Laminate

Abstract

To provide a laminate with good durability.SOLUTION: A laminate comprises a base material, an inorganic layer stacked on the base material, and a surface treatment layer in contact with the inorganic layer. The inorganic layer includes SiOxNy, where x is 0.01 or more and 8 or less, and y is 0.01 or more and 8 or less. The surface treatment layer is formed using a surface treatment agent containing a fluorine-containing silane compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a laminate.

Background Art

[0002] It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of a substrate. A layer obtained from a surface treatment composition containing a fluorine-containing compound is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. Patent Document 1 describes a surface treatment agent containing a perfluoro(poly)ether group-containing silane compound.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a laminate having good durability.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects. [1] A laminate comprising a substrate, an inorganic layer laminated on the substrate, and a surface treatment layer in contact with the inorganic layer, wherein the inorganic layer contains SiO x N y wherein x is 0.01 or more and 8 or less, and y is 0.01 or more and 8 or less, and the surface treatment layer is formed using a surface treatment agent containing a fluorine-containing silane compound. [2] ​The laminate according to [1], wherein the ratio y / x of y to x is from 0.01 to 1. [3] The laminate according to [1] or [2], wherein the thickness of the inorganic layer is from 1 nm to 35 nm. [4] The laminate according to any one of [1] to [3], wherein the refractive index of the inorganic layer with respect to light having a wavelength of 550 nm is from 1.3 to 2.0. [5] The fluorine-containing silane compound is represented by the following formula (1) or (2): [Chemical formula] [wherein: R F1 is, in each occurrence, independently of one another, Rf 1 -R F -O q - or a fluoroalkyl group; R F2 is -Rf 2 p -R F -O q - or a fluoroalkylene group; Rf 1 is, in each occurrence, independently of one another, a C 1-16 alkyl group which may be substituted by one or more fluorine atoms; Rf 2 is a C 1-6 alkylene group which may be substituted by one or more fluorine atoms; R F is, in each occurrence, independently of one another, a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded; p is 0 or 1; q is, in each occurrence, independently of one another, 0 or 1; R Si is, in each occurrence, independently of one another, a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded; At least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X A is, independently of one another, a single bond or an organic group having a valence of 2 to 10; α is an integer from 1 to 9; β is an integer from 1 to 9; γ is, independently of one another, an integer from 1 to 9.] The laminate according to any one of [1] to [3], comprising at least one fluorine-containing silane compound represented by the formula: [6] Forming an inorganic layer on a substrate by reactive sputtering, and Applying a surface treatment agent to the surface of the inorganic layer to form a surface treatment layer, The inorganic layer contains SiO x N y and x is 0.01 or more and 8 or less, y is 0.01 or more and 8 or less, The surface treatment layer contains a fluorine-containing silane compound, a method for producing a laminate. [Advantages of the Invention

[0006] The laminate of the present disclosure has good durability. [Embodiments for Carrying Out the Invention

[0007] The laminate of the present disclosure includes a substrate, an inorganic layer laminated on the substrate, and a surface treatment layer in contact with the inorganic layer, The inorganic layer contains SiO x N y and The surface treatment layer is formed using a surface treatment agent containing a fluorine-containing silane compound. x is 0.01 or more and 8 or less, and y is 0.01 or more and 8 or less.

[0008] The present disclosure can provide a laminate having good durability, preferably, a laminate having good artificial sweat resistance, steel wool abrasion resistance, and ethanol eraser abrasion resistance.

[0009] (Substrate) Substrates that can be used in the present disclosure can be composed of, for example, glass, resin (natural or synthetic resin, which may be a common plastic material), OCA (Optical Clear Adhesive), polarizing plate metal, ceramics, semiconductors (such as silicon, germanium, etc.), electronic devices, fibers (woven fabrics, non-woven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building members, etc., sanitary products, and any suitable material.

[0010] In a preferred embodiment, the above substrate is glass, resin, polarizing plate, OCA (Optical Clear Adhesive) or metal, preferably glass, resin, polarizing plate or OCA (Optical Clear Adhesive).

[0011] As the above glass, sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and fused silica glass are preferred, and chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass are particularly preferred.

[0012] For example, when the laminate to be manufactured is an optical member, the material constituting the surface of the base material may be a material for an optical member, such as glass or transparent plastic. Further, when the laminate to be manufactured is an optical member, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the base material. For the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic substances that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO2 and / or SiO for the outermost layer thereof. When the laminate to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the base material (glass). Further, depending on its specific specifications and the like, the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a matte film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, and the like.

[0013] The shape of the above base material is not particularly limited, and may be, for example, plate-like, film, or other forms. Further, the surface region of the base material on which the surface treatment layer is to be formed may be at least a part of the base material surface, and can be appropriately determined according to the use and specific specifications of the laminate to be manufactured.

[0014] (Inorganic layer) The above inorganic layer is laminated on the above base material. The inorganic layer may or may not be in contact with the base material. In one aspect, the inorganic layer may be in contact with the base material. In another aspect, another layer may exist between the base material and the inorganic layer.

[0015] The above inorganic layer contains SiO x N y and. In the present disclosure, SiOx N y means an amorphous material containing Si, O and N. SiO x N y is considered to contain SiO2 and SiN, but is not limited thereto.

[0016] In the above SiO x N y x can be 0.01 or more and 8 or less, preferably 0.1 or more and 6 or less, more preferably 0.5 or more and 4 or less. Also, in the above SiO x N y y can be 0.01 or more and 8 or less, preferably 0.01 or more and 5 or less, more preferably 0.01 or more and 2 or less.

[0017] In the above SiO x N y The ratio y / x of y to x can be preferably 0.01 or more and 1 or less, more preferably 0.01 or more and 0.8 or less.

[0018] The above x and y can be measured by X-ray photoelectron spectroscopy (XPS).

[0019] The proportion of SiO x N y contained in the inorganic layer can be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, still more preferably 95% by mass or more and 100% by mass or less.

[0020] The refractive index of the inorganic layer with respect to light with a wavelength of 550 nm can be preferably 1.2 or more and 2.0 or less, more preferably 1.3 or more and 2.0 or less, still more preferably 1.35 or more and 2.0 or less, even more preferably 1.35 or more and 1.9 or less, and even more preferably 1.35 or more and 1.8 or less. The refractive index of the above inorganic layer can be measured by an ellipsometer.

[0021] The thickness of the inorganic layer is preferably 1 nm or more and 35 nm or less, more preferably 3 nm or more and 20 nm or less, and even more preferably 5 nm or more and 15 nm or less. The thickness of the inorganic layer can be measured by a laser microscope.

[0022] The inorganic layer can be formed by a reactive sputtering method. The reactive sputtering method can typically be a method of forming a film by reacting a metal target with oxygen and / or nitrogen. In one aspect, an inorganic layer can be formed by reacting a silicon target with oxygen and nitrogen to form a film on the substrate. An inert gas such as argon may coexist during film formation.

[0023] In one aspect, an inorganic layer can be formed by sputtering a silicon target while flowing argon gas, oxygen, and nitrogen.

[0024] The discharge power during the sputtering is preferably 3 kW or more and 10 kW or less, more preferably 4 kW or more and 8 kW or less, and even more preferably 5 kW or more and 7 kW or less.

[0025] The flow rate of the argon gas is preferably 100 sccm or more and 400 sccm or less, more preferably 150 sccm or more and 350 sccm or less, and even more preferably 150 sccm or more and 200 sccm or less. The flow rate of oxygen is preferably more than 0 sccm and 300 sccm or less, preferably 10 sccm or more and 200 sccm or less, and even more preferably 10 sccm or more and 150 sccm or less. The flow rate of nitrogen is preferably more than 0 sccm and 300 sccm or less, more preferably 10 sccm or more and 200 sccm or less, and even more preferably 10 sccm or more and 150 sccm or less.

[0026] The argon gas flow rate Q Ar with respect to the oxygen flow rate Q O2 and the nitrogen flow rate Q N2 of the total ratio (Q O2 +Q N2 ) / Q ArIt can preferably be 0.01 or more and 5 or less, more preferably 0.1 or more and 3 or less, and still more preferably 0.25 or more and 2 or less.

[0027] The pressure during the sputtering is preferably 1×10 -1 Torr or less, more preferably 7×10 -2 Torr or less, and still more preferably 5×10 -2 Torr or less. For example, it may be 1×1 -2 Torr or more.

[0028] The sputtering time can preferably be 60 seconds or more and 1,200 seconds or less, more preferably 120 seconds or more and 900 seconds or less, and still more preferably 240 seconds or more and 600 seconds or less.

[0029] Before forming the inorganic layer on the substrate, the substrate may be cleaned.

[0030] (Surface treatment layer) The surface treatment layer is in contact with the inorganic layer. The surface treatment layer can be formed by a surface treatment agent, and the surface treatment agent contains a fluorine-containing silane compound.

[0031] The fluorine-containing silane compound is a compound containing at least a fluorine-containing group and silane, and preferably has the following formulas (1) and (2):

Chemical formula

[0032] As used herein, "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, i.e., a group capable of detaching from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), etc., and preferably -OR j (i.e., an alkoxy group). R jExamples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. The hydroxyl group in the hydrolyzable silyl group is not particularly limited, but may be one generated by hydrolysis of the hydrolyzable group.

[0033] As used herein, the term "organic group" means a monovalent group containing carbon. Unless otherwise specified, the organic group can be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain of the hydrocarbon group. Note that when simply indicating "organic group", it means a monovalent organic group. The term "divalent organic group" means a divalent group containing carbon. Such divalent organic groups are not particularly limited, but examples include divalent groups obtained by further removing one hydrogen atom from an organic group.

[0034] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, and is a group obtained by removing one hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but may be substituted by one or more substituents, C 1-20 Hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc., can be mentioned. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Also, the hydrocarbon group may contain one or more ring structures.

[0035] As used herein, the substituents of the "hydrocarbon group" are not particularly limited, but examples include halogen atoms, C which may be substituted by one or more halogen atoms. 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10A cycloalkyl group, C 3-10 An unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, C 6-10 One or more groups selected from an aryl group and a 5- to 10-membered heteroaryl group are exemplified.

[0036] As used herein, the "alkyl group" is, unless otherwise specified, for example, C 1-12 (Preferably C 1-6 , more preferably C 1-3 , still more preferably C1) alkyl groups (e.g., methyl group, ethyl group, propyl group, isopropyl group). The "alkyl group" may be linear or branched, but is preferably linear. Also, the "alkyl group" may contain a functional group.

[0037] In the above formula (1), R F1 is, in each occurrence, independently of each other, Rf 1 -R F -O q - or a fluoroalkyl group. In one embodiment, R F1 is preferably Rf 1 -R F -O q -, and in another embodiment, R F1 is preferably a fluoroalkyl group. When R F1 is Rf 1 -R F -O q -, the compound represented by the formula (1) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.

[0038] In the above formula (2), R F2 is -Rf 2 p -R F -O q - or a fluoroalkylene group. In one embodiment, R F2 is preferably Rf 2 p -R F -Oq - and, in another embodiment, R F2 is preferably a fluoroalkylene group. When R F2 is Rf 2 p -R F -O q -, the compound represented by the formula (2) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.

[0039] In the above formula, Rf 1 is, in each occurrence, independently, a C 1-16 alkyl group which may be substituted by one or more fluorine atoms.

[0040] The "C 1-16 alkyl group" in the alkyl group which may be substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-16 alkyl group, particularly a C 1-6 alkyl group, more preferably a linear C 1-3 alkyl group, particularly a C 1-6 alkyl group, particularly a C 1-3 alkyl group.

[0041] The above Rf 1 is preferably a C 1-16 alkyl group substituted by one or more fluorine atoms, more preferably a CF2H-C 1-15 perfluoroalkylene group, and even more preferably a C 1-16 perfluoroalkyl group.

[0042] The above C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, more preferably a linear C 1-6 perfluoroalkyl group, particularly a C 1-3A perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0043] In the above formula, Rf 2 is a C 1-6 alkylene group which may be substituted by one or more fluorine atoms.

[0044] The "C 1-6 alkylene group" in the above-mentioned C 1-6 alkylene group which may be substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-3 alkylene group, more preferably a linear C 1-3 alkylene group.

[0045] The above Rf 2 is preferably a C 1-6 alkylene group substituted by one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, even more preferably a C 1-3 perfluoroalkylene group.

[0046] The above C 1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0047] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0048] In the above formula, q is, in each occurrence, independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0049] In the above formulas (1) and (2), R F is, in each occurrence, independently, a divalent fluoropolyether group.

[0050] R F is preferably the following: -(OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 - [wherein: R Fa is, in each occurrence, independently, a hydrogen atom, a fluorine atom or a chlorine atom, h1 is an integer from 1 to 6, h2 is an integer from 4 to 8, h3 is an integer of 0 or more, h4 is an integer of 0 or more, provided that the sum of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of presence of each repeating unit enclosed in parentheses with h3 and h4 is arbitrary in the formula.] and may contain a group represented by

[0051] In one embodiment, R F can be linear or branched. R F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [wherein: R Fa is, in each occurrence, independently, a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e, and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, when all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.] is a group represented by.

[0052] R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.

[0053] a, b, c, d, e, and f may preferably each independently be an integer from 0 to 100.

[0054] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0055] These repeating units may be linear, branched, or may contain a ring structure. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10)- may be, for example, -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0056] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, wear durability, etc. of the surface treatment layer can be improved.

[0057] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the coefficient of kinetic friction of the surface treatment layer can be increased.

[0058] In one embodiment, R F may contain a ring structure.

[0059] The ring structure may be a three-membered ring, four-membered ring, five-membered ring, or six-membered ring described below.

[0060]

Chemical formula

[0061] The above ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0062] The repeating unit having a ring structure may preferably be the following unit.

[0063]

Chemical formula

[0064] In one aspect, the above repeating unit is linear. By making the above repeating unit linear, the surface slipperiness, wear durability, etc. of the surface treatment layer can be improved.

[0065] In one aspect, the above repeating unit is branched. By making the above repeating unit branched, the coefficient of kinetic friction of the surface treatment layer can be increased.

[0066] In one aspect, R F is, in each occurrence, independently a group represented by any of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.]; -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200, the sum of c, d, e, and f is 2 or more, the order of existence of each repeating unit enclosed in parentheses with subscripts c, d, e, or f is arbitrary in the formula.]; -(R 6 -R 7 ) g- (f3) [Wherein, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, and g is an integer from 2 to 100.]; -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [Wherein, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g’ is an integer from 2 to 100, R r is

[0067]

Chemical formula

[0068] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2). In one aspect, e is 0. In another aspect, e is 1.

[0069] In the above formula (f2), e and f are each independently, preferably integers of 5 to 200, more preferably 10 to 200. Further, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f -represented groups. In another embodiment, the formula (f2) may be a group represented by -(OC2F4) e -(OCF2) f -.

[0070] In the above formula (f3), R 6 is preferably OCF2 or OC2F4, more preferably OCF2. In the above (f3), R 7 is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F10 and OC6F 12 may be either linear or branched, preferably linear. In this embodiment, the above formula (f3) is preferably -(OCF2-OC2F4) g -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g .

[0071] In the above formula (f4), R 6 , R 7 and g have the same meanings as described in the above formula (f3) and have similar embodiments. R 6’ , R 7’ and g' have the same meanings as R 6 , R 7 and g described in the above formula (f3) respectively and have similar embodiments. R r is preferably

[0072]

Chemical formula

[0073]

Chemical formula

[0074] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0075] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0076] In one embodiment, the above R F is a group represented by the above formula (f1).

[0077] In one embodiment, the above R F is a group represented by the above formula (f2).

[0078] In one embodiment, the above R F is a group represented by the above formula (f3).

[0079] In one embodiment, the above R F is a group represented by the above formula (f4).

[0080] In one embodiment, the above R F is a group represented by the above formula (f5).

[0081] In one embodiment, the above R F is a group represented by the above formula (f6).

[0082] In one embodiment, the fluorine-containing silane compound contained in the surface treatment layer preferably contains a structure represented by the above formula (f1), (f2), (f3), (f5) or (f6) from the viewpoint of the slipperiness of the surface treatment layer, more preferably contains a structure represented by the above formula (f1) or (f2), and even more preferably contains a structure represented by the above formula (f1).

[0083] In another embodiment, the fluorine-containing silane compound that may be contained in the surface treatment layer preferably contains a structure represented by the above formula (f1), (f2), (f3), (f4), (f5) or (f6), more preferably contains a structure represented by the above formula (f1) or (f2), and even more preferably contains a structure represented by the above formula (f2).

[0084] The above R FIn this case, the ratio of e to f (hereinafter referred to as "e / f ratio") is from 0.1 to 10, preferably from 0.2 to 5, more preferably from 0.2 to 2, still more preferably from 0.2 to 1.5, and even more preferably from 0.2 to 0.85. By setting the e / f ratio to 10 or less, the slipperiness, wear durability, and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the more improved the slipperiness and wear durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The larger the e / f ratio, the more improved the stability of the compound.

[0085] R F1 The fluoroalkyl group represented by is a group in which the hydrogen atoms contained in the alkyl group are replaced by fluorine atoms, and may be linear or branched. The above R F1 The fluoroalkyl group represented by is preferably a C 1-50 fluoroalkyl group, more preferably a C 1-20 fluoroalkyl group, still more preferably a C 1-16 fluoroalkyl group, for example, a C 1-10 fluoroalkyl group, and further a C 1-6 fluoroalkyl group, particularly a C 1-3 fluoroalkyl group may also be acceptable. In one embodiment, the R F1 The fluoroalkyl group represented by is a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. In such an embodiment, the above perfluoroalkyl group is preferably a linear or branched C 1-50 perfluoroalkyl group, more preferably a linear or branched C 1-20 perfluoroalkyl group, still more preferably a linear or branched C 1-16 perfluoroalkyl group, for example, a linear or branched C 1-10 perfluoroalkyl group, and further a linear or branched C 1-6 perfluoroalkyl group, particularly a linear or branched C 1-3 perfluoroalkyl group may also be acceptable.

[0086] R F2 The fluoroalkylene group represented by is a group in which the hydrogen atoms contained in the alkylene group are replaced by fluorine atoms, and it may be linear or branched. The above R F2 The fluoroalkylene group represented by is preferably a C 1-50 fluoroalkylene group, more preferably a C 1-20 fluoroalkylene group, even more preferably a C 1-16 fluoroalkylene group. For example, a C 1-10 fluoroalkylene group, and further a C 1-6 fluoroalkylene group, particularly a C 1-3 fluoroalkylene group may also be used. In one aspect, the R F2 The fluoroalkylene group represented by is a perfluoroalkylene group in which all hydrogen atoms are replaced by fluorine atoms. In such an aspect, the above perfluoroalkylene group is preferably a linear or branched C 1-50 perfluoroalkylene group, more preferably a linear or branched C 1-20 perfluoroalkylene group, even more preferably a linear or branched C 1-16 perfluoroalkylene group. For example, a linear or branched C 1-10 perfluoroalkylene group, and further a linear or branched C 1-6 perfluoroalkylene group, particularly a linear or branched C 1-3 perfluoroalkylene group may also be used.

[0087] In the above fluorine-containing silane compound, R F1 and R F2 The number average molecular weight of the part is not particularly limited. For example, it is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, R F1 and R F2 The number average molecular weight of is 19 The value measured by 19F-NMR.

[0088] In another aspect, R F1 and R F2 The number average molecular weight of the moiety can be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0089] In another aspect, R F1 and R F2 The number average molecular weight of the moiety can be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.

[0090] In the above formulas (1) and (2), R Si is, in each occurrence, independently, a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded, and at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0091] Here, the "hydrolyzable group" means a group that can undergo a hydrolysis reaction, that is, a group that can be detached from the main skeleton of the compound by a hydrolysis reaction. Examples of the hydrolyzable group include -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, halogen (wherein R j represents a substituted or unsubstituted C 1-4 alkyl group), and the like.

[0092] In a preferred aspect, R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0093] In a preferred aspect, R Si is the following formula (S1), (S2), (S3), or (S4):

Chemical formula

[0094] In the above formula, R 11 is, in each occurrence, independently a hydroxyl group or a hydrolyzable group.

[0095] R 11 is preferably, in each occurrence, independently a hydrolyzable group.

[0096] R 11 is preferably, in each occurrence, independently -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). R j Examples include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one aspect, R j is a methyl group, and in another aspect, R j is an ethyl group.

[0097] In the above formula, R 12 is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0098] R 12 Among them, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.

[0099] In the above formula, n1 is (SiR11 n1 R 12 3-n1 ) is an integer from 0 to 3, independent for each unit. However, when R Si is a group represented by the formula (S1) or (S2), in the R Si moieties at the ends of the formula (1) and the formula (2) (hereinafter, also simply referred to as the "end moieties" of the formula (1) and the formula (2)), n1 is from 1 to 3 (SiR 11 n1 R 12 3-n1 ) units are present at least one. That is, in such end moieties, all n1 do not simultaneously become 0. In other words, in the end moieties of the formula (1) and the formula (2), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.

[0100] n1 is, independent for each (SiR 11 n1 R 12 3-n1 ) unit, preferably an integer from 1 to 3, more preferably 2 to 3, and still more preferably 3.

[0101] In the above formula, X 11 is, independently for each occurrence, a single bond or a divalent organic group. Such a divalent organic group is preferably -R 28 -O x -R 29 -(wherein R 28 and R 29 are, independently for each occurrence, a single bond or a C 1-20 alkylene group, and x is 0 or 1). Such a C 1-20 alkylene group may be linear or branched, but is preferably linear. Such a C 1-20 alkylene group is preferably a C 1-10 alkylene group, more preferably a C 1-6 alkylene group, and still more preferably a C 1-3 alkylene group.

[0102] In one embodiment, X 11is, independently at each occurrence, -C 1-6 alkylene - O - C 1-6 alkylene - or - O - C 1-6 alkylene -.

[0103] In a preferred embodiment, X 11 is, independently at each occurrence, a single bond or a linear C 1-6 alkylene group, preferably a single bond or a linear C 1-3 alkylene group, more preferably a single bond or a linear C 1-2 alkylene group, even more preferably a linear C 1-2 alkylene group.

[0104] In the above formula, R 13 is, independently at each occurrence, a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably a C 1-20 alkyl group. Such a C 1-20 alkyl group may be linear or branched, but is preferably linear.

[0105] In a preferred embodiment, R 13 is, independently at each occurrence, a hydrogen atom or a linear C 1-6 alkyl group, preferably a hydrogen atom or a linear C 1-3 alkyl group, preferably a hydrogen atom or a methyl group.

[0106] In the above formula, t is, independently at each occurrence, an integer of 2 or more.

[0107] In a preferred embodiment, t is, independently at each occurrence, an integer from 2 to 10, preferably an integer from 2 to 6.

[0108] In the above formula, R 14 is, independently at each occurrence, a hydrogen atom, a halogen atom or - X 11 - SiR 11 n1 R 12 3-n1It is. Such a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R 14 is a hydrogen atom.

[0109] In the above formula, R 15 is, in each occurrence, independently of one another, a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group having 1 to 6 carbon atoms.

[0110] In one embodiment, R 15 is, in each occurrence, independently of one another, an oxygen atom, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group having 1 to 6 carbon atoms.

[0111] In a preferred embodiment, R 15 is a single bond.

[0112] In one embodiment, formula (S1) is the following formula (S1-a).

Chemical formula

[0113] In a preferred embodiment, formula (S1) is the following formula (S1-b).

Chemical formula

[0114] In the above formula, R a1 is, in each occurrence, independently of one another, -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 is as follows.

[0115] The above Z 1 is, in each occurrence, independently of one another, an oxygen atom or a divalent organic group. Incidentally, the structure described as Z 1 below is bonded on the right side to (SiR 21 p1 R 22 q1 R 23 r1 ).

[0116] In a preferred embodiment, Z 1 is a divalent organic group.

[0117] In a preferred embodiment, Z 1 does not include those that form a siloxane bond with the Si atom to which Z 1 is bonded. Preferably, in formula (S3), (Si-Z 1 -Si) does not include a siloxane bond.

[0118] The above Z 1 is preferably a C 1-6 alkylene group, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer from 0 to 6, for example, an integer from 1 to 6, and z2 is an integer from 0 to 6, for example, an integer from 1 to 6), or -(CH2) z3 -phenylene-(CH2) z4 -(wherein z3 is an integer from 0 to 6, for example, an integer from 1 to 6, and z4 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6The alkylene group may be linear or branched, but is preferably linear. These groups may be substituted, for example, with one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but is preferably unsubstituted.

[0119] In a preferred embodiment, Z 1 is a C 1-6 alkylene group or -(CH2) z3 -phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -. When Z 1 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0120] In another preferred embodiment, the above Z 1 is a C 1-3 alkylene group. In one embodiment, Z 1 can be -CH2CH2CH2-. In another embodiment, Z 1 can be -CH2CH2-.

[0121] The above R 21 is, in each occurrence, independently, -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ .

[0122] The above Z 1’ is, in each occurrence, independently, an oxygen atom or a divalent organic group. Incidentally, the structure described as Z 1’ below is bonded to the right side (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ).

[0123] In a preferred embodiment, Z1’ is a divalent organic group.

[0124] In a preferred embodiment, Z 1’ is such that it does not include those that form a siloxane bond with the Si atom to which Z 1’ is bonded. Preferably, in formula (S3), (Si-Z 1’ -Si) does not include a siloxane bond.

[0125] The above Z 1’ is preferably a C 1-6 alkylene group, -(CH2) z1’ -O-(CH2) z2’ -(wherein, z1’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z2’ is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH2) z3’ -phenylene-(CH2) z4’ -(wherein, z3’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z4’ is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted by one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but is preferably unsubstituted.

[0126] In a preferred embodiment, Z 1’ is a C 1-6 alkylene group or -(CH2) z3’ -phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ -. When Z 1’ is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0127] In another preferred embodiment, the above Z 1’ is a C 1-3 alkylene group. In one embodiment, Z 1’can be -CH2CH2CH2-. In another embodiment, Z 1’ can be -CH2CH2-.

[0128] Each occurrence of the above R 21’ is independently, in each occurrence, -Z 1” -SiR 22” q1” R 23” r1” is as follows.

[0129] Each occurrence of the above Z 1” is independently, in each occurrence, an oxygen atom or a divalent organic group. Hereinafter, the structure described as Z 1” is bonded to the right side (SiR 22” q1” R 23” r1” ).

[0130] In a preferred embodiment, Z 1” is a divalent organic group.

[0131] In a preferred embodiment, Z 1” does not include those that form a siloxane bond with the Si atom to which Z 1” is bonded. Preferably, in formula (S3), (Si-Z 1” -Si) does not include a siloxane bond.

[0132] Each occurrence of the above Z 1” is preferably a C 1-6 alkylene group, -(CH2) z1” -O-(CH2) z2” -(wherein z1” is an integer from 0 to 6, for example, an integer from 1 to 6, and z2” is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH2) z3” -phenylene-(CH2) z4” -(wherein z3” is an integer from 0 to 6, for example, an integer from 1 to 6, and z4” is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, C1-6 an alkyl group, C 2-6 an alkenyl group, and C 2-6 an alkynyl group, and may be substituted with one or more substituents selected therefrom, but is preferably unsubstituted.

[0133] In a preferred embodiment, Z 1” is a C 1-6 alkylene group or -(CH2) z3” -phenylene-(CH2) z4” -, preferably -phenylene-(CH2) z4” -. Z 1” When Z is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0134] In another preferred embodiment, the above Z 1” is a C 1-3 alkylene group. In one embodiment, Z 1” can be -CH2CH2CH2-. In another embodiment, Z 1” can be -CH2CH2-.

[0135] The above R 22” is, in each occurrence, independently a hydroxyl group or a hydrolyzable group.

[0136] The above R 22” is preferably, in each occurrence, independently a hydrolyzable group.

[0137] The above R 22” is preferably, in each occurrence, independently -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (wherein R j represents a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). R jExamples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, alkyl groups, especially unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0138] The above R 23” is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0139] In the above R 23” , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.

[0140] The above q1” is, in each occurrence, independently an integer from 0 to 3, and the above r1” is, in each occurrence, independently an integer from 0 to 3. Note that the sum of q1” and r1” is 3 in the (SiR 22” q1” R 23” r1” ) unit.

[0141] The above q1” is, for each (SiR 22” q1” R 23” r1” ) unit, independently preferably an integer from 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0142] The above R 22’ is, in each occurrence, independently a hydroxyl group or a hydrolyzable group.

[0143] R 22’ is preferably, in each occurrence, independently a hydrolyzable group.

[0144] R 22’ is preferably, in each occurrence, independently of one another, -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), more preferably -OR j (i.e., an alkoxy group). As R j , there may be mentioned unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group; substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0145] The above R 23’ is, in each occurrence, independently of one another, a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0146] R 23’ in, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0147] The above p1' is, in each occurrence, independently of one another, an integer of 0 to 3, q1' is, in each occurrence, independently of one another, an integer of 0 to 3, and r1' is, in each occurrence, independently of one another, an integer of 0 to 3. It should be noted that the sum of p', q1' and r1' is 3 in the (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) unit.

[0148] In one aspect, p1’ is 0.

[0149] In one aspect, p1’ may be, independently for each (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred aspect, p1’ is 3.

[0150] In one aspect, q1’ is, independently for each (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) unit, an integer from 1 to 3, preferably an integer from 2 to 3, more preferably 3.

[0151] In one aspect, p1’ is 0 and q1’ is, independently for each (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) unit, an integer from 1 to 3, preferably an integer from 2 to 3, even more preferably 3.

[0152] The above R 22 is, independently for each occurrence, a hydroxyl group or a hydrolyzable group.

[0153] R 22 is preferably, independently for each occurrence, a hydrolyzable group.

[0154] R 22 is preferably, independently for each occurrence, -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (in these formulas, R j is a substituted or unsubstituted C 1-4(which represents an alkyl group), more preferably -OR j (i.e., an alkoxy group). R j Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0155] The above R 23 is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0156] In R 23 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.

[0157] The above p1 is, in each occurrence, independently an integer from 0 to 3, q1 is, in each occurrence, independently an integer from 0 to 3, and r1 is, in each occurrence, independently an integer from 0 to 3. It should be noted that the sum of p1, q1, and r1 is 3 in the (SiR 21 p1 R 22 q1 R 23 r1 ) unit.

[0158] In one embodiment, p1 is 0.

[0159] In one embodiment, p1 is (SiR 21 p1 R 22 q1 R 23 r1) Independently for each unit, it may be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1 is 3.

[0160] In one embodiment, q1 is (SiR 21 p1 R 22 q1 R 23 r1 ) Independently for each unit, it is an integer from 1 to 3, preferably an integer from 2 to 3, more preferably 3.

[0161] In one embodiment, p1 is 0 and q1 is (SiR 21 p1 R 22 q1 R 23 r1 ) Independently for each unit, it is an integer from 1 to 3, preferably an integer from 2 to 3, even more preferably 3.

[0162] In the above formula, R b1 is, independently for each occurrence, a hydroxyl group or a hydrolyzable group.

[0163] The above R b1 is preferably, independently for each occurrence, a hydrolyzable group.

[0164] The above R b1 is preferably, independently for each occurrence, -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (wherein, in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). R jExamples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0165] In the above formula, R c1 is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0166] In the above R c1 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0167] The above k1 is, in each occurrence, independently an integer of 0 to 3, l1 is, in each occurrence, independently an integer of 0 to 3, and m1 is, in each occurrence, independently an integer of 0 to 3. Note that the sum of k1, l1 and m1 is 3 in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit.

[0168] In one embodiment, k1 is, for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit, independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0169] In the above formulas (1) and (2), R SiWhen it is a group represented by the formula (S3), preferably, at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group are present at the terminal portions of the formula (1) and the formula (2).

[0170] In a preferred embodiment, the group represented by the formula (S3) is -Z 1 -SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2).), -Z 1’ -SiR 22’ q1’ R 23’ r1’ (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2).), or -Z 1” -SiR 22” q1” R 23” r1” (wherein q1'' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1'' is an integer of 0 to 2).) and has any one of them. Z 1 , Z 1’ , Z 1” , R 22 , R 23 , R 22’ , R 23’ , R 22” , and R 23” have the same meanings as described above.

[0171] In a preferred embodiment, in the formula (S3), when R 21’ is present, in at least one, preferably all of the R 21’ , q1'' is an integer of 1 to 3, preferably 2 or 3, more preferably 3.

[0172] In a preferred embodiment, in the formula (S3), when R 21 is present, in at least one, preferably all of the R 21In this case, p1' is 0, q1' is an integer from 1 to 3, preferably 2 or 3, more preferably 3.

[0173] In a preferred embodiment, in formula (S3), R a1 when present, at least one, preferably all, of the R a1 In this case, p1 is 0, q1 is an integer from 1 to 3, preferably 2 or 3, more preferably 3.

[0174] In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

[0175] R d1 is, in each occurrence, independently of one another, -Z 2 -CR 31 p2 R 32 q2 R 33 r2 is.

[0176] Z 2 is, in each occurrence, independently of one another, a single bond, an oxygen atom or a divalent organic group. Incidentally, the structure described as Z 2 below is bonded on the right side to (CR 31 p2 R 32 q2 R 33 r2 ).

[0177] In a preferred embodiment, Z 2 is a divalent organic group.

[0178] The above Z 2 is preferably a C 1-6 alkylene group, -(CH2) z5 -O-(CH2) z6 -(wherein z5 is an integer from 0 to 6, for example an integer from 1 to 6, and z6 is an integer from 0 to 6, for example an integer from 1 to 6) or, -(CH2) z7 -phenylene-(CH2)z8 -(wherein, z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, C 1-6 alkyl group, C 2-6 alkenyl group, and C 2-6 alkynyl group, and may be substituted with one or more substituents selected therefrom, but is preferably unsubstituted.

[0179] In a preferred embodiment, Z 2 is a C 1-6 alkylene group or -(CH2) z7 -phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 -. When Z 2 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0180] In another preferred embodiment, the above Z 2 is a C 1-3 alkylene group. In one embodiment, Z 2 can be -CH2CH2CH2-. In another embodiment, Z 2 can be -CH2CH2-.

[0181] R 31 is, in each occurrence, independently of one another, -Z 2’ -CR 32’ q2’ R 33’ r2’ .

[0182] Z 2’ is, in each occurrence, independently of one another, a single bond, an oxygen atom or a divalent organic group. Incidentally, the structure described as Z 2’ below is bonded to the right side by (CR 32’ q2’ R 33’ r2’ ).

[0183] The above Z 2’ is preferably a C 1-6 alkylene group, -(CH2) z5’ -O-(CH2) z6’ -(wherein, z5’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z6’ is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH2) z7’ -phenylene-(CH2) z8’ -(wherein, z7’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z8’ is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, C 1-6 alkyl group, C 2-6 alkenyl group, and C 2-6 alkynyl group, and may be substituted by one or more substituents selected therefrom, but is preferably unsubstituted.

[0184] In a preferred embodiment, Z 2’ is a C 1-6 alkylene group or -(CH2) z7’ -phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ -. When Z 2’ is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0185] In another preferred embodiment, the above Z 2’ is a C 1-3 alkylene group. In one embodiment, Z 2’ can be -CH2CH2CH2-. In another embodiment, Z 2’ can be -CH2CH2-.

[0186] The above R 32’ is, in each occurrence, independently, -Z 3 -SiR 34 n2 R 35 3-n2 is.

[0187] The above Z 3 is, in each occurrence, independently, a single bond, an oxygen atom or a divalent organic group. Incidentally, hereinafter, the structure described as Z 3 has the right side bonded to (SiR 34 n2 R 35 3-n2 ).

[0188] In one embodiment, Z 3 is an oxygen atom.

[0189] In one embodiment, Z 3 is a divalent organic group.

[0190] The above Z 3 is preferably a C 1-6 alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein, z5” is an integer from 0 to 6, for example, an integer from 1 to 6, and z6” is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH2) z7” -phenylene-(CH2) z8” -(wherein, z7” is an integer from 0 to 6, for example, an integer from 1 to 6, and z8” is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted by one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but is preferably unsubstituted.

[0191] In a preferred embodiment, Z 3 is a C 1-6 alkylene group or -(CH2) z7” -phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” -. When Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0192] In another preferred embodiment, the above Z 3 is a C 1-3 alkylene group. In one embodiment, Z 3 can be -CH2CH2CH2-. In another embodiment, Z 3 can be -CH2CH2-.

[0193] The above R 34 is, in each occurrence, independently a hydroxyl group or a hydrolyzable group.

[0194] R 34 is preferably, in each occurrence, independently a hydrolyzable group.

[0195] R 34 is preferably, in each occurrence, independently -OR j , -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). As R j , examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0196] The above R 35 is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0197] The above R35 In this case, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0198] In the above formula, n2 is, for each (SiR 34 n2 R 35 3-n2 ) unit, independently an integer of 0 to 3. However, when R Si is a group represented by the formula (S4), at the terminal portions of the formulas (1) and (2), n2 is 1 to 3 and at least one (SiR 34 n2 R 35 3-n2 ) unit exists. That is, in such terminal portions, all n2 do not simultaneously become 0. In other words, at the terminal portions of the formulas (1) and (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0199] n2 is, for each (SiR 34 n2 R 35 3-n2 ) unit, independently preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3.

[0200] The above R 33’ is, in each occurrence, independently a hydrogen atom, a hydroxyl group or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0201] In the above R 33’ , the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2H (wherein s is an integer from 1 to 6, preferably an integer from 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6). More preferably, it is C 1-20 alkyl group, still more preferably C 1-6 alkyl group, particularly preferably a methyl group.

[0202] In one embodiment, R 33’ is a hydroxyl group.

[0203] In another embodiment, R 33’ is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0204] Each occurrence of q2’ is independently an integer from 0 to 3, and each occurrence of r2’ is independently an integer from 0 to 3. Incidentally, the sum of q2’ and r2’ is 3 in the (CR 32’ q2’ R 33’ r2’ ) unit.

[0205] q2’ is preferably an integer from 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (CR 32’ q2’ R 33’ r2’ ) unit.

[0206] Each occurrence of R 32 is independently -Z 3 -SiR 34 n2 R 35 3-n2 . Such -Z 3 -SiR 34 n2 R 35 3-n2 is as defined in R 32’ above.

[0207] The above R 33 is, in each occurrence, independently, a hydrogen atom, a hydroxyl group or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0208] The above R 33 in, the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 H (wherein s is, in each occurrence, independently, an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6).), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, particularly preferably a methyl group.

[0209] In one embodiment, R 33 is a hydroxyl group.

[0210] In another embodiment, R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0211] The above p2 is, in each occurrence, independently, an integer of 0 to 3, q2 is, in each occurrence, independently, an integer of 0 to 3, and r2 is, in each occurrence, independently, an integer of 0 to 3. Incidentally, the sum of p2, q2 and r2 is 3 in the (CR 31 p2 R 32 q2 R 33 r2 ) unit.

[0212] In one embodiment, p2 is 0.

[0213] In one embodiment, p2 may be independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit. In a preferred embodiment, p2 is 3.

[0214] In one embodiment, q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit, and is independent of each other.

[0215] In one embodiment, p2 is 0, and q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit, and is independent of each other.

[0216] The above R e1 is, in each occurrence, independently -Z 3 -SiR 34 n2 R 35 3-n2 . Such -Z 3 -SiR 34 n2 R 35 3-n2 is as defined in the above R 32’ .

[0217] The above R f1 is, in each occurrence, independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0218] In the above R f1 , the monovalent organic group is preferably C 1-20An alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6). More preferably, it is a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, particularly preferably a methyl group.

[0219] In one embodiment, R f1 is a hydroxyl group.

[0220] In another embodiment, R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0221] The above k2 is, in each occurrence, independently an integer of 0 to 3, l2 is, in each occurrence, independently an integer of 0 to 3, and m2 is, in each occurrence, independently an integer of 0 to 3. It should be noted that the sum of k2, l2, and m2 is 3 in the (CR d1 k2 R e1 l2 R f1 m2 ) unit.

[0222] In the above formulas (1) and (2), when R Si is a group represented by the formula (S4), preferably, at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group are present at the terminal portions of the formulas (1) and (2).

[0223] In one embodiment, when R Si is a group represented by the formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 353-n2 ) In each of the terminal portions of Formula (1) and Formula (2), there are two or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3, and particularly preferably 3.

[0224] In a preferred embodiment, in Formula (S4), when R 32’ is present, at least one, preferably all of the R 32’ , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3.

[0225] In a preferred embodiment, in Formula (S4), when R 32 is present, at least one, preferably all of the R 32 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3.

[0226] In a preferred embodiment, in Formula (S4), when R e1 is present, at least one, preferably all of the R a1 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3.

[0227] In a preferred embodiment, in Formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0228] The above R g1 and R h1 are each independently, in each occurrence, -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2R f1 m2 is. Here, R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 have the same meanings as described above.

[0229] In a preferred embodiment, R g1 and R h1 are each independently, -Z 4 -SiR 11 n1 R 12 3-n1 is.

[0230] The above Z 4 is, in each occurrence, independently, a single bond, an oxygen atom, or a divalent organic group. Note that the structure described as Z 4 below is bonded to the right side by (SiR 11 n1 R 12 3-n1 ).

[0231] In one embodiment, Z 4 is an oxygen atom.

[0232] In one embodiment, Z 4 is a divalent organic group.

[0233] The above Z 4 is preferably a C 1-6 alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein z5” is an integer from 0 to 6, for example, an integer from 1 to 6, and z6” is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH2) z7” -phenylene-(CH2) z8” -(wherein z7” is an integer from 0 to 6, for example, an integer from 1 to 6, and z8” is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6The alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, C 1-6 alkyl group, C 2-6 alkenyl group, and C 2-6 alkynyl group, and may be substituted with one or more substituents selected therefrom, but is preferably unsubstituted.

[0234] In a preferred embodiment, Z 4 is a C 1-6 alkylene group or -(CH2) z7” -phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” -. When Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0235] In another preferred embodiment, the above Z 4 is a C 1-3 alkylene group. In one embodiment, Z 4 can be -CH2CH2CH2-. In another embodiment, Z 4 can be -CH2CH2-.

[0236] In one embodiment, R Si is a group represented by formula (S2), (S3), (S4) or (S5). These compounds can form a surface treatment layer having high surface slipperiness.

[0237] In one embodiment, R Si is a group represented by formula (S3), (S4) or (S5). Since these compounds have a plurality of hydrolyzable groups at one end, they can strongly adhere to the substrate and form a surface treatment layer having high wear durability.

[0238] In one embodiment, R Siis a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, a surface treatment layer having higher wear durability can be formed.

[0239] In one embodiment, R Si is a group represented by formula (S1).

[0240] In one embodiment, R Si is a group represented by formula (S2).

[0241] In one embodiment, R Si is a group represented by formula (S3).

[0242] In one embodiment, R Si is a group represented by formula (S4).

[0243] In one embodiment, R Si is a group represented by formula (S5).

[0244] In the above formulas (1) and (2), X A is understood to be a linker that connects the fluoropolyether moiety (R F1 and R F2 ) that mainly provides water repellency and surface slipperiness, etc., and the moiety (R Si ) that provides the binding ability between the inorganic layer. Therefore, the X A may be a single bond or any group as long as the compounds represented by formulas (1) and (2) can exist stably.

[0245] In the above formula (1), α is an integer from 1 to 9, and β is an integer from 1 to 9. These α and β can vary according to the valence of X A . The sum of α and β is the same as the valence of X A . For example, when X A is a decavalent organic group, the sum of α and β is 10, and for example, α can be 9 and β can be 1, α can be 5 and β can be 5, or α can be 1 and β can be 9. Also, X AWhen it is a divalent organic group, α and β are 1.

[0246] In the above formula (2), γ is an integer from 1 to 9. γ can vary according to A the valence of X. That is, γ is a value obtained by subtracting 1 from the valence of X. A

[0247] X A is, independently of each other, a single bond or a divalent to decavalent organic group;

[0248] The divalent to decavalent organic group in the above X A is preferably a divalent to octavalent organic group. In one aspect, such a divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group. In another aspect, such a divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.

[0249] In one aspect, X A is a single bond or a divalent organic group, α is 1, and β is 1.

[0250] In one aspect, X A is a single bond or a divalent organic group, and γ is 1.

[0251] In one aspect, X A is a trivalent to hexavalent organic group, α is 1, and β is 2 to 5.

[0252] In one aspect, X A is a trivalent to hexavalent organic group, and γ is 2 to 5.

[0253] In one aspect, X A is a trivalent organic group, α is 1, and β is 2.

[0254] In one aspect, X A is a trivalent organic group, and γ is 2.

[0255] XA When it is a single bond or a divalent organic group, Formulas (1) and (2) are represented by the following Formulas (1') and (2').

Chemical formula

[0256] In one embodiment, X A is a single bond.

[0257] In another embodiment, X A is a divalent organic group.

[0258] In one embodiment, X A is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [Wherein: R 51 represents a single bond, -(CH2) s5 -, or an o-, m-, or p-phenylene group, preferably -(CH2) s5 -, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2, X 51 represents -(X 52 ) l5 -, X 52 is, in each occurrence, independently, -O-, -S-, o-, m-, or p-phenylene group, -C(O)O-, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -, -O-CONR 54 -, -NR 54 -, and -(CH2) n5 - selected from the group consisting of, R 53 is, in each occurrence, independently, a phenyl group, C 1-6An alkyl group or C 1-6 represents an alkoxy group, preferably a phenyl group or C 1-6 alkyl group, more preferably a methyl group, R 54 in each occurrence, independently represents a hydrogen atom, a phenyl group or C 1-6 alkyl group (preferably a methyl group), m5, in each occurrence, independently represents an integer from 1 to 100, preferably an integer from 1 to 20, n5, in each occurrence, independently represents an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, l5 represents an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the order of existence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary] Examples of the divalent organic group represented by. Here, X A (typically the hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, C 1-3 alkyl group and C 1-3 fluoroalkyl group. In a preferred embodiment, X A is not substituted with these groups.

[0259] In a preferred embodiment, the above X A each independently represents -(R 51 ) p5 -(X 51 ) q5 -R 52 -. R 52 represents a single bond, -(CH2) t5 - or o-, m- or p-phenylene group, preferably -(CH2) t5 -. t5 represents an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Here, R 52 (typically R52 The hydrogen atom) is one or more substituents selected from a fluorine atom, C 1-3 alkyl group and C 1-3 fluoroalkyl group, and may be substituted. In a preferred embodiment, R 56 is not substituted by these groups.

[0260] Preferably, the above X A are each independently a single bond, C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 52 - [wherein, R 51 and R 52 are as defined above, X 53 is -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -Si(R 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-, -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 53 )2- (In the formula, R 53 , R 54 and m5 have the same meaning as above, u5 represents an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 or 3; X 54 teeth, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (In the formula, each symbol has the same meaning as above.) represents.] It could be.

[0261] More preferably, the above X A are each independently single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -, -(CH2) s5 -X53 -(CH2) t5 - -X 54 - or -X 54 -(CH2) t5 - [wherein, X 53 , X 54 , s5 and t5 have the same meanings as defined above.] is.

[0262] More preferably, the above X A are each independently a single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -(CH2) t5 - or -X 54 -(CH2) t5 - [wherein each symbol has the same meaning as defined above.] may be.

[0263] In a preferred embodiment, the above X A are each independently a single bond C 1-20 an alkylene group, -(CH2) s5 -X 53 - or -(CH2) s5 -X 53 -(CH2) t5 - [wherein X 53 is -O-, -CONR 54 -, or -O-CONR 54 -, and R 54 represents, in each occurrence, independently of one another, a hydrogen atom, a phenyl group or a C 1-6 alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20.] may be.

[0264] In a preferred embodiment, the above X A are each independently -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [wherein R 54 is, in each occurrence, independently a hydrogen atom, a phenyl group or a C 1-6 alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20.] can be.

[0265] In one embodiment, the above X A are each independently a single bond, a C 1-20 alkylene group, -(CH2) s5 -O-(CH2) t5 - -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 - -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, or -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [wherein R 53, m5, s5, t5, and u5 have the same meanings as defined above, and v5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. is.

[0266] In the above formula, -(C v H 2v )- may be linear or branched, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0267] Each of the above X A may be independently substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). In one embodiment, X A is unsubstituted.

[0268] In addition, each of the above X A is bonded to R F1 or R F2 on the left side of each formula, and is bonded to R Si on the right side.

[0269] In one embodiment, each of X A may be independently other than -O-C 1-6 alkylene group.

[0270] In another embodiment, examples of X A include the following groups:

Chemical formula

Chemical formula

Chemical formula

[0271] Specific examples of the above X A are, for example: A single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -CH2OCF2CHFOCF2-、 -CH2OCF2CHFOCF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-、 -CH2OCH2CF2CF2OCF2-、 -CH2OCH2CF2CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -(CH2)5-、 -(CH2)6-、 -CO-、 -CONH-、 -CONH-CH2-、 -CONH-(CH2)2-、 -CONH-(CH2)3-、 -CONH-(CH2)4-、 -CONH-(CH2)5-、 -CONH-(CH2)6-、 -CON(CH3)-CH2-、 -CON(CH3)-(CH2)2-、 -CON(CH3)-(CH2)3-、 -CON(CH3)-(CH2)4-、 -CON(CH3)-(CH2)5-、 -CON(CH3)-(CH2)6-、 -CON(Ph)-CH2-(where Ph means phenyl), -CON(Ph)-(CH2)2-(where Ph means phenyl), -CON(Ph)-(CH2)3-(where Ph means phenyl), -CON(Ph)-(CH2)4-(where Ph means phenyl), -CON(Ph)-(CH2)5-(where Ph means phenyl), -CON(Ph)-(CH2)6-(where Ph means phenyl), -CONH-(CH2)2NH(CH2)3-、 -CONH-(CH2)6NH(CH2)3-、 -CH2O-CONH-(CH2)3-、 -CH2O-CONH-(CH2)6-、 -S-(CH2)3-、 -(CH2)2S(CH2)3-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -C(O)O-(CH2)3-、 -C(O)O-(CH2)6-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、 -OCH2-、 -O(CH2)3-、 -OCFHCF2-、

Chem.

[0272] In yet another embodiment, X A is, independently of each other, a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 -. In the formula, x1, y1 and z1 are each independently an integer from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula.

[0273] In the above formula, R 16 is, in each occurrence, independently of each other, an oxygen atom, a phenylene, a carbazolylene, -NR 18 - (wherein R 18 represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, R 18 is an oxygen atom or a divalent polar group.

[0274] The above-mentioned "divalent polar group" is not particularly limited, and examples thereof include -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 - (in these formulas, R 19 represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.

[0275] In the above formula, R 17 is, in each occurrence, independently of each other, a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0276] In yet another aspect, X A Examples thereof include the following groups:

Chemical formula

Chemical formula

[0277] The radical scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation. Examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.

[0278] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. Examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxysinnamates, oxamides, oxanilides, benzoxazinones, benzoxazoles.

[0279] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include

Chemical formula

[0280] In this embodiment, X A can each independently be an organic group having a valence of 3 to 10.

[0281] In yet another embodiment, examples of X A include the following groups:

Chemical formula

[0282] In one embodiment, the above R 25 is a single bond, C1-20 an alkylene group, C 3-20 a cycloalkylene group, C 5-20 an arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -. In the above, R 57 and R 59 are each independently a single bond, C 1-20 an alkylene group, C 3-20 a cycloalkylene group, or C 5-20 an arylene group. In the above, X 58 is -O-, -S-, -CO-, -O-CO- or -COO-.

[0283] In one aspect, the above R 26 and R 27 are each independently a hydrocarbon, or a group having at least one atom selected from N, O and S in the end or main chain of the hydrocarbon, preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -,-R 36 -CHR 38 2- etc. are exemplified. Here, R 36 are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R 37 is N, O or S, preferably N or O. R 38 is -R 45 -R 46 -R 45 -,-R 46 -R 45 - or -R 45 -R 46 -. Here, R 45 are each independently an alkyl group having 1 to 6 carbon atoms. R 46 is N, O or S, preferably O.

[0284] In this aspect, X Amay each independently be an organic group having a valence of 3 to 10.

[0285] In yet another aspect, X A has, for example, the following: [Chemical formula] [wherein X a is a single bond or a divalent organic group.] Groups represented by

[0286] The above X a is a single bond or a divalent linking group directly bonded to the isocyanurate ring. X a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent organic group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.

[0287] X a has, for example, the following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (wherein X 121 to X 124 are each independently H, F, OH, or -OSi(OR 121 )3 (wherein the three Rs 121 are each independently an alkyl group having 1 to 4 carbon atoms).), The above X a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is bonded to CX 121 X 122 ). x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.) The group represented by is more preferred.)

[0288] The above X a1 is preferably -O- or -C(=O)O-.

[0289] The above X a is preferably the following formula: -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - (where m11 is an integer from 1 to 3, m12 is an integer from 1 to 3, and m13 is an integer from 1 to 3.) The group represented by, -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - (where m14 is an integer from 1 to 3, m15 is an integer from 1 to 3, and m16 is an integer from 1 to 3.) The group represented by, -(CF2) m17 -(CH2) m18 - (where m17 is an integer from 1 to 3, m18 is an integer from 1 to 3.) The group represented by, -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - (where m19 is an integer from 1 to 3, m20 is an integer from 1 to 3, and m21 is an integer from 1 to 3.) The group represented by, or -(CH2) m22 - (where m22 is an integer from 1 to 3.) The group represented by is particularly preferred.)

[0290] The above X a is not particularly limited, but specifically, -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, -(CF2) n5 -(n5 is an integer from 0 to 4.), -(CF2) n5 -(CH2) m5 -(n5 and m5 are each independently an integer from 0 to 4.), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- etc. can be mentioned.

[0291] In this embodiment, X A can each independently be a divalent or trivalent organic group.

[0292] The fluorine-containing silane compound represented by the above formula (1) or formula (2) is not particularly limited, but can have an average molecular weight of 5×10 2 ~1×10 5 . Among such ranges, it is preferable from the viewpoint of wear durability to have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000. Note that such "average molecular weight" refers to the number average molecular weight, and the "average molecular weight" 19 is the value measured by F-NMR.

[0293] The content of the fluorine-containing silane compound represented by the above formula (1) or (2) can be preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less in the total 100% by mass of the above fluorine-containing silane compound.

[0294] The content of the above fluorine-containing silane compound can be preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, still more preferably 0.04 to 25.0% by mass, particularly preferably 0.05 to 20.0% by mass in 100% by mass of the above surface treatment agent. By setting the content of the above fluorine-containing silane compound within the above range, higher water and oil repellency can be obtained.

[0295] The content rate of the above fluoropolyether group-containing silane compound is preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, still more preferably 0.04 to 25.0% by mass, and particularly preferably 0.05 to 20.0% by mass in 100% by mass of the above surface treatment agent. By setting the content of the above fluoropolyether group-containing silane compound within the above range, higher water and oil repellency can be obtained. In the composition of the present disclosure, the non-volatile content may be the part obtained by removing the solvent from the total amount of the composition.

[0296] The above surface treatment agent may further contain a solvent. By containing a solvent, the handleability of the composition becomes good. When a layer is formed using such a composition, the formed layer can be a continuous thin film. Further, such a composition can contribute to the formation of a thin film with an arbitrary film thickness.

[0297] The above solvent is not particularly limited. For example, perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (for example, C6F 13CH2CH3 (e.g., AsahiKlin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorola (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Limited), etc. alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., AsahiKlin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroether is preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0298] The boiling point (under atmospheric pressure) of the above solvent can preferably be less than 105 °C, more preferably 90 °C or less, and even more preferably 80 °C or less. When the above solvent has a boiling point within the above range, when the surface treatment agent of the present disclosure is applied to the above inorganic layer, it can be vaporized relatively easily without applying heating or the like, and the time and energy required for the surface treatment step can be reduced. The lower limit of such a boiling point is not particularly limited, but can be, for example, 30 °C or more, preferably 50 °C or more.

[0299] The content of the above solvent can preferably be 50 to 99.7% by mass, more preferably 60 to 99.7% by mass, even more preferably 70 to 99.7% by mass, and particularly preferably 80 to 99.7% by mass in the total 100% by mass of the above surface treatment agent.

[0300] The surface treatment agent of the present disclosure may further contain a (non-reactive) fluoropolyether compound that can be understood as a fluorinated oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorinated oil"), a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil"), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, and the like. It should be noted that other components are components different from the above-mentioned fluorinated silane compound and solvent.

[0301] The fluorinated oil is not particularly limited, and examples thereof include compounds (perfluoro(poly)ether compounds) represented by the following general formula (4). Rf 5 -(OC4F8) a” -(OC3F6) b” -(OC2F4) c” -(OCF2) d” -Rf 6 ···(4) In the formula, Rf 5 represents a C 1-16 alkyl group which may be substituted by one or more fluorine atoms (preferably a perfluoroalkyl group of C 1-16 ), Rf 6 represents a C 1-16 alkyl group which may be substituted by one or more fluorine atoms (preferably a perfluoroalkyl group of C 1-16 ), a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 are more preferably each independently a C 1-3 perfluoroalkyl group. "a", "b", "c" and "d" each represent the number of four repeating units of perfluoro(poly)ether that constitutes the main skeleton of the polymer, and are each an integer of 0 or more and 300 or less, independent of each other. The sum of "a", "b", "c" and "d" is greater than 30, preferably 40 to 300, more preferably 50 to 300. The order of presence of each repeating unit enclosed in parentheses with the subscript "a", "b", "c" or "d" is arbitrary in the formula. Among these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and (OCF2CF(C2F5)), but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)- and (OCF2CF(CF3)), and is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be any of -(OCF2CF2)- and (OCF(CF3)), but is preferably -(OCF2CF2)-.

[0302] Examples of the perfluoro(poly)ether compound represented by the above general formula (4) include compounds (which may be one or more mixtures) represented by any of the following general formulas (4a) and (4b). Rf 5 -(OCF2CF2CF2) b” -Rf 6 ···(4a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 ···(4b) In these formulas, Rf 5 and Rf 6is as described above; in formula (4a), b” is an integer of 1 or more and 100 or less; in formula (4b), a” and b” are each independently an integer of 0 or more and 30 or less, and c” and d” are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit enclosed in parentheses with subscripts a”, b”, c”, d” is arbitrary in the formula.

[0303] From another perspective, the fluorine-containing oil is represented by the general formula Rf 3 -F (wherein Rf 3 is a C 5-16 perfluoroalkyl group.) and may be a compound represented by the formula. It may also be a chlorotrifluoroethylene oligomer.

[0304] The above fluorine-containing oil may preferably have a number average molecular weight of 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more. Further, the above fluorine-containing oil may preferably have a number average molecular weight of 30000 or less, more preferably 20000 or less, and even more preferably 10000 or less. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0305] The above fluorine-containing oil may be contained in the above surface treatment agent in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass. In one aspect, the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. Substantially free of fluorine-containing oil means that it may contain no fluorine-containing oil or may contain a very small amount of fluorine-containing oil.

[0306] In one aspect, the number average molecular weight of the fluorine-containing oil may be made smaller than the number average molecular weight of the fluorine-containing silane compound. By setting the average molecular weight in this way, it is possible to form a cured product having high wear durability and high surface slipperiness while suppressing a decrease in the transparency of the surface treatment layer obtained from such a compound.

[0307] The fluorine-containing oil contributes to improving the surface slipperiness of the layer formed by the surface treatment agent of the present disclosure.

[0308] As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be a so-called straight silicone oil and a modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

[0309] In the surface treatment agent of the present disclosure, such silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the fluorine-containing silane compounds of the present disclosure (in the case of two or more kinds, the total thereof, the same applies hereinafter).

[0310] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

[0311] Examples of the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted by one or more fluorine atoms, such as methanol, ethanol, iso-propanol, tert-butanol, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH. By adding these alcohols to the surface treatment agent, the stability of the surface treatment agent is improved, and the compatibility between the fluorine-containing silane compound and the solvent is also improved.

[0312] The above alcohols are preferably contained in the surface treatment agent in an amount of 0.1 to 5 times, more preferably 0.5 to 3 times, and even more preferably 0.8 to 1.2 times the molar ratio relative to the above metal compound. By setting the content ratio of the alcohols within the above range, the stability of the surface treatment layer can be further improved.

[0313] Examples of the above catalyst include acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), transition metals (such as Ti, Ni, Sn, etc.), and the like.

[0314] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound of the present disclosure and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.

[0315] Examples of other components include, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.

[0316] The above surface treatment layer can be formed by applying a surface treatment agent to the above inorganic layer. The application of such a surface treatment agent can be carried out by applying it so as to cover the above inorganic layer. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.

[0317] Examples of wet coating methods include dipping coating, spin coating, brush coating, flow coating, spray coating, roll coating, gravure coating, and similar methods, and spray coating is preferred.

[0318] Examples of the dry coating method include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of the vapor deposition method (usually the vacuum vapor deposition method) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0319] Furthermore, coating by the atmospheric pressure plasma method is also possible.

[0320] When using the wet coating method, the surface treatment agent of the present disclosure can be diluted with a solvent and then applied to the substrate surface. From the viewpoints of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (for example, C6F 13CH2CH3 (e.g., AsahiKlin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorola (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Limited), etc. of alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., AsahiKlin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroether is preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0321] When using the dry coating method, the surface treatment agent of the present disclosure may be directly subjected to the dry coating method, or may be diluted with the above-mentioned solvent and then subjected to the dry coating method.

[0322] The formation of the layer of the surface treatment agent is preferably carried out such that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of the wet coating method, after diluting the surface treatment agent of the present disclosure with a solvent, a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before applying it to the inorganic layer surface.

[0323] Any suitable acid or base can be used as the catalyst. Examples of acid catalysts include acetic acid, formic acid, trifluoroacetic acid, etc. Examples of base catalysts include ammonia, organic amines, etc.

[0324] After applying the surface treatment agent, it may be dried if necessary. Such drying can promote the hydrolysis and dehydration condensation of the fluorine-containing silane compound described later, and solvents and the like can be removed.

[0325] The drying of the precursor layer can preferably be carried out at a temperature of 0°C or higher and 60°C or lower, more preferably 5°C or higher and 50°C or lower, still more preferably 10°C or higher and 30°C or lower, and can preferably be carried out for a time of 1 hour or longer and 48 hours or shorter, more preferably 3 hours or longer and 24 hours or shorter, still more preferably 6 hours or longer and 12 hours or shorter.

[0326] According to the present disclosure, a laminate with good durability can be provided. In one aspect, in such a laminate, preferably, the artificial sweat resistance, steel wool abrasion resistance, and ethanol eraser abrasion resistance can be made good. Therefore, the laminate of the present disclosure can be suitably used as a functional thin film. It can be preferably used for various substrates, for example, substrates in electronic devices.

[0327] Therefore, the present disclosure further relates to an optical material including the laminate.

[0328] Examples of optical materials preferably include various optical materials in addition to those for displays as exemplified later: for example, cathode ray tubes (CRT; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display), etc., or protection plates for those displays, or those with an antireflection film treatment on their surfaces.

[0329] The laminate of the present disclosure is not particularly limited, but can be an optical member. Examples of the optical member include the following: lenses such as glasses; front protection plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disk surfaces of optical disks such as Blu-ray (registered trademark) disks, DVD disks, CD-Rs, and MOs; optical fibers; display surfaces of watches, etc.

[0330] In addition, the laminate of the present disclosure may be a medical device or a medical material. Further, the laminate having the layer obtained by the present disclosure may be an interior or exterior automotive member. Examples of the exterior material include the following: windows, light covers, and exterior camera covers. Examples of the interior material include the following: instrument panel covers, navigation system touch panels, and decorative interior materials.

[0331] Furthermore, the laminate of the present disclosure may be an electronic device. Such electronic devices include portable terminal devices such as smartphones, tablets, notebook PCs, and cameras; wearable devices such as smartwatches; and display devices such as TVs, liquid crystal displays, organic EL displays, and inorganic EL displays.

[0332] The laminate of the present disclosure has been described in detail above. Note that the laminate of the present disclosure and the method for manufacturing the laminate, etc. are not limited to those exemplified above.

Examples

[0333] The present invention will be described more specifically by the following examples, but the present invention is not limited thereto.

[0334] (Examples 1 to 6, Comparative Examples 1 to 3) (1) In the chamber of a vacuum magnetron sputtering apparatus (NVT-1600A), a polycrystalline silicon target with a purity of 99.999% or more was installed. 0.12 g of a solution prepared by dissolving the fluorine-containing silane compound shown below in hydrofluoroether (manufactured by 3M, Novec7200) to a solid content of 20% by mass and steel wool were respectively filled into 16 copper pellets and evenly installed in the chamber. Further, chemically strengthened glass was installed in the chamber.

[0335] [Chemical formula]

[0336] (2) The inside of the chamber of the vacuum magnetron sputtering apparatus was evacuated to a vacuum of less than 4.0×10 -2 Torr by a vacuum pump, and the glass substrate was irradiated with an ion beam to clean the substrate surface. (Ion source voltage: 790 V, Ar flow rate: 1000 sccm, O2 flow rate: 300 sccm, irradiation time: 600 seconds)

[0337] (3) After cleaning the substrate, the vacuum state was maintained, and the pressure was reduced to less than 3.0×10 -5 Torr. Ar, O2, and N2 gases were flowed from both ends of the target, and a voltage was applied to form a SiO x N y layer under the conditions shown in Examples 1 to 6 and Comparative Examples 1 to 5 (output, Ar flow rate / O2 flow rate / N2 flow rate, sputtering time).

[0338] (4) Thereafter, the copper pellets filled with the fluorine-containing silane compound were evaporated by resistance heating under the conditions of an output of 25%, a current of 2.2 A, and a time of 900 s to form a surface treatment layer on the substrate.

[0339] [Table 1]

[0340] SiO x N y The x and y of the layer were measured using X-ray photoelectron spectroscopy (XPS). Apparatus: PHI5000 Versaprobe-III manufactured by ULVAC-PHI X-ray source: Monochromatic AlKα (25 W) Detection area: 100×100 μm Detection angle: 45 degrees Pass energy: 56 eV The x:y ratio was quantified by the percentages of Si2p, O1s, and N1s in the obtained spectrum.

[0341] The treated substrates described in Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to steel wool wear durability evaluation, ethanol eraser wear durability evaluation, and alkaline artificial sweat durability evaluation.

[0342] For the steel wool wear durability, the substrate with the surface treatment layer was horizontally placed in a reciprocating wear device, and steel wool (#0000, dimensions 5 mm×10 mm×10 mm) was brought into contact, and a 1000 gf weight was applied thereon. Then, with the load applied, the steel wool was reciprocated at a speed of 60 rpm and a distance of 60 mm. The water contact angle (2 μL) was measured every 2000 wear cycles, and the evaluation was terminated when the contact angle became less than 100 degrees.

[0343] For the ethanol eraser wear durability, the substrate with the surface treatment layer was horizontally placed in a reciprocating wear device, and an eraser (manufactured by Minoan, diameter 6 mm) was brought into contact. Further, 2 mL of ethanol (purity 99.7% or higher) was dropped, and a 1000 gf weight was applied thereon. Then, with the load applied, the eraser was reciprocated at a speed of 40 rpm and a distance of 40 mm. The water contact angle (2 μL) was measured every 1500 wear cycles, and the evaluation was terminated when the contact angle became less than 100 degrees.

[0344] For the alkaline artificial sweat durability, the treated substrate was wrapped with a clean dust-free cloth and placed in a plastic sealed bag, and then 25 mL of artificial sweat was added so that the dust-free cloth was sufficiently wetted. (The artificial sweat was prepared by mixing 20 g of NaCl, 17.5 g of NH4Cl, 5 g of urea, 15 mL of 85% lactic acid, and 2.5 mL of acetic anhydride, and then adding an aqueous NaOH solution so that the pH became 9.5.)

[0345] After that, the sealed bag is placed in a high-temperature and high-humidity machine in a sealed state and stored at 70°C for 48 hours. After storage, the surface of the substrate is washed with water and left standing at room temperature for 2 hours, and then the water contact angle and appearance are evaluated. The water contact angle is measured at 5 points on the surface of the substrate. For the appearance evaluation, water vapor is sprayed onto the surface of the substrate, and the degree of appearance change is visually observed.

[0346] When all 5 measured values of the water contact angle are 110 degrees or more and there is no appearance change: ◎, when the 5-point average value of the water contact angle is 110 degrees or more and the area of the portion where the appearance has changed (area is 4 mm 2 or less) is 3 or less: 〇, when the 5-point average value of the water contact angle is 100 degrees or more and less than 110 degrees and the area of the portion where the appearance has changed (area is 100 mm 2 or less) is 5 or less: △, when the 5-point average value of the water contact angle is less than 100 degrees and the area of the portion where the appearance has changed (area is 30% or more of the entire substrate) is 5 or less: ×.

[0347] It was confirmed that the laminates described in Examples 1 to 6 are excellent in steel wool abrasion durability, ethanol eraser abrasion durability, and alkaline artificial sweat durability.

Industrial Applicability

[0348] The laminate of the present disclosure has good durability and is suitable for use in displays such as cathode ray tubes (CRTs; e.g., personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), or protective plates for these displays, or optical materials such as those with an antireflection film treatment on their surfaces; lenses such as glasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and portable information terminals; disk surfaces of optical disks such as Blu-ray (registered trademark) disks, DVD disks, CD-Rs, and MOs; optical fibers; optical members such as the display surfaces of watches; medical devices or medical materials; windows, light covers, and external camera covers. Examples of interior materials include: interior and exterior automotive components such as instrument panel covers, navigation system touch panels, and decorative interior materials; portable terminal devices such as smartphones, tablets, notebook PCs, and cameras; wearable devices such as smartwatches; display devices such as TVs, liquid crystal displays, organic EL displays, and inorganic EL displays, etc.

Claims

1. A laminate comprising a substrate, an inorganic layer laminated on the substrate, and a surface treatment layer in contact with the inorganic layer, The inorganic layer is made of SiO ｘ N ｙ Including, where x is 0.01 or more and 8 or less, where y is 0.01 or more and 8 or less, and the surface treatment layer is formed using a surface treatment agent containing a fluorine-containing silane compound.

2. The laminate according to Claim 1, wherein the ratio y / x of y to x is 0.01 to 1.

3. The laminate according to Claim 1, wherein the thickness of the inorganic layer is 1 nm or more and 35 nm or less.

4. The laminate according to Claim 1, wherein the refractive index of the inorganic layer with respect to light having a wavelength of 550 nm is 1.3 or more and 2.0 or less.

5. The fluorine-containing silane compound is represented by the following formula (1) or (2): 【Chemical Formula 1】 [wherein: R Ｆ１ is, in each occurrence independently, Rf １ -R Ｆ -O ｑ - or a fluoroalkyl group; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - or a fluoroalkylene group; Rf １ is, in each occurrence, independently, a C １－１６ alkyl group which may be substituted by one or more fluorine atoms; Rf ２ is an alkylene group which may be substituted by one or more fluorine atoms; １－６ ​ R Ｆ is, in each occurrence, independently a divalent fluoropolyether group; p is 0 or 1; q is independently 0 or 1 at each occurrence; R Ｓｉ is, in each occurrence, independently, a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded; At least one R Ｓｉ is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ each independently represents a single bond or an organic group having a valence of 2 to 10; α is an integer from 1 to 9; β is an integer from 1 to 9; γ is independently an integer from 1 to 9. ] The laminate according to any one of Claims 1 to 4, comprising at least one fluorine-containing silane compound represented by the formula.

6. Forming an inorganic layer on a substrate by reactive sputtering, and Applying a surface treatment agent to the surface of the inorganic layer to form a surface treatment layer, The inorganic layer contains SiO ｘ N ｙ and includes where x is 0.01 or more and 8 or less, where y is 0.01 or more and 8 or less, and the surface treatment layer contains a fluorine-containing silane compound, a method for manufacturing a laminate.

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