized surface by vacuum deposition, yielding a glass substrate having the antireflection layer (ar) formed thereon as substrate (s). Subsequently, using a dip coater (model DC4300 manufactured by Aiden Co., Ltd.), the substrate (s) was immersed in the intermediate layer (c) forming solution under the conditions of an immersion time of 10 seconds and a pull-up speed of 10 mm / s to form a film.

[0410] Next, OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd. was prepared as the organosilicon compound (A), FAS13E (C6F 13 -C2H4-Si(OC2H5)3, manufactured by Tokyo Chemical Industry Co., Ltd.), FC-3283 (C9F 21 N, Fluorinert, manufactured by 3M Company) is mixed and stirred at room temperature for a predetermined time to obtain a solution for forming a water-repellent layer (r). Here, OPTOOL (registered trademark) UF503 is an organosilicon compound having a monovalent group and a hydrolyzable group having a perfluoropolyether structure, each bonded to a silicon atom. In the solution for forming the water-repellent layer (r), the proportion of the organosilicon compound (A) is 0.425% by mass, and the proportion of the organosilicon compound (B) is 0.05% by mass when the solution for forming the water-repellent layer (r) is set to 100% by mass as a whole. A dip coater (model DC4300) manufactured by Aiden Co., Ltd. is used to form a film on the coating surface of the intermediate layer (c) forming solution (the coating surface of the intermediate layer (c) forming solution on the anti-reflective coating of the above-mentioned substrate) with an immersion time of 10 seconds and a pulling speed of 10 mm / second. Thereafter, wet heat curing is performed at 50°C and 80% RH for 30 minutes.

[0411] [Examples 1-2 to 1-9]

[0412] A laminate was obtained in the same manner as in Example 1-1, except that the concentration and type of the organosilicon compound (C) or the type of solvent (E) were changed as shown in Tables 1-1 and 1-2. In the table, KBM-603 represents N-2-(aminoethyl)-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., FAS9E represents C4F9-C2H4-Si(OC2H5)3 (manufactured by Tokyo Chemical Industry Co., Ltd.), and FAS3M represents CF3-C2H4-Si(OCH3)3 (manufactured by Tokyo Chemical Industry Co., Ltd.). DSX represents OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd., an organosilicon compound in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are each bonded to a silicon atom.

[0413] [Comparative Example 1-1]

[0414] A laminated body in which a substrate (s) and a water-repellent layer (r) were sequentially laminated was obtained in the same manner as in Example 1-1, except that the intermediate layer (c) was not formed and the water-repellent layer (r) was formed directly on the substrate (s). It should be noted that in Comparative Example 1-1, since the intermediate layer (c) was not formed, strictly speaking, the layer (c) before the water-repellent layer (r) is not present as specified in the present invention. However, the arithmetic mean height of the layer (c) before the water-repellent layer (r) is laminated in a preferred embodiment of the present invention. However, the arithmetic mean height Sa of the surface on which the water-repellent layer (r) is laminated is significant in determining the arithmetic mean height Sa of the surface on which the water-repellent layer (r) is laminated. From the perspective of the arithmetic mean height Sa of the surface on which the water-repellent layer (r) is laminated, the arithmetic mean height Sa of the surface on which the water-repellent layer (r) is laminated in Comparative Example 2-1 can also be referred to as the arithmetic mean height Sa of the substrate (s), and is the same value as the arithmetic mean height Sa of the substrate (s) before the layer (c) is formed (i.e., the ratio of the absolute value of the arithmetic mean height is 100%).

[0415] The laminates obtained in Examples and Comparative Examples were evaluated by the following methods.

[0416] (1-1) Initial contact angle and initial sliding angle

[0417] A 1 μL drop of water was dropped onto the water-repellent layer (r) of the obtained laminate, and the contact angle of 1 μL of water was measured by the θ / 2 method using a contact angle meter (DM700, manufactured by Kyowa Interface Science Co., Ltd.).

[0418] In addition, 20 μL of water droplets were dripped onto the water-repellent layer (r) of the obtained laminate, and the water sliding angle was measured using the above-mentioned contact angle measuring device (DM700, manufactured by Kyowa Interface Science Co., Ltd.) by the sliding method (analysis method: tangent method, tilting method: continuous tilting, sliding detection: after sliding, movement judgment: advancing angle, sliding judgment distance: 5 dots).

[0419] (1-2) Contact angle and sliding angle after wear resistance test

[0420] 16 stacked sheets of KimWipe Wiper S-200 manufactured by Nippon Paper Crecia Co., Ltd. were mounted on a 15 mm square elastomer (acrylic plate with a thickness of 1 mm). A load of 200 g was applied to the water-repellent layer (r) of the resulting laminate, and abrasion resistance was performed 20,000 times with a stroke of 30 mm and 70 r / min (70 back and forth times per minute). The slip angle after the abrasion resistance test was measured in the same manner as in the above (1-1) at approximately the center of the abrasion position.

[0421] 1 μL of water was dropped onto the water-repellent layer (r) after the abrasion resistance test, and the contact angle of 1 μL of water was measured by the θ / 2 method using a contact angle measurement device (DM700, manufactured by Kyowa Interface Science Co., Ltd.).

[0422] (1-3) Surface reflectivity

[0423] The spectral reflectance at a wavelength of 530 nm was determined using a Konica Minolta colorimeter (CM-3700A, illuminant: D65) using a 2-degree viewing field (illuminant C) according to JIS Z8701 on the surface of the laminate facing the water-repellent layer (r). The reflectance was calculated by subtracting 4.2% surface reflection loss and 4.2% back reflection loss from these values. The surface reflectance of the anti-reflection layer of the substrate (s), measured in the same manner as above, was 1.7%.

[0424] (1-4) Measurement of Fluorine and Nitrogen Amounts on the Water-Repellent Layer (r) Surface Based on XPS

[0425] The fluorine content (F1s) and nitrogen content on the surface of the water-repellent layer (r) were measured using JFS-9010 manufactured by JEOL Ltd. with an excitation X-ray of MgKα, an X-ray output of 110 W, a photoelectron departure angle of 45°, and a penetration energy of 50 eV.

[0426] (1-5) Dynamic friction coefficient

[0427] The coefficient of kinetic friction on the surface of the water-repellent layer (r) was measured using artificial leather under the following conditions using a constant load test using a friction gear (surface tester TYPE: 38) manufactured by Shinto Scientific Co., Ltd. Additionally, the coefficient of kinetic friction was measured after a wear resistance test under the same conditions as described in (1-2) above.

[0428] Load converter: 1.442mV / V

[0429] Load: 1000g

[0430] Moving distance: 20mm

[0431] Moving speed: 600mm / min

[0432] Number of samples: 210

[0433] (1-6) Determination of the arithmetic mean height Sa

[0434] The surfaces of the substrate (s) before the intermediate layer (c) was formed and the layer (c) before the water-repellent layer (r) was formed were observed at a magnification of 100 times using an Olympus laser microscope LEXT OSL4000. The arithmetic mean height Sa was evaluated in accordance with ISO 25178. The arithmetic mean height Sa is the average value of N = 3. The arithmetic mean height of the substrate (s) before the intermediate layer (c) was formed was set as Sa(s), and the arithmetic mean height of the intermediate layer (c) before the layer (r) was formed was set as Sa(c).

[0435] The results of Examples 1-1 to 1-9 and Comparative Example 1-1 are shown in Table 1-1 and Table 1-2.

[0436] [Table 1-1]

[0437]

[0438] [Table 1-2]

[0439]

[0440] [Example 2-1]

[0441] Preparation of solution for forming intermediate layer (c)

[0442] A solution obtained by mixing 0.25% by mass of a reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.), which is the same compound used in Example 1-1 above, as an organic silicon compound (C), and 99.75% by mass of hexane as a solvent (E) was stirred at room temperature to obtain a solution for forming layer (c).

[0443] Preparation of substrate(s)

[0444] The coating solution was applied to NL3-SP (size The surface of the substrate (1.1 mm thick at the center) was heat-cured, and a urethane-based impact-resistant coating (primer layer) with a thickness of approximately 1 μm and a silicone-based scratch-resistant hard coating layer with a thickness of approximately 2 μm were laminated in this order. Next, a multilayer anti-reflective coating (anti-reflective layer (ar)) composed of inorganic oxides (silicon dioxide and zirconium oxide) with a thickness of approximately 0.4 μm was formed on the silicone-based scratch-resistant hard coating layer (hard coating layer) by vacuum deposition, thereby obtaining a plastic eyeglass lens as the substrate (s). The substrate (s) was then immersed in the solution for forming the intermediate layer (c) using a dip coater (model DC4300) manufactured by Aiden Co., Ltd. under the conditions of an immersion time of 10 seconds and a pull-up speed of 10 mm / second to form a film.

[0445] Next, OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd. was prepared as the organosilicon compound (A), FAS13E (C6F 13 -C2H4-Si(OC2H5)3, manufactured by Tokyo Chemical Industry Co., Ltd.), FC-3283 (C9F 21 N, Fluorinert, manufactured by 3M Company) was mixed and stirred at room temperature for a predetermined time to obtain a solution for forming a water-repellent layer (r). For the solution for forming a water-repellent layer (r), the proportion of the organosilicon compound (A) was 0.425% by mass, and the proportion of the organosilicon compound (B) was 0.05% by mass when the total mass of the solution for forming a water-repellent layer (r) was 100%. A dip coater (model DC4300) manufactured by Aiden Co., Ltd. was used to form a film on the coating surface of the intermediate layer (c) forming solution (the coating surface of the intermediate layer (c) forming solution on the anti-reflective coating of the above-mentioned substrate) under the conditions of immersion time: 10 seconds and pulling speed 10 mm / second. Thereafter, wet heat curing was performed at 50°C 80% RH for 30 minutes.

[0446] [Example 2-2]

[0447] A laminate was obtained in the same manner as in Example 2-1 except that the solvent (E) of the solution for forming the intermediate layer (c) was changed from hexane to butyl acetate.

[0448] [Comparative Example 2-1]

[0449] A laminated body in which a substrate (s) and a water-repellent layer (r) were sequentially laminated was obtained in the same manner as in Example 2-1, except that the water-repellent layer (r) was formed directly on the substrate (s) without forming the layer (c). It should be noted that in Comparative Example 2-1, no layer (c) was formed, and therefore, strictly speaking, the intermediate layer (c) prior to the formation of the water-repellent layer (r) specified in the present invention did not exist. However, in a preferred embodiment of the present invention, the arithmetic mean height of the layer (c) prior to the formation of the water-repellent layer (r) is significant in determining the arithmetic mean height of the surface on which the water-repellent layer (r) is laminated. From the perspective of the arithmetic mean height Sa of the surface on which the water-repellent layer (r) is laminated, the arithmetic mean height Sa of the surface on which the water-repellent layer (r) is laminated in Comparative Example 2-1, which can also be referred to as the arithmetic mean height Sa of the substrate (s), is the same value as the arithmetic mean height Sa of the substrate (s) prior to the formation of the intermediate layer (c) (i.e., the ratio of the absolute values of the arithmetic mean heights is 100%).

[0450] Examples 2-1, 2-2, and Comparative Example 2-1 were evaluated by the following methods.

[0451] (2-1) Initial contact angle and initial sliding angle

[0452] 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 the drop method (analysis method: ellipse fitting method) using a contact angle measuring device (DM-500 / DM-SA manufactured by Kyowa Interface Science Co., Ltd.).

[0453] 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 the above-mentioned contact angle measuring device (DM-500 / DM-SA, manufactured by Kyowa Interface Science Co., Ltd.) by the sliding method (analysis method: true circle fitting method, tilt method: continuous tilt, sliding detection: before sliding, movement judgment: forward and backward, sliding judgment distance: 10 dots).

[0454] (2-2) Contact angle and sliding angle after wear resistance test

[0455] 16 stacked sheets of KimWipe Wiper S-200 manufactured by Nippon Paper Crecia Co., Ltd. were installed on a 15 mm square elastomer (Plastic eraser model 1156SMTR00 manufactured by Maped Formula (France)). A load of 200 g was applied to the water-repellent layer (r) of the resulting laminate, and an abrasion resistance test was performed by wiping 20,000 times with a stroke of 30 mm and 90 r / min (90 times back and forth in 1 minute). The slip angle after the abrasion resistance test was measured in the same manner as above (2-1).

[0456] 1 μL of water was dropped onto the water-repellent layer (r) after the abrasion resistance test, and the contact angle of water was measured using a contact angle measuring device (DM-500 / DM-SA, manufactured by Kyowa Interface Science Co., Ltd.) by the drop method (analysis method: ellipse fitting method).

[0457] (2-3) Surface reflectivity

[0458] The surface reflectance of the water-repellent layer (r) of the laminate was measured using an Olympus lens reflectometer (model: USPM-RU, light source: halogen lamp) using a 10x objective lens. The spectral reflectance at a wavelength of 530 nm was calculated using a D65 illuminant and a 10° field of view. The surface reflectance of the anti-reflection layer of the substrate (s), measured in the same manner as above, was 1.07%.

[0459] (2-4) Measurement of the Fluorine and Nitrogen Amounts on the Water-Repellent Layer (r) Surface Based on XPS

[0460] The fluorine content (F1s) and nitrogen content on the surface of the water-repellent layer (r) were measured using JFS-9010 manufactured by JEOL Ltd. with an excitation X-ray of MgKα, an X-ray output of 110 W, a photoelectron departure angle of 45°, and a penetration energy of 50 eV.

[0461] (2-5) Dynamic friction coefficient

[0462] The coefficient of kinetic friction on the surface of the water-repellent layer (r) was measured using a constant load test using a friction gear (surface tester type 38) manufactured by Shinto Scientific Co., Ltd., using artificial leather under the following measurement conditions. The coefficient of kinetic friction was also measured after the wear resistance test was performed under the same conditions as described in (2-2) above.

[0463] Load converter: 1.442mV / V

[0464] Load: 1000g

[0465] Moving distance: 20mm

[0466] Moving speed: 600mm / min

[0467] Number of samples: 210

[0468] (2-6) Determination of the arithmetic mean height Sa

[0469] The arithmetic mean height Sa was measured by the same method as that used to evaluate Examples 1-1 to 1-6 and Comparative Example 1-1 described above.

[0470] Table 2 shows the results of Examples 2-1, 2-2, and Comparative Example 2-1.

[0471] [Table 2]

[0472]

[0473] Furthermore, according to Table 1, Examples 1-1 to 1-6 exhibited good contact angles and sliding-off angles after the wear resistance test, indicating excellent wear resistance, and the absolute value of Sa(c) / the absolute value of Sa(s), a preferred requirement of the present invention, was less than 100%. On the other hand, Comparative Example 1-1, which did not include an intermediate layer (c), exhibited significantly poor contact angles and sliding-off angles after the wear resistance test, resulting in poor wear resistance.

[0474] According to Table 2, Examples 2-1 and 2-2 exhibited good contact angles and sliding-off angles after the wear resistance test, indicating excellent wear resistance. The absolute value of Sa(c) / the absolute value of Sa(s), a preferred requirement of the present invention, was less than 100%. On the other hand, Comparative Example 2-1, which did not include an intermediate layer (c), exhibited significantly poor contact angles and sliding-off angles after the wear resistance test, resulting in poor wear resistance.

[0475] Industrial applicability

[0476] The laminate of the present invention can be preferably formed into a film on display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, automobiles, window glass for buildings, metal products such as cookware, ceramic products such as tableware, and plastic automotive parts, and is therefore industrially useful. Furthermore, it is preferably used in kitchens, bathrooms, washstands, mirrors, and other items around toilets, as well as in goggles and eyeglass lenses.

Claims

1. A laminated body, characterized in that: The invention comprises, in order: a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r); The intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) represented by the following formula (c2) or a vapor-deposited layer of the organosilicon compound (C). In the formula (c2), R x20 and R x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x20 When there are multiple, multiple R x20 Can be different, R x21 When there are multiple, multiple R x21 Can be different, Rf 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, Rf x20 When there are multiple, multiple Rf x20 Can be different, Rf x21 When there are multiple, multiple Rf x21 Can be different, R x22 and R x23 are each independently an alkyl group having 1 to 20 carbon atoms, R x22 and R x23 When there are multiple, multiple R x22 and R x23 Can be different, X 20 and X 21 are each independently a hydrolyzable group, X 20 and X 21 When there are multiple, multiple X 20 and X 21 Can be different, p20 is an integer of 1 to 30, and 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 substituted with an amine skeleton -NR 100 -, R in the amine skeleton 100 is a hydrogen atom or an alkyl group, the amine skeleton -NR 100 The number of - is 2 to 5, p22 and p23 are each independently an integer of 1 to 3, p20-{C(R x20 )(R x21 )}-、p21 -{C(Rf x20 )(Rf x21 )}- does not need p20 or p21 to be continuous, and can be bonded in any order, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 , The water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) represented by the following formula (a3) and having a number average molecular weight of 7000 or more. The laminate satisfies the following requirement (1): (1) After an abrasion resistance test in which a load of 200 g is applied to the water-repellent layer (r) side surface of the laminate per an area of 1.5 cm×1.5 cm and the laminate is wiped 20,000 times, the water sliding angle is 10° or less, In the formula (a3), R 30 is a perfluoroalkyl group with 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 It is an alkyl group having 1 to 3 carbon atoms.

2. The laminate according to claim 1, wherein The mixed composition (ca) further contains 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 in which one or more hydrogen atoms are replaced by fluorine atoms, or a fluorine atom, R b11 、R b12 、R b13 and R b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R b11 When there are multiple, multiple R b11 Can be different, R b12 When there are multiple, multiple R b12 Can be different, R b13 When there are multiple, multiple R b13 Can be different, R b14 When there are multiple, multiple R b14 Can be different, Rf 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, Rf b11 When there are multiple, multiple Rf b11 Can be different, Rf b12 When there are multiple, multiple Rf b12 Can be different, Rf b13 When there are multiple, multiple Rf b13 Can be different, Rf b14 When there are multiple, multiple Rf b14 Can be different, R b15 is an alkyl group with 1 to 20 carbon atoms, R b15 When there are multiple, multiple R b15 Can be different, A 1 is -O-, -C(=O)-O-, -O-C(=O)-, -NR-, - NRC(=O)- or -C(=O)NR-, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms, and A 1 When there are multiple A 1 Can be different, A 2 A is a hydrolyzable group. 2 When there are multiple 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, Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c 、b11-{C(R b11 )(R b12 )}-、b12 -{C(Rf b11 )(Rf b12 )}-、b13-{Si(R b13 )(R b14 )}-、b14-{Si(Rf b13 )(Rf b14 )}-、b15 -A 1 -As long as Rf b10 -、-Si(A 2 ) c (R b15 ) 3-c The -O- radicals are not connected to -O- or -F, and the radicals are arranged and bonded in any order.

3. The laminate according to claim 2, 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.

4. The laminate according to claim 1 or 2, wherein The organosilicon compound (C) is a compound represented by the following formula (c2-2), (Rx 25 ) 3-p25 (X 23 ) p25 Si-C w H 2w -Si(X 22 ) p24 (R x24 ) 3-p24 (c2-2) In the formula (c2-2), X 22 and X 23 are each independently a hydrolyzable group, X 22 and X 23 When there are multiple, multiple X 22 and X 23 Can be different, R x24 and R x25 are each independently an alkyl group having 1 to 20 carbon atoms, R x24 and R x25 When there are multiple, multiple R x24 and R x25 Can be different, for -C w H 2w -, at least one of the methylene groups in a part thereof is substituted with an amine skeleton -NR 100 -, R 100 is a hydrogen atom or an alkyl group, the amine skeleton -NR 100 The number of - is 2 to 5, w is an integer of 1 to 30, excluding the number of methylene groups substituted with the amine skeleton, and p24 and p25 are each independently an integer of 1 to 3.

5. The laminate according to claim 1 or 2, wherein The properties measured on the surface of the water-repellent layer further satisfy at least one of the following requirements (1′) and (3), (1') The contact angle of water after the wear resistance test is 90° or more, (3) The initial sliding angle of water is less than 21°.

6. The laminate according to claim 1 or 2, wherein The properties measured on the surface of the water-repellent layer further satisfy the following requirement (4), (4) The dynamic friction coefficient after the wear resistance test is 0.40 or less.

7. The laminate according to claim 1 or 2, wherein The surface of the water-repellent layer (r) side of the laminate has a F content of 5 atomic % or more and a N content of 0.15 atomic % or more as measured by XPS.

8. The laminate according to claim 1 or 2, wherein The ratio of the absolute value of the arithmetic mean height Sa(c) of the intermediate layer (c) before laminating the water-repellent layer (r) to the absolute value of the arithmetic mean height Sa(s) of the substrate (s) before laminating the intermediate layer (c), that is, the absolute value of Sa(c) / the absolute value of Sa(s), is less than 100%.

9. The laminate according to claim 1 or 2, wherein The substrate(s) has an antireflection layer formed on a glass layer or a resin layer. 10 . A spectacle lens comprising the laminate according to claim 1 .

11. A method for producing a laminate comprising, in order: a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r); The manufacturing method comprises the following steps: a step of coating the anti-reflection layer of the substrate (s) having the anti-reflection layer with a mixed composition (cc) of an organosilicon compound (C) represented by the following formula (c2), a step of applying a mixed composition (ca) comprising an organosilicon compound (A) represented by the following formula (a3) and having a number average molecular weight of 7,000 or more to the coating surface of the mixed composition (cc); and a step of curing the mixed composition (cc) and the mixed composition (ca), forming the intermediate layer (c) from the coating layer of the mixed composition (cc), and forming the water-repellent layer (r) from the coating layer of the mixed composition (ca); In the formula (c2), R x20 and R x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x20 When there are multiple, multiple R x20 Can be different, R x21 When there are multiple, multiple R x21 Can be different, Rf 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, Rf x20 When there are multiple, multiple Rf x20 Can be different, Rf x21 When there are multiple, multiple Rf x21 Can be different, R x22 and R x23 are each independently an alkyl group having 1 to 20 carbon atoms, R x22 and R x23 When there are multiple, multiple R x22 and R x23 Can be different, X 20 and X 21 are each independently a hydrolyzable group, X 20 and X 21 When there are multiple, multiple X 20 and X 21 Can be different, p20 is an integer of 1 to 30, and p21 is an integer of 0 to 30, and at least one of the repeating units enclosed in parentheses and labeled with p20 or p21 is substituted with an amine skeleton -NR 100 -, R in the amine skeleton 100 is a hydrogen atom or an alkyl group, the amine skeleton -NR 100 The number of - is 2 to 5, p22 and p23 are each independently an integer of 1 to 3, p20-{C(R x20 )(R x21 )}-、p21 -{C(Rf x20 )(Rf x21 )}- does not need p20 or p21 to be continuous, and can be bonded in any order, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 , In the formula (a3), R 30 is a perfluoroalkyl group with 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 It is an alkyl group having 1 to 3 carbon atoms.

12. A method for producing a laminate, characterized in that: The laminate comprises, in order: a substrate (s) having an antireflection layer, an intermediate layer (c) provided on the antireflection layer side of the substrate, and a water-repellent layer (r); The manufacturing method comprises the following steps: The steps of forming the intermediate layer (c) by evaporating an organosilicon compound (C) represented by the following formula (c2) on the anti-reflection surface of the substrate (s) having the anti-reflection layer, and coating the intermediate layer (c) with a mixed composition (ca) of an organosilicon compound (A) represented by the following formula (a3) and having a number average molecular weight of 7,000 or more and curing the mixed composition (ca) to form the water-repellent layer (r) from the coating layer of the mixed composition (ca); In the formula (c2), R x20 and R x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R x20 When there are multiple, multiple R x20 Can be different, R x21 When there are multiple, multiple R x21 Can be different, Rf 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, Rf x20 When there are multiple, multiple Rf x20 Can be different, Rf x21 When there are multiple, multiple Rf x21 Can be different, R x22 and R x23 are each independently an alkyl group having 1 to 20 carbon atoms, R x22 and R x23 When there are multiple, multiple R x22 and R x23 Can be different, X 20 and X 21 are each independently a hydrolyzable group, X 20 and X 21 When there are multiple, multiple X 20 and X 21 Can be different, p20 is an integer of 1 to 30, and p21 is an integer of 0 to 30, and at least one of the repeating units enclosed in parentheses and labeled with p20 or p21 is substituted with 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 )}- does not need p20 or p21 to be continuous, and can be bonded in any order, with both ends being -Si(X 20 ) p22 (R x22 ) 3-p22 and -Si(X 21 ) p23 (R x23 ) 3-p23 , In the formula (a3), R 30 is a perfluoroalkyl group with 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 It is an alkyl group having 1 to 3 carbon atoms.

13. The method for producing a laminate according to claim 11 or 12, wherein: The antireflection layer of the substrate (s) is subjected to a hydrophilic treatment before coating the mixed composition (cc) or before vapor deposition of the organosilicon compound (C), and the mixed composition (cc) is coated on the hydrophilicized surface or the organosilicon compound (C) is vapor deposited.

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