Antifouling article

Abstract

The present invention relates to an article having a substrate, an intermediate layer, and a surface treatment layer, wherein the intermediate layer is on the substrate, the surface treatment layer is on the intermediate layer, and is formed from a surface treatment agent containing a fluorine-containing silane compound, and the intermediate layer contains a Ce-containing layer.

Description

Technical Field

[0001] This invention relates to stain-resistant articles. Background Technology

[0002] It is known that when certain types of fluorinated silane compounds are used for surface treatment of substrates, they can provide excellent water repellency, oil repellency, and stain resistance. The layer obtained from the surface treatment agent containing the fluorinated silane compound (hereinafter also referred to as the "surface treatment layer") is applied as a so-called functional film on various substrates such as glass, plastics, fibers, sanitary products, and building materials (Patent Documents 1 and 2).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-218639

[0006] Patent Document 2: Japanese Patent Application Publication No. 2017-082194 Summary of the Invention

[0007] The technical problem that the invention aims to solve

[0008] While the fluorinated silane compounds described in Patent Document 1 or Patent Document 2 can provide surface treatment layers with excellent functions, articles seeking surface treatment layers with higher friction durability are preferred.

[0009] The purpose of this invention is to provide an article with a surface treatment layer that has higher friction durability.

[0010] Technical solutions for solving technical problems

[0011] The present invention includes the following methods.

[0012] [1] An article having a substrate, an intermediate layer and a surface treatment layer, wherein the intermediate layer is located on the substrate, the surface treatment layer is located on the intermediate layer and is formed by a surface treatment agent containing a fluorinated silane compound, and the intermediate layer includes a Ce-containing layer.

[0013] [2] The article as described in [1] above, wherein the Ce-containing layer also contains Si.

[0014] [3] The article as described in [1] or [2] above, wherein the Ce-containing layer comprises a composite oxide containing Si and Ce.

[0015] [4] The article as described in [2] or [3] above, wherein the molar ratio of Si to Ce in the Ce-containing layer is 10:90 to 99.99:0.01.

[0016] [5] The article as described in any one of [1] to [4] above, wherein the intermediate layer further contains an alkali metal or an alkaline earth metal.

[0017] [6] The article as described in [5] above, wherein the concentration of the alkali metal and alkaline earth metal in the intermediate layer is 0.1 to 30 mol%.

[0018] [7] The article as described in any one of [1] to [6] above, wherein the thickness of the Ce-containing layer is 0.1 to 100 nm.

[0019] [8] The article as described in any one of [1] to [7] above, wherein the intermediate layer is composed of a Ce-containing layer.

[0020] [9] The article as described in any one of [1] to [7] above, wherein the intermediate layer further comprises a silicon oxide layer on the Ce-containing layer.

[0021]

[10] The article as described in [9] above, wherein the thickness of the silicon oxide layer is 0.1 nm to 100 nm.

[0022]

[11] The article as described in any one of [1] to

[10] above, wherein the fluorinated silane compound is at least one compound containing a fluorinated polyether group as shown in formula (1) or (2).

[0023] R F1 α -X A -R Si β (1)

[0024] R Si γ -X A -R F2 -X A -R Si γ (2)

[0025] In equations (1) and (2):

[0026] R F1 Rf, independently 1 -R F -O q -;

[0027] R F2 -Rf 2 p -R F -O q -;

[0028] Rf 1Each is an independent C that can be substituted by one or more fluorine atoms. 1-16 alkyl;

[0029] Rf 2 C atoms that can be substituted by one or more fluorine atoms 1-6 Alkylene;

[0030] R F Each is independently a divalent fluorinated polyether group;

[0031] p is 0 or 1;

[0032] q can be 0 or 1 independently;

[0033] R Si Each of these is a monovalent group, independently containing a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group.

[0034] At least 1 R Si It is a monovalent group containing Si atoms bonded with hydroxyl groups or hydrolyzable groups;

[0035] X A Each is an independent single bond or an organic group with a valence of 2 to 10.

[0036] α is an integer from 1 to 9;

[0037] β is an integer from 1 to 9;

[0038] γ can be an independent integer from 1 to 9.

[0039]

[12] The article as described in

[11] above, wherein R F Each can be expressed independently as follows:

[0040] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - The group shown.

[0041] [In the formula, R] Fa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom.

[0042] a, b, c, d, e, and f are each independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0043]

[13] Items as described in

[12] above, wherein Rf 1 C independently 1－16 Perfluoroalkyl, Rf 2 C independently 1－6 Perfluoroalkylene, R Fa It is a fluorine atom.

[0044]

[14] The article as described in any one of

[11] to

[13] above, wherein R F Each occurrence is independently represented by a group as shown in formula (f1), (f2), (f3), (f4), (f5), or (f6).

[0045] -(OC3F6) d -(OC2F4) e -(f1)

[0046] [In equation (f1), d is an integer from 1 to 200, and e is 0 or 1.]

[0047] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0048] In equation (f2), c and d are independent integers from 0 to 30;

[0049] e and f are independent integers from 1 to 200;

[0050] The sum of c, d, e, and f is an integer between 10 and 200;

[0051] The order in which repeating units marked with subscripts c, d, e, or f and enclosed in parentheses exist in the formula is arbitrary.

[0052] -(R) 6 -R 7 ) g -(f3)

[0053] In equation (f3), R 6 It is either OCF2 or OC2F4;

[0054] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or a combination of two or three groups selected from these groups;

[0055] g is an integer from 2 to 100.

[0056] -(R) 6 -R 7 ) g -R r -(R) 7’ -R 6’ ) g’ -(f4)

[0057] In equation (f4), R 6 It is either OCF2 or OC2F4.

[0058] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or combinations of two or three groups independently selected from these groups,

[0059] R 6’ It is either OCF2 or OC2F4.

[0060] R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or combinations of two or three groups independently selected from these groups,

[0061] g is an integer from 2 to 100.

[0062] g' is an integer from 2 to 100.

[0063] R r for:

[0064]

[0065] (In the formula, * indicates the bonding position.)

[0066] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f5)

[0067] [In equation (f5), e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the equation.]

[0068] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f6)

[0069] [In equation (f6), f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the equation.]

[0070]

[15] An article as described in any one of

[11] to

[14] above, wherein R Si It is a group represented by the following formula (S1), (S2), (S3), (S4) or (S5).

[0071]

[0072] -SiR 11 n1 R 12 3-n1 (S2)

[0073] -SiR a1 k1 R b1 l1 Rc 1 m1 (S3)

[0074] -CR d1 k2 R e1 l2 R f1 m2 (S4)

[0075] -NR g1 R h1 (S5)

[0076] In equations (S1), (S2), (S3), (S4), and (S5):

[0077] R 11Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0078] R 12 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0079] n1 in each (SiR) 11 n1 R 12 3-n1 Each unit contains an independent integer from 0 to 3;

[0080] X 11 Each occurrence is independently a single bond or a divalent organic group;

[0081] R 13 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0082] t is an integer greater than 2 at each occurrence;

[0083] R 14 Each occurrence is independently represented by a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3-n1 ;

[0084] R 15 Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 1 to 6 carbon atoms;

[0085] R a1 Each occurrence is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ;

[0086] Z 1 Each occurrence is independently represented by an oxygen atom or a divalent organic group;

[0087] R 21 Each occurrence is independently represented by -Z. 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ;

[0088] R 22 Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0089] R 23 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0090] p1 is an integer from 0 to 3 independently at each occurrence;

[0091] q1 is an integer from 0 to 3 at each occurrence;

[0092] r1 is an integer from 0 to 3 independently at each occurrence;

[0093] The sum of p1, q1, and r1 in SiR 21 p1 R 22 q1 R 23 r1 The unit is 3;

[0094] The sum of p1, q1, and r1 is 3;

[0095] Z 1’ Each occurrence is independently represented by an oxygen atom or a divalent organic group;

[0096] R 21’ Each occurrence is independently represented by -Z. 1” -SiR 22” q1” R 23” r1” ;

[0097] R 22’ Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0098] R 23’ Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0099] p1' is an integer from 0 to 3, which appears independently at each location;

[0100] q1' is an integer from 0 to 3 independently at each occurrence;

[0101] r1' is an integer from 0 to 3 independently at each occurrence;

[0102] The sum of p1', q1', and r1' in SiR 21’ p1’ R 22’ q1’ R 23’ r1’ The unit is 3;

[0103] Z 1”Each occurrence is independently represented by an oxygen atom or a divalent organic group;

[0104] R 22” Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0105] R 23” Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0106] q1” is an integer from 0 to 3, which appears independently at each occurrence;

[0107] r1” is an integer from 0 to 3, which appears independently at each occurrence;

[0108] The sum of q1” and r1” in SiR 22” q1” R 23” r1” The unit is 3;

[0109] R b1 Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0110] R c1 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0111] k1 is an independent integer from 0 to 3 at each occurrence;

[0112] l1 is an integer from 0 to 3 independently at each occurrence;

[0113] m1 is an integer from 0 to 3 at each occurrence;

[0114] The sum of k1, l1, and m1 in SiR a1 k1 R b1 l1 R c1 m1 The unit is 3;

[0115] R d1 Each occurrence is independently represented by -Z. 2 -CR 31 p2 R 32 q2 R 33 r2 ;

[0116] Z 2 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group;

[0117] R 31 Each occurrence is independently represented by -Z.2’ -CR 32’ q2’ R 33’ r2’ ;

[0118] R 32 Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 ;

[0119] R 33 Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0120] p2 is an integer from 0 to 3 independently at each occurrence;

[0121] q2 is an integer from 0 to 3 independently at each occurrence;

[0122] r2 is an integer from 0 to 3 independently at each occurrence;

[0123] The sum of p2, q2, and r2 in SiR 31 p2 R 32 q2 R 33 r2 The unit is 3;

[0124] Z 2’ Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group;

[0125] R 32’ Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 ;

[0126] R 33’ Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0127] q2' is an integer from 0 to 3 independently at each occurrence;

[0128] r2' is an integer from 0 to 3 independently at each occurrence;

[0129] The sum of q2' and r2' in SiR 32’ q2’ R 33’ r2’ The unit is 3;

[0130] Z3 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group;

[0131] R 34 Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0132] R 35 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group;

[0133] n2 is an integer from 0 to 3 independently at each occurrence;

[0134] R e1 Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 ;

[0135] R f1 Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0136] k2 is an integer from 0 to 3 independently at each occurrence;

[0137] l2 is an integer from 0 to 3 independently at each occurrence;

[0138] m2 is an integer from 0 to 3 at each occurrence;

[0139] The sum of k2, l2, and m2 in CR d1 k2 R e1 l2 R f1 m2 The unit is 3;

[0140] R g1 and R h1 Each occurrence is independently represented by -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 l2 R f1 m2 ;

[0141] Z 4 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group;

[0142] In formulas (S1), (S2), (S3), (S4), and (S5), there exists at least one Si atom bonded with a hydroxyl group or a hydrolyzable group.

[0143]

[16] An article as described in any one of

[11] to

[15] above, wherein X A Each is an independent single bond or a divalent organic group, with α, β, and γ being 1.

[0144]

[17] The article as described in any one of

[11] to

[15] above, wherein,

[0145] X A Each is an independent trivalent organic group.

[0146] α is 1 and β is 2, or α is 2 and β is 1.

[0147] γ is 2.

[0148]

[18] The article as described in any one of [1] to

[17] above, wherein the substrate is a glass substrate.

[0149]

[19] A film-forming material comprising silicon oxide and cerium oxide, wherein the molar ratio of silicon atoms to cerium atoms is 10:90 to 99.99:0.01.

[0150]

[20] The film-forming material as described in

[19] above further contains an alkali metal or alkaline earth metal, wherein the alkali metal or alkaline earth metal is 0.1 to 30 mol relative to the silicon atoms, cerium atoms and the total amount of alkali metal and alkaline earth metal.

[0151] Invention Effects

[0152] According to the present invention, it is possible to provide articles with a surface treatment layer having higher friction durability. Detailed Implementation

[0153] The article of the present invention has a substrate, an intermediate layer on the substrate, and a surface treatment layer on the intermediate layer formed by a surface treatment agent containing a fluorinated silane compound, wherein the intermediate layer includes a Ce-containing layer.

[0154] The substrates that can be used in this invention may be made of, for example, glass, resin (natural or synthetic resin, such as conventional plastic materials), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building materials, hygiene products, or any suitable material.

[0155] For example, when the item to be manufactured is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic.

[0156] In one approach, a layer (or film), such as a hard coating or an anti-reflective layer, can be formed on the surface (outermost layer) of the substrate. The anti-reflective layer can be either a single-layer or multi-layer anti-reflective layer. Examples of inorganic materials that can be used for anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic materials can be used alone or in combination of two or more (e.g., in the form of a mixture). In the case of a multi-layer anti-reflective layer, SiO2 and / or SiO are preferably used as the outermost layer. When the article to be manufactured is an optical component, particularly an optical glass component for a touch panel, a thin film using, for example, indium tin oxide (ITO) or indium zinc oxide, can also be used, with a transparent electrode on a portion of the surface of the substrate (glass). In addition, depending on its specific specifications, the substrate may also have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a frosting film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc.

[0157] In another approach, the surface of the substrate does not have any of the aforementioned arbitrary layers. That is, the intermediate layers are disposed on the substrate in a directly connected manner.

[0158] The shape of the substrate is not particularly limited; for example, it can be a plate, a film, or other forms. Furthermore, the surface area of ​​the substrate to which the surface treatment layer is to be formed only needs to be at least a portion of the substrate surface, and can be appropriately determined according to the intended use and specific specifications of the article to be manufactured.

[0159] In one approach, the substrate described above can be a substrate whose surface portion is composed of a material that originally possesses hydroxyl groups. Examples of such materials include glass, and also metals (especially base metals), ceramics, semiconductors, etc., with a natural oxide film or thermal oxide film formed on their surface. In cases where the substrate, such as resin, has insufficient hydroxyl groups, or does not originally possess hydroxyl groups, hydroxyl groups can be introduced into the substrate surface or increased by performing certain pretreatments. Examples of such pretreatments include plasma treatment (e.g., corona discharge) or ion beam irradiation. Plasma treatment can also be appropriately utilized to introduce or increase hydroxyl groups into the substrate surface and to clean the substrate surface (removing foreign matter, etc.). Another example of the aforementioned pretreatments is a method that uses the LB method (Langmuir-Blodgett method) or chemical adsorption to pre-form a film of an interfacial adsorbent with carbon-carbon unsaturated bonds on the substrate surface as a monolayer, and then breaks the unsaturated bonds under an atmosphere containing oxygen or nitrogen.

[0160] In another embodiment, the aforementioned substrate may be a substrate whose surface portion is composed of a material containing an organosilicon compound having one or more other reactive groups, such as Si-H groups, or an alkoxysilane.

[0161] In a preferred embodiment, the substrate is glass. Preferably, sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass are preferred; particularly preferred are chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

[0162] The aforementioned intermediate layer is located on the aforementioned substrate.

[0163] By adding the aforementioned intermediate layer, the durability of the surface treatment layer can be improved. Durability refers to weather resistance, abrasion resistance, and other properties.

[0164] The intermediate layer can be formed in contact with the substrate, or it can be formed on the substrate with other layers in between. In a preferred embodiment, the intermediate layer is formed in contact with the substrate.

[0165] The aforementioned intermediate layer includes a Ce-containing layer. A Ce-containing layer refers to a layer containing cerium (Ce) atoms.

[0166] The Ce is preferably contained in the Ce-containing layer in the form of an oxide. This oxide can also be a composite oxide with other metal atoms.

[0167] Here, composite oxides include oxides in which oxides of multiple elements form a homogeneous phase, so-called solid solutions, and oxides in which oxides of multiple elements form a heterogeneous phase. Preferably, the aforementioned composite oxides are composed of solid solutions forming a homogeneous phase.

[0168] In one embodiment, the Ce-containing layer is composed of cerium oxide. Here, "the Ce-containing layer is composed of cerium oxide" means that other components, such as metal atoms in any state as elements, ions, salts, oxides, etc., are permitted to be present in the Ce-containing layer as an unavoidable trace component.

[0169] Cerium oxides can also include oxides in different oxidation states. For example, cerium oxides can contain CeO. x (x=1~2) Oxides with different oxidation states. In a preferred embodiment, the cerium oxide is CeO2.

[0170] In another embodiment, the Ce-containing layer may also contain other metal atoms. These metal atoms may exist as individual oxides, or as composite oxides with Ce or composite oxides without Ce.

[0171] In this specification, metal atoms also include half-metal atoms such as B, Si, Ge, Sb, As, and Te.

[0172] The other metal atoms mentioned above can be, for example, one or more atoms selected from transition metals of groups 3 to 11 and typical metallic elements of groups 12 to 15 of the periodic table. Preferably, the other metal atoms can be transition metal atoms of groups 3 to 11, more preferably transition metal atoms of groups 3 to 7, and even more preferably transition metal atoms of groups 4 to 6.

[0173] In one embodiment, the other metal atoms mentioned above may be one or more metal atoms selected from Si, Y, Ru, In, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Bi.

[0174] In a preferred embodiment, the Ce-containing layer also contains Si.

[0175] In a preferred embodiment, the Ce and Si are contained in the Ce-containing layer in the form of a composite oxide. That is, the Ce-containing layer contains a composite oxide containing Ce and Si.

[0176] In another embodiment, the Ce and Si are contained in the Ce-containing layer in the form of their respective oxides.

[0177] The oxides mentioned above can also include oxides in different oxidation states. For example, they can contain cerium oxide, such as CeO. x(x = 1~2), silicon oxide is SiO y Oxides with different oxidation states (y = 1 to 2). In a preferred embodiment, cerium oxide is CeO2 and silicon oxide is SiO2.

[0178] In a preferred embodiment, the metal atoms contained in the Ce-containing layer are substantially only Si and Ce. Here, "the metal atoms contained in the Ce-containing layer are substantially only Si and Ce" means that other metal atoms are allowed to be present in the Ce-containing layer as an unavoidable trace component.

[0179] In one embodiment, the molar ratio of Si to Ce in the Ce-containing layer can be 10:90 to 99.99:0.01 (Si:Ce), preferably 40:60 to 99.99:0.01, more preferably 60:40 to 99:1, further preferably 90:10 to 99:1, and particularly preferably 90:10 to 98:2. By keeping the molar ratio of Si to Ce within the above range, the durability of the surface treatment layer can be improved. Furthermore, when the molar ratio of Si to Ce varies depending on the depth, the molar ratio of Si to Ce in the Ce-containing layer can be its average value.

[0180] The composition and proportion of the aforementioned intermediate layers, including the Ce layer, can be determined through surface analysis. Methods for surface analysis include X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOFMS). XPS is a typical example.

[0181] As an apparatus for determining the composition and proportion of the intermediate layer using X-ray photoelectron spectroscopy, XPS or the ULVAC PHI 5000 VersaProbe II can be used. For XPS analysis, a 25W monochromatic AlKα line can be used as the X-ray source, the photoelectron detection area can be set to 1400 μm × 300 μm, the photoelectron detection angle can be set to a range of 20 degrees to 90 degrees (e.g., 20 degrees, 45 degrees, 90 degrees), the channel energy can be set to 23.5 eV, and Ar ions can be used for sputtering. Using the above apparatus and measurement conditions, the peak areas of the C1s, O1s, F1s, Si2p orbitals and appropriate orbitals of other metals can be observed, and the atomic ratios of carbon, oxygen, fluorine, silicon, and other metals can be calculated, thereby determining the composition of the stack. As suitable orbitals for other metals, examples include atomic number 5 (B) as a 1s orbital, atomic numbers 13–14, 21–31 (Al–Si, Sc–Ga) as 2p orbitals, atomic numbers 32–33, 39–52 and 58 (Ge–As, Y–Te, Ce) as 3d orbitals, and atomic numbers 72–83 (Hf–Bi) as 4f orbitals.

[0182] Alternatively, depth-oriented analysis of the intermediate layer can be performed. For XPS analysis, a 25W monochromatic AlKα line can be used as the X-ray source, with the photoelectron detection area set to 1400μm × 300μm, the photoelectron detection angle set to a range of 20°–90° (e.g., 20°, 45°, 90°), the channel energy set to 23.5 eV, and Ar ions used for sputtering. By using Ar ion sputtering, the intermediate layer is etched from SiO2 to 100nm. At each etched depth, the peak areas of the O1s, Si2p orbitals, and appropriate orbitals of other metals are observed, and the atomic ratios of oxygen, silicon, and other metals are calculated. This allows the determination of the composition within the intermediate layer. As suitable orbitals for other metals, examples include atomic number 5 (B) as a 1s orbital, atomic numbers 13–14, 21–31 (Al–Si, Sc–Ga) as 2p orbitals, atomic numbers 32–33, 39–52 and 58 (Ge–As, Y–Te, Ce) as 3d orbitals, and atomic numbers 72–83 (Hf–Bi) as 4f orbitals.

[0183] By adjusting the photoelectron detection angle of the XPS analysis, the detection depth can be appropriately adjusted. For example, by setting it to a shallower angle close to 20 degrees, the detection depth can be around 3 nm; on the other hand, by setting it to a deeper angle close to 90 degrees, the detection depth can be around 10 nm.

[0184] Furthermore, in compositional analysis using XPS, when Si and other elements in the substrate are detected, the amount of Si in the substrate can be calculated from the amount of specific atoms in the substrate, for example, when the substrate is glass, based on the amount of trace metal atoms (e.g., Al, Na, K, B, Ca, Mg, Sn, etc.) detected. This amount is then subtracted from the measurement results, thereby allowing the composition of the intermediate layer to be calculated.

[0185] In one embodiment, the intermediate layer may further contain an alkali metal or an alkaline earth metal, preferably an alkali metal. By containing an alkali metal in the intermediate layer, the friction durability and weather resistance of the surface-treated layer can be improved. The alkali metal and alkaline earth metal contained in the intermediate layer may be contained in the Ce-containing layer, in other layers, or in both layers.

[0186] The alkali metals and alkaline earth metals in the intermediate layer can exist uniformly, or they can segregate on the surface of the intermediate layer (surface treatment layer side). Preferably, the alkali metals and alkaline earth metals in the intermediate layer are segregated on the surface of the intermediate layer.

[0187] Examples of alkali metals mentioned above include Li, Na, K, Rb, Cs, and Fr. Na or K are preferred, and Na is more preferred.

[0188] Examples of alkaline earth metals include Be, Mg, Ca, Sr, Ba, and Ra. Mg or Ca are preferred among these alkaline earth metals.

[0189] The content of alkali metals and alkaline earth metals in the intermediate layer (the total content when multiple metals are present) is not particularly limited, but is preferably 0.1 to 30 mol% relative to the total number of metal atoms contained in the intermediate layer, more preferably 0.1 to 20 mol%, even more preferably 0.1 to 15 mol%, and even more preferably 0.5 to 15 mol%, for example, 1.0 to 15 mol% or 1.0 to 10 mol%. By keeping the concentration of alkali metals and alkaline earth metals in the intermediate layer within the above range, the friction durability and weather resistance of the surface treatment layer can be improved. In addition, by keeping the concentration of alkali metals and alkaline earth metals in the intermediate layer preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, the friction durability of the surface treatment layer can be further improved.

[0190] The aforementioned intermediate layers can be single-layered or multi-layered. Furthermore, the boundaries of the intermediate layers are defined portions of the composition that differ clearly in the thickness direction; the layers above and below these boundaries can be considered different layers. Portions where the composition gradually changes in the thickness direction are not boundaries; these regions are considered as a single layer.

[0191] In one approach, the intermediate layer is a single layer.

[0192] In the case where the intermediate layer is a single layer, the intermediate layer is a Ce-containing layer.

[0193] When the intermediate layer is a single layer, the Ce-containing layer preferably contains both Si and Ce. In the aforementioned Ce-containing layer, Si atoms are preferably present on the surface in contact with the surface treatment layer. By having Si atoms present on the surface treatment layer side of the Ce-containing layer, the friction durability, weather resistance, and other properties of the surface treatment layer can be improved.

[0194] In one embodiment, in the Ce-containing layer containing Si and Ce, the Si concentration gradient preferably increases gradually towards the surface treatment layer. By making the Si concentration gradient gradually increase towards the surface treatment layer, the friction durability, weather resistance, and other properties of the surface treatment layer can be improved.

[0195] In another approach, the intermediate layers are multiple.

[0196] In the case where the above-mentioned intermediate layer is multi-layered, the intermediate layer includes a Ce-containing layer and a Si-containing layer.

[0197] In one embodiment, the intermediate layer consists of a Ce-containing layer and a Si-containing layer.

[0198] In a preferred embodiment, the intermediate layer further comprises a Si-containing layer on top of the Ce-containing layer. That is, the intermediate layer comprises: a Ce-containing layer located on the substrate side; and a Si-containing layer located on the Ce-containing layer and in contact with the surface treatment layer. By arranging the Ce-containing layer and the Si-containing layer in the above order, the friction durability, weather resistance, and other properties of the surface treatment layer can be improved.

[0199] In a preferred embodiment, the intermediate layer consists of a Ce-containing layer located on the substrate and a Si-containing layer located directly on the Ce-containing layer.

[0200] The thickness of the aforementioned intermediate layer (total thickness of all layers in the case of multiple layers) is not particularly limited, and can be, for example, 1.0 nm or more, preferably 2.0 nm or more, and more preferably 3.0 nm or more. By setting the thickness of the intermediate layer to 1.0 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. Furthermore, the thickness of the aforementioned intermediate layer (total thickness of all layers in the case of multiple layers) is not particularly limited, and can be, for example, 120 nm or less, preferably 60 nm or less, more preferably 25 nm or less, even more preferably 15 nm or less, and particularly preferably 10 nm or less. By making the thickness of the intermediate layer 120 nm or less, the transparency of the article can be further improved. The thickness of the aforementioned intermediate layer (total thickness of all layers in the case of multiple layers) is preferably 1.0 to 120 nm, more preferably 2.0 to 60 nm, even more preferably 2.0 to 25 nm, and even more preferably 3.0 nm to 10 nm.

[0201] The thickness of the Ce-containing layer is not particularly limited, and can be, for example, 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and even more preferably 3.0 nm or more. By making the thickness of the Ce-containing layer 0.1 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. Furthermore, the thickness of the Ce-containing layer is not particularly limited, and can be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. By making the thickness of the Ce-containing layer 100 nm or less, the transparency of the article can be further improved. The thickness of the Ce-containing layer is preferably 0.1 to 100 nm, more preferably 1.0 to 50 nm, even more preferably 2.0 to 20 nm, and even more preferably 3.0 nm to 10 nm.

[0202] When present, the thickness of the layer containing other metals is not particularly limited, but can be, for example, 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and even more preferably 3.0 nm or more. By making the thickness of the layer containing other metals 0.1 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. Furthermore, the thickness of the aforementioned layer containing other metals is not particularly limited, but can be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. By making the thickness of the layer containing other metals 100 nm or less, the transparency of the article can be further improved. The thickness of the aforementioned layer containing other metals is preferably 0.1 to 100 nm, more preferably 1.0 to 50 nm, even more preferably 2.0 to 20 nm, and even more preferably 3.0 nm to 10 nm.

[0203] In particular, when present, the thickness of the Si-containing layer is not particularly limited, for example, it can be 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and even more preferably 3.0 nm or more. By making the thickness of the Si-containing layer 1.0 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. In addition, the thickness of the Si-containing layer is not particularly limited, for example, it can be 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. By making the thickness of the Si-containing layer 100 nm or less, the transparency of the article can be further improved. The thickness of the Si-containing layer is preferably 0.1 to 100 nm, more preferably 1.0 to 50 nm, even more preferably 2.0 to 20 nm, and even more preferably 3.0 nm to 10 nm.

[0204] In a preferred embodiment, the intermediate layer is composed of a Ce-containing layer located on the substrate and a Si-containing layer located directly on the Ce-containing layer. The thickness of the Ce-containing layer is 0.1–20 nm, preferably 1.0–10 nm, and the thickness of the Si-containing layer is 0.1–20 nm, preferably 1.0–10 nm.

[0205] The thickness of each layer can be determined by combining XPS analysis and sputtering. Specifically, by performing the aforementioned depth-direction analysis, the location where the composition undergoes a clear change is taken as the boundary of each layer, and the sputtering depth is measured, thereby enabling the determination of the layer thickness.

[0206] There are no particular limitations on the method for forming the intermediate layer. For example, sputtering, ion beam assisted deposition, vacuum evaporation (preferably electron beam heating), CVD (chemical vapor deposition), atomic layer deposition, etc. are used. Vacuum evaporation or sputtering is preferred.

[0207] The sputtering methods mentioned above can include DC (direct current) sputtering, AC (alternating current) sputtering, RF (high frequency) sputtering, and RAS (radical-assisted) sputtering. These sputtering methods can be either diode sputtering or magnetron sputtering.

[0208] In the case of film formation by sputtering, a substrate is placed in a chamber containing a mixture of inert gas and oxygen as an intermediate layer forming material, and the target material is selected to form the desired composition for film formation. In this case, the type of inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used.

[0209] The pressure within the chamber composed of a mixture of inert gas and oxygen is not particularly limited, but by setting it to a range of 0.5 Pa or less, the surface roughness of the formed film can easily reach a preferred range. This can be attributed to the following reasoning: When the pressure within the chamber composed of the mixture of inert gas and oxygen is below 0.5 Pa, the mean free path of the film-forming molecules can be ensured, allowing the molecules to reach the substrate with more energy. Therefore, it can be considered that the recombination of film-forming molecules can be promoted, resulting in a film with a relatively dense and smooth surface. The lower limit of the pressure within the chamber composed of the mixture of inert gas and oxygen is not particularly limited, but it is desirable to be, for example, 0.1 Pa or more.

[0210] In the above-mentioned method for forming the intermediate layer, a film-forming material containing cerium oxide is used.

[0211] In a preferred embodiment, the film-forming material contains silicon oxide and cerium oxide.

[0212] In the aforementioned film-forming materials containing silicon oxide and cerium oxide, the molar ratio of silicon atoms to cerium atoms is preferably 10:90 to 99.99:0.01 (Si:Ce), more preferably 10:90 to 99:1, even more preferably 10:90 to 95:5, further preferably 20:80 to 90:10, and particularly preferably 40:60 to 80:20. By maintaining the molar ratio of Si to Ce in the film-forming material within the above range, the durability of the surface treatment layer can be improved.

[0213] (Preparation of film-forming materials)

[0214] Specific examples of film-forming material forms include powders, melts, sintered bodies, granules, and fragments. From an operational point of view, melts, sintered bodies, and granules are preferred.

[0215] Here, a melt refers to a solid obtained by melting film-forming material powder at high temperature and then cooling and solidifying it. A sintered body refers to a solid obtained by sintering film-forming material powder; as needed, it can be used as a substitute for the film-forming material powder by pressing powder into a molded body. A granulated body refers to a solid obtained by mixing film-forming material powder with a liquid medium (such as water or organic solvent) to obtain granules, and then drying the granules.

[0216] Film-forming materials can be manufactured, for example, by the following methods.

[0217] • A method for mixing silicon oxide powder with cerium oxide powder to obtain a film-forming material powder.

[0218] • A method for obtaining granules by mixing the powder of the above-mentioned film-forming material with water, and then drying the granules to obtain granulated film-forming material.

[0219] • A method of drying a mixture of silicon-containing powder (e.g., powder composed of silicon oxide, silica sand, silica gel), cerium-containing powder (e.g., powder of cerium oxide, carbonate, sulfate, nitrate, oxalate, hydroxide) and water, and then firing the dried mixture or a molded body formed therefrom to obtain a sintered body.

[0220] A method for obtaining a melt by melting silicon-containing powders (e.g., powders composed of silicon oxide, silica sand, silica gel) and cerium-containing powders (e.g., powders of cerium oxides, carbonates, sulfates, nitrates, oxalates, hydroxides) at high temperature and then cooling and solidifying the melt.

[0221] • A method of reacting a silicon-containing alkoxide or chloride (e.g., tetramethoxysilane, tetraethoxysilane, tetraisopropylsilane, tetrachlorosilane) and a cerium-containing alkoxide (e.g., cerium isopropoxy) with water, drying the resulting oxide solid, pressing it into shape, and then firing it to obtain a sintered body.

[0222] • A method in which either silicon or cerium is reacted with an oxide when using the above-mentioned alkoxide, the resulting oxide solid is dried, pressed into shape, and then fired to obtain a sintered body; etc.

[0223] In a preferred embodiment, the film-forming material contains, in addition to silicon oxide and cerium oxide, an alkali metal or alkaline earth metal, preferably an alkali metal.

[0224] The aforementioned alkali metals and alkaline earth metals are present in the form of ions, oxides, or salts.

[0225] Relative to the total amount of silicon atoms, cerium atoms, and alkali metals and alkaline earth metals, the aforementioned alkali metals and alkaline earth metals preferably contain 0.1 to 30 mol%, more preferably 0.1 to 20 mol%, even more preferably 0.1 to 15 mol%, and even more preferably 0.5 to 15 mol%, for example, 1.0 to 15 mol% or 1.0 to 10 mol%. By ensuring that the concentration of alkali metals in the film-forming material is within the above range, the friction durability, weather resistance, etc., of the surface treatment layer can be improved.

[0226] In one embodiment, the aforementioned film-forming material is a vapor-deposited material.

[0227] The surface treatment layer is located on the intermediate layer. Preferably, the surface treatment layer is directly above the intermediate layer, that is, at the position where it is in contact with the intermediate layer.

[0228] The aforementioned surface treatment layer can be formed by a surface treatment agent containing a fluorinated silane compound.

[0229] When used in this specification, "monovalent organic group" refers to a monovalent group containing carbon. There is no particular limitation on what constitutes a monovalent organic group; it can be a hydrocarbon group or its derivative. A hydrocarbon derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, or carbonyloxy groups at the end of the hydrocarbon group or in the molecular chain. Where only "organic group" is used, it refers to a monovalent organic group. Furthermore, "divalent to decavalent organic group" refers to a divalent to decavalent group containing carbon. There is no particular limitation on what constitutes a divalent to decavalent organic group; examples include divalent to decavalent groups obtained by further removing 1 to 9 hydrogen atoms from an organic group. For example, there is no particular limitation on what constitutes a divalent organic group; examples include divalent groups obtained by further removing one hydrogen atom from an organic group.

[0230] When used in this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group formed by removing one hydrogen atom from a hydrocarbon. There are no particular limitations on the hydrocarbon group; examples include C atoms that can be substituted by one or more substituents. 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon groups" can be any of the following: straight-chain, branched, or cyclic; and can be any of the following: saturated or unsaturated. In addition, hydrocarbon groups can also contain one or more ring structures.

[0231] When used in this specification, the term "hydrocarbon group" is not particularly limited, and can include, for example, groups selected from halogen atoms, groups that can be substituted by one or more halogen atoms, and C. 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 3-10 cycloalkyl, C 3-10Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6-10 One or more groups selected from aryl and 5- to 10-membered heteroaryl groups.

[0232] As used in this specification, "hydrolyzable group" refers to a group capable of undergoing a hydrolysis reaction; that is, a group that can be removed from the main skeleton of a compound through a hydrolysis reaction. Examples of hydrolyzable groups include -OR j -OCOR j -ON=CR j 2. -NR j 2. -NHR j -NCO, halogens (in these formulas, R) j C indicates substitution or non-substitution. 1-4 Alkyl groups, etc.

[0233] The above-mentioned fluorinated silane compound is at least one fluorinated silane compound represented by formula (1) or (2):

[0234] R F1 α -X A -R Si β (1)

[0235] R Si γ -X A -R F2 -X A -R Si γ (2).

[0236] [In the formula, R] F1 Each occurrence is independently represented by Rf. 1 -R F -O q -;

[0237] R F2 -Rf 2 p -R F -O q -,

[0238] Rf 1 Each occurrence is independently a C atom that can be substituted by one or more fluorine atoms. 1-16 alkyl;

[0239] Rf 1 C atoms that can be substituted by one or more fluorine atoms 1-6 Alkylene

[0240] RF Each occurrence is independently a divalent fluorinated polyether group;

[0241] p is 0 or 1,

[0242] q is 0 or 1 independently at each occurrence;

[0243] R Si Each occurrence is independently a monovalent group containing a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group;

[0244] At least 1 R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups;

[0245] X A Each can be independently a single bond or a divalent to decavalent organic group.

[0246] α is an integer from 1 to 9;

[0247] β is an integer from 1 to 9;

[0248] γ can be an independent integer from 1 to 9.

[0249] In equation (1) above, R F1 Each occurrence is independently represented by Rf. 1 -R F -O q -

[0250] In equation (2) above, R F2 -Rf 2 p -R F -O q -

[0251] In the above formula, Rf 1 Each occurrence is independently a C atom that can be substituted by one or more fluorine atoms. 1－16 alkyl.

[0252] The above C atoms that can be substituted by one or more fluorine atoms 1－16 The "C" in alkyl 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Alkyl groups, especially C 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially C 1－3 alkyl.

[0253] The above Rf 1 Preferably, C atoms are substituted with one or more fluorine atoms. 1－16Alkyl groups, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0254] The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0255] In the above formula, Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene.

[0256] The above C atoms that can be substituted by one or more fluorine atoms 1－6 The "C" in alkylene 1－6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0257] The above Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene groups.

[0258] The above C 1－6 Perfluoroalkylene groups can be straight-chain or branched, with straight-chain or branched C4 groups being preferred. 1－3 Perfluoroalkylene, more preferably straight-chain C 1－3 Perfluoroalkylene compounds, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0259] In the above formula, p is either 0 or 1. In one approach, p is 0. In another approach, p is 1.

[0260] In the above formula, q is independently 0 or 1 at each occurrence. In one case, q is 0. In another case, q is 1.

[0261] In equations (1) and (2) above, R F Each of the occurrences is independently divalent fluorinated polyether group.

[0262] R F It can contain the following formulas:

[0263] -(OC) h1 R Fa 2h1 ) h3 -(OC) h2 R Fa 2h2－2 ) h4 - The group shown.

[0264] [In the formula: R] Fa Each occurrence is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom.

[0265] h1 is an integer from 1 to 6.

[0266] h2 is an integer from 4 to 8.

[0267] h3 is an integer greater than or equal to 0.

[0268] h4 is an integer greater than or equal to 0.

[0269] Wherein, the sum of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of the repeating units marked with h3 and h4 and enclosed in parentheses in the formula is arbitrary.

[0270] In one approach, R F It can be linear or branched. R F The preferred formula is as follows:

[0271] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - The group shown.

[0272] [In the formula, R] Fa Each occurrence is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom.

[0273] a, b, c, d, e, and f are each an independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is greater than or equal to 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula. Where, when all R... Fa When the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f must be 1 or higher.

[0274] R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom. Wherein, when all R...Fa When the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.

[0275] a, b, c, d, e, and f can each be an integer from 0 to 100 independently.

[0276] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, it can be 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, and even more preferably 60 or less, for example, it can be 50 or less or 30 or less.

[0277] These repeating units can be linear or branched. For example, -(OC6F 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 - can be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can 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)-(that is, R in the above formula) Fa The fluorine atom can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. The fluorine atom -(OC2F4)- can be any one of -(OCF2CF2)- and -(OCF(CF3))-.

[0278] In one embodiment, the repeating units are in a straight chain shape. By making the repeating units in a straight chain shape, the surface lubricity and wear resistance of the surface treatment layer can be improved.

[0279] In one embodiment, the repeating units are branched. By making the repeating units branched, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0280] In one approach, R F It can contain ring structures.

[0281] The above-mentioned ring structure can be a ternary ring, a quaternary ring, a quinary ring, or a hexaternary ring.

[0282]

[0283] [In the formula, * indicates the bond position.]

[0284] The aforementioned ring structure is preferably a four-membered ring, a five-membered ring, or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

[0285] The repeating unit with a ring structure is preferably the following unit.

[0286]

[0287] [In the formula, * indicates the bond position.]

[0288] In one approach, R F Each occurrence is independently represented by a group as shown in any of the following formulas (f1) to (f6).

[0289] -(OC3F6) d -(OC2F4) e -(f1)

[0290] [In equation (f1), d is an integer from 1 to 200, and e is 0 or 1.]

[0291] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0292] In equation (f2), c and d are independent integers above 0 and below 30, and e and f are independent integers above 1 and below 200.

[0293] The sum of c, d, e, and f is 2 or more.

[0294] The order in which repeating units marked with subscripts c, d, e, or f and enclosed in parentheses exist in the formula is arbitrary.

[0295] -(R) 6 -R 7 ) g -(f3)

[0296] In equation (f3), R 6 It is either OCF2 or OC2F4.

[0297] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected independently from these groups,

[0298] g is an integer from 2 to 100.

[0299] -(R) 6 -R 7 ) g -R r -(R) 7’ -R 6’ ) g’ -(f4)

[0300] In equation (f4), R 6 It is either OCF2 or OC2F4.

[0301] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected independently from these groups,

[0302] R 6’ It is either OCF2 or OC2F4.

[0303] R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected independently from these groups,

[0304] g is an integer from 2 to 100.

[0305] g' is an integer from 2 to 100.

[0306] R r for:

[0307]

[0308] (In the formula, * indicates the bonding position.)

[0309] -(OC6F 12 ) a -(OC5F) 10 ) b-(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f5)

[0310] [In equation (f5), e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the equation.]

[0311] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f6)

[0312] [In equation (f6), f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the equation.]

[0313] In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, and for example, an integer from 25 to 35. In the above formula (f1), OC3F6 is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). In one embodiment, e is 0. In another embodiment, e is 1. In the above formula (f1), (OC2F4) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2).

[0314] In the above formula (f2), e and f are each preferably integers from 5 to 200, more preferably from 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, 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 - The group shown. In another embodiment, formula (f2) can be -(OC2F4). e-(OCF2) f - The group shown.

[0315] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7 Preferably, the group is 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. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8; examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4- etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g - or - (OC2F4 - OC4F8) g -.

[0316] In the above equation (f4), R 6 R 7 The meanings of 'g' and 'g' are the same as those recorded in equation (f3) above, and they follow the same pattern. 6’ R 7’ The meanings of and g' are respectively the same as those of R recorded in the above formula (f3). 6 R 7 It has the same meaning as g and follows the same pattern. R r Preferred options are:

[0317]

[0318] [In the formula, * indicates the bond position.]

[0319] More preferably:

[0320]

[0321] [In the formula, * indicates the bond position.]

[0322] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0323] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0324] In one approach, the aforementioned R F The group is represented by the formula (f1) above.

[0325] In one approach, the aforementioned R F The group is shown in the above formula (f2).

[0326] In one approach, the aforementioned R F The group is represented by formula (f3) or (f4) above.

[0327] In one approach, the aforementioned R F The group is represented by the formula (f3) above.

[0328] In one approach, the aforementioned R F The group is represented by the formula (f4) above.

[0329] In one approach, the aforementioned R F The group is represented by the formula (f5) above.

[0330] In one approach, the aforementioned R F The group is represented by the formula (f6) above.

[0331] The above R FIn this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the slip properties, wear resistance, and chemical resistance (e.g., resistance to artificial sweat) of the surface treatment layer obtained from this compound can be further improved. The smaller the e / f ratio, the better the slip properties and wear resistance of the surface treatment layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the better the stability of the compound.

[0332] In the above-mentioned fluorinated silane compounds, R F1 and R F2 The number-average molecular weight of the fraction is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, R... F1 and R F2 The number average molecular weight is obtained through 19 Values ​​measured by F-NMR.

[0333] In another way, R F1 and R F2 The number average molecular weight of the fraction is 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.

[0334] In another way, R F1 and R F2 The number average molecular weight of the fraction can be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0335] In equations (1) and (2) above, R Si Each occurrence is independently a monovalent group containing a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group, with at least one R. Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups.

[0336] Here, "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction; that is, a group that can be removed from the main skeleton of a compound through a hydrolysis reaction. Examples of hydrolyzable groups include -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHRj , -NCO, halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl groups, etc.

[0337] In the preferred method, R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups.

[0338] In the preferred method, R Si It is a group represented by the following formula (S1), (S2), (S3), (S4) or (S5).

[0339]

[0340] -SiR 11 n1 R 12 3-n1 (S2)

[0341] -SiR a1 k1 R b1 l1 R c1 m1 (S3)

[0342] -CR d1 k2 R e1 2R f1 m2 (S4)

[0343] -NR g1 R h1 (S5)

[0344] In the above formula, R 11 Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0345] R 11 Preferably, each occurrence is an independently hydrolyzable group.

[0346] R 11 Ideally, -OR should be used independently at each occurrence. j -OCOR j -ON=CR j 2. -NR j 2. -NHR j -NCO or halogen (in these formulas, R) j C indicates substitution or non-substitution. 1-4 Alkyl group, more preferably -OR j (i.e., alkoxy group). As R jExamples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0347] In the above formula, R 12 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0348] In R 12 In this context, the monovalent organic group is preferably C. 1-20 Alkyl, more preferably C 1-6 Alkyl groups, more preferably methyl groups.

[0349] In the above formula, n1 is in each (SiR 11 n1 R 12 3-n1 Each element contains an independent integer from 0 to 3. In R... Si In the case of groups represented by formula (S1) or formula (S2), the R at the end of formulas (1) and (2) Si Part (hereinafter sometimes simply referred to as the “end part” of equations (1) and (2)) has at least one n1 of 1 to 3 (SiR) 11 n1 R 12 3-n1 ) unit. That is, in this terminal part, all n1 are not simultaneously 0. In other words, in the terminal part of formulas (1) and (2), there is at least one Si atom bonded with a hydroxyl or hydrolyzable group.

[0350] n1 in each (SiR) 11 n1 R 12 3-n1 The units are preferably integers of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0351] In the above formula, X 11 Each occurrence is independently a single bond or a divalent organic group. The divalent organic group is preferably -R. 28 -O x -R 29 -(where R) 28 and R 29 Each occurrence is independently a single bond or a C. 1－20 Alkylene, x is 0 or 1. The C 1－20The alkylene group can be straight-chain or branched, preferably straight-chain. The C 1－20 Alkylene is preferably C 1－10 Alkylene, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0352] In one manner, X 11 Each occurrence is independently represented by -C. 1－6 Alkylene-O-C 1－6 alkylene- or -O-C 1－6 Alkylene-.

[0353] In the preferred method, X 11 Each occurrence of C is independently a single bond or a linear chain. 1－6 Alkylene, preferably single-bonded or straight-chain C 1－3 Alkylene, more preferably a single bond or a straight-chain C 1－2 Alkylene, more preferably straight-chain C 1－2 Alkylene.

[0354] In the above formula, R 13 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably C. 1－20 Alkyl group. The C 1－20 Alkyl groups can be straight-chain or branched, but are preferably straight-chain.

[0355] In the preferred method, R 13 Each occurrence is independently a hydrogen atom or a straight-chain C. 1－6 Alkyl groups, preferably hydrogen atoms or straight-chain C atoms. 1－3 Alkyl group, preferably a hydrogen atom or a methyl group.

[0356] In the above formula, t is an integer greater than 2 at each occurrence.

[0357] In the preferred embodiment, t is an integer from 2 to 10 at each occurrence, preferably an integer from 2 to 6.

[0358] In the above formula, R 14 Each occurrence is independently represented by a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 The 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 It is a hydrogen atom.

[0359] In the above formula, R 15Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 1 to 6 carbon atoms.

[0360] In one approach, R 15 Each occurrence is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 1 to 6 carbon atoms.

[0361] In the preferred method, R 15 It is a single key.

[0362] In one approach, equation (S1) is the following equation (S1-a).

[0363]

[0364] [In the formula,

[0365] R 11 R 12 R 13 X 11 The meanings of n1 and n1 are the same as those recorded in the above formula (S1);

[0366] t1 and t2 are each independently an integer of 1 or more at each occurrence, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, for example an integer of 1 to 5 or an integer of 2 to 5;

[0367] The order in which the repeating units labeled t1 and t2, enclosed in parentheses, exist in the formula is arbitrary.

[0368] In the preferred embodiment, equation (S1) is the following equation (S1-b).

[0369]

[0370] [In the formula, R] 11 R 12 R 13 X 11 The meanings of n1 and t are the same as those stated in the above formula (S1).

[0371] In the above formula, R a1 Each occurrence is independently represented by -Z. 1 -SiR 21 p1 R 22 q1 R 23 r1 .

[0372] The above Z 1 Each occurrence is independently represented by an oxygen atom or a divalent organic group. Hereinafter, it is denoted as Z. 1The right side of the structure and (SiR) 21 p1 R 22 q1 R 23 r1 ) bond.

[0373] In the preferred method, Z 1 It is a divalent organic group.

[0374] In the preferred method, Z 1 Excluding Z 1 The Si atoms that are bonded form siloxane bonds. Preferably, in formula (S3) (Si-Z) 1 -Si) does not contain siloxane bonds.

[0375] The above Z 1 C is preferred 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 -(where 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 -Phenylidene-(CH2) z4 —(In the formula, z3 is an integer from 0 to 6, for example, an integer from 1 to 6; z4 is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0376] In the preferred method, Z 1 C 1－6 Alkylene or -(CH2) z3 -Phenylidene-(CH2) z4 -, preferably -phenylene-(CH2) z4 - In Z 1 In the case of this group, lightfastness, especially UV resistance, can be further improved.

[0377] In other preferred embodiments, the above Z 1 C 1－3 Alkylene. In one manner, Z 1 It can be -CH2CH2CH2-. In another way, Z 1 It can be -CH2CH2-.

[0378] The above R 21Each occurrence is independently represented by -Z. 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ .

[0379] The above Z 1’ Each occurrence is independently represented by an oxygen atom or a divalent organic group. Hereinafter, it is denoted as Z. 1’ The right side of the structure and (SiR) 21’ p1’ R 22’ q1’ R 23’ r1’ ) bond.

[0380] In the preferred method, Z 1’ It is a divalent organic group.

[0381] In the preferred method, Z 1’ Excluding Z 1’ The Si atoms that are bonded form siloxane bonds. Preferably, in formula (S3), (Si-Z 1’ -Si) does not contain siloxane bonds.

[0382] The above Z 1’ C is preferred 1－6 Alkylene, -(CH2) z1’ -O-(CH2) z2’ -(where 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’ -Phenylidene-(CH2) z4’ —(In the formula, z3' is an integer from 0 to 6, for example, an integer from 1 to 6; z4' is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0383] In the preferred method, Z 1’ C 1－6 Alkylene or -(CH2) z3’ -Phenylidene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ - In Z 1’When the above-mentioned groups are present, the lightfastness, especially the UV resistance, can be further improved.

[0384] In other preferred embodiments, the above Z 1’ C 1－3 Alkylene. In one manner, Z 1’ It can be -CH2CH2CH2-. In another way, Z 1’ It can be -CH2CH2-.

[0385] The above R 21’ Each occurrence is independently represented by -Z. 1” -SiR 22” q1” R 23” r1” .

[0386] The above Z 1” Each occurrence is independently represented by an oxygen atom or a divalent organic group. Furthermore, it is hereinafter denoted as Z. 1” The right side of the structure and (SiR) 22” q1” R 23” r1” (Combined)

[0387] In the preferred method, Z 1” It is a divalent organic group.

[0388] In the preferred method, Z 1” Excluding Z 1” The Si atoms that are bonded form siloxane bonds. Preferably, in formula (S3), (Si-Z 1” -Si) does not contain siloxane bonds.

[0389] The above Z 1” C is preferred 1－6 Alkylene, -(CH2) z1” -O-(CH2) z2” -(where 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” -Phenylidene-(CH2) z4” —(In the formula, z3” is an integer from 0 to 6, for example, an integer from 1 to 6; z4” is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0390] In the preferred method, Z 1” C 1－6 Alkylene or -(CH2) z3” -Phenylidene-(CH2) z4 "-, preferably -phenylene-(CH2) z4” - In Z 1” When the above-mentioned groups are present, the lightfastness, especially the UV resistance, can be further improved.

[0391] In other preferred embodiments, the above Z 1” C 1－3 Alkylene. In one manner, Z 1” It can be -CH2CH2CH2-. In another way, Z 1” It can be -CH2CH2-.

[0392] The above R 22” Each occurrence is independently represented by a hydroxyl group or a hydrolyzable group.

[0393] The above R 22” Preferably, each occurrence is an independently hydrolyzable group.

[0394] The above R 22” Ideally, each occurrence should be independently represented as -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl group, more preferably -OR j (i.e., alkoxy group). As R j Examples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0395] The above R 23” Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0396] The above R 23” In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0397] The aforementioned q1” is an independent integer from 0 to 3 at each occurrence, and the aforementioned r1” is an independent integer from 0 to 3 at each occurrence. Furthermore, the sum of q1” and r1” is within (SiR) 22” q1” R 23” r1” The value in unit ) is 3.

[0398] The above q1” in each (SiR 22” q1” R 23” r1” The units are preferably integers from 1 to 3, more preferably from 2 to 3, and even more preferably 3.

[0399] The above R 22’ Each occurrence is independently represented by a hydroxyl group or a hydrolyzable group.

[0400] R 22’ Preferably, each occurrence is an independently hydrolyzable group.

[0401] R 22’ Ideally, each occurrence should be independently represented as -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl group, more preferably -OR j (i.e., alkoxy group). As R j Examples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0402] The above R 23’ Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0403] In R 23’ In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0404] In the above examples, p1' is an independent integer from 0 to 3 at each occurrence, q1' is an independent integer from 0 to 3 at each occurrence, and r1' is an independent integer from 0 to 3 at each occurrence. The sum of p', q1', and r1' is within the range (SiR). 21’ p1’ R 22’ q1’ R 23’ r1’ The value in unit ) is 3.

[0405] In one mode, p1' is 0.

[0406] In one manner, p1' in each (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each of the units can be an integer from 1 to 3, an integer from 2 to 3, or 3. In the preferred embodiment, p1' is 3.

[0407] In one manner, q1' in each (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0408] In one mode, p1' is 0, and q1' is in each (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0409] The above R 22 Each occurrence is independently represented by a hydroxyl group or a hydrolyzable group.

[0410] R 22 Preferably, each occurrence is an independently hydrolyzable group.

[0411] R 22 Ideally, each occurrence should be independently represented as -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution.1－4 Alkyl group, more preferably -OR j (i.e., alkoxy group). As R j Examples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0412] The above R 23 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0413] In R 23 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0414] In the above examples, p1, q1, and r1 are each independent integers from 0 to 3 at their respective occurrences. The sum of p1, q1, and r1 is within the range (SiR). 21 p1 R 22 q1 R 23 r1 The value in unit ) is 3.

[0415] In one mode, p1 is 0.

[0416] In one manner, p1 in each (SiR) 21 p1 R 22 q1 R 23 r1 Each of the units can be an integer from 1 to 3, an integer from 2 to 3, or 3. In the preferred embodiment, p1 is 3.

[0417] In one approach, q1 is in each (SiR) 21 p1 R 22 q1 R 23 r1 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0418] In one mode, p1 is 0, and q1 is in each (SiR) 21 p1 R 22q1 R 23 r1 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0419] In the above formula, R b1 Each occurrence is independently represented by a hydroxyl group or a hydrolyzable group.

[0420] The above R b1 Preferably, each occurrence is an independently hydrolyzable group.

[0421] The above R b1 Ideally, each occurrence should be independently represented as -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl group, more preferably -OR j (i.e., alkoxy group). As R j Examples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0422] In the above formula, R c1 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0423] The above R c1 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0424] In the above examples, k1, l1, and m1 are each independent integer from 0 to 3 at each occurrence. The sum of k1, l1, and m1 is within the range (SiR). a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3.

[0425] In one approach, k1 is in each (SiR)a1 k1 R b1 l1 R c1 m1 Each of the units is an independent integer from 1 to 3, preferably 2 or 3, more preferably 3. In the preferred embodiment, k1 is 3.

[0426] In equations (1) and (2) above, R Si In the case of the group shown in formula (S3), it is preferable that at least two Si atoms bonded with hydroxyl or hydrolyzable groups are present at the end portions of formulas (1) and (2).

[0427] In a preferred embodiment, the group represented by formula (S3) has -Z 1 -SiR 22 q1 R 23 r1 (In the formula, q1 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer from 0 to 2), -Z 1’ -SiR 22’ q1’ R 23’ r1’ (In the formula, q1' is an integer from 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer from 0 to 2) or -Z 1” -SiR 22” q1” R 23” r1” (In the formula, q1” is any one of an integer from 1 to 3, preferably 2 or 3, more preferably 3, and r1” is any one of an integer from 0 to 2.) Z 1 Z 1’ Z 1” R 22 R 23 R 22’ R 23’ R 22” and R 23” The meaning is the same as above.

[0428] In the preferred embodiment, R exists in equation (S3). 21’ In the case of at least one, preferably all R 21’ In this context, q1” is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0429] In the preferred embodiment, R exists in equation (S3). 21 In the case of at least one, preferably all R 21 In this context, p1' is 0, and q1' is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0430] In the preferred embodiment, R exists in equation (S3). a1 In the case of at least one, preferably all R a1 In this context, p1 is 0, and q1 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0431] In the preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

[0432] R d1 Each occurrence is independently represented by -Z. 2 -CR 31 p2 R 32 q2 R 33 r2 .

[0433] Z 2 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 2 The right side of the structure and (CR 31 p2 R 32 q2 R 33 r2 ) bond.

[0434] In the preferred method, Z 2 It is a divalent organic group.

[0435] The above Z 2 C is preferred 1－6 Alkylene, -(CH2) z5 -O-(CH2) z6 - (where 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 -Phenylidene-(CH2) z8 —(In the formula, z7 is an integer from 0 to 6, for example, an integer from 1 to 6; z8 is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0436] In the preferred method, Z 2 C 1－6 Alkylene or -(CH2) z7-Phenylidene-(CH2) z8 -, preferably -phenylene-(CH2) z8 - In Z 2 When the above-mentioned groups are present, the lightfastness, especially the UV resistance, can be further improved.

[0437] In other preferred embodiments, the above Z 2 C 1－3 Alkylene. In one manner, Z 2 It can be -CH2CH2CH2-. In another way, Z 2 It can be -CH2CH2-.

[0438] R 31 Each occurrence is independently represented by -Z. 2’ -CR 32’ q2’ R 33’ r2’ .

[0439] Z 2’ Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 2’ The right side of the structure and (CR 32’ q2’ R 33’ r2’ ) bond.

[0440] The above Z 2’ C is preferred 1－6 Alkylene, -(CH2) z5’ -O-(CH2) z6’ -(where 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’ -Phenylidene-(CH2) z8’ —(In the formula, z7' is an integer from 0 to 6, for example, an integer from 1 to 6; z8' is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0441] In the preferred method, Z 2’ C 1－6 Alkylene or -(CH2) z7’ -Phenylidene-(CH2) z8’ -, preferably -phenylene-(CH2)z8’ - In Z 2’ When the above-mentioned groups are present, the lightfastness, especially the UV resistance, can be further improved.

[0442] In other preferred embodiments, the above Z 2’ C 1－3 Alkylene. In one manner, Z 2’ It can be -CH2CH2CH2-. In another way, Z 2’ It can be -CH2CH2-.

[0443] The above R 32’ Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 .

[0444] The above Z 3 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 3 The right side of the structure and (SiR) 34 n2 R 35 3－n2 ) bond.

[0445] In one approach, Z 3 It is an oxygen atom.

[0446] In one approach, Z 3 It is a divalent organic group.

[0447] The above Z 3 C is preferred 1－6 Alkylene, -(CH2) z5” -O-(CH2) z6” -(where 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” -Phenylidene-(CH2) z8” —(In the formula, z7” is an integer from 0 to 6, for example, an integer from 1 to 6; z8” is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0448] In the preferred method, Z 3 C1－6 Alkylene or -(CH2) z7” -Phenylidene-(CH2) z8” -, preferably -phenylene-(CH2) z8” - In Z 3 When the above-mentioned groups are present, the lightfastness, especially the UV resistance, can be further improved.

[0449] In other preferred embodiments, the above Z 3 C 1－3 Alkylene. In one manner, Z 3 It can be -CH2CH2CH2-. In another way, Z 3 It can be -CH2CH2-.

[0450] The above R 34 Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0451] R 34 Preferably, each occurrence is an independently hydrolyzable group.

[0452] R 34 Ideally, each occurrence should be independently represented as -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl group, more preferably -OR j (i.e., alkoxy group). As R j Examples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0453] The above R 35 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0454] The above R 35 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0455] In the above formula, n2 is in each (SiR) 34n2 R 35 3－n2 Each element contains an independent integer from 0 to 3. In R... Si In the case of the group shown in formula (S4), at least one (SiR) group with n2 of 1 to 3 exists at the end portion of formulas (1) and (2). 34 n2 R 35 3－n2 ) unit. That is, in this terminal part, all n2 are not simultaneously 0. In other words, in the terminal part of formulas (1) and (2), there is at least one Si atom bonded with a hydroxyl or hydrolyzable group.

[0456] n2 in each (SiR) 34 n2 R 35 3－n2 The units are preferably integers from 1 to 3, more preferably from 2 to 3, and even more preferably 3.

[0457] The above R 33’ Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0458] The above R 33’ In this context, the monovalent organic group is preferably C. 1－20 Alkyl or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (In the formula, s is an integer from 1 to 6, preferably an integer from 2 to 4; t1 is 1 or 0, preferably 0; 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 C. 1－20 Alkyl groups, more preferably C4 1－6 Alkyl groups, particularly preferably methyl groups.

[0459] In one approach, R 33’ It is a hydroxyl group.

[0460] In another way, R 33’ It is a monovalent organic group, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0461] The aforementioned q2' is an independent integer from 0 to 3 at each occurrence, and the aforementioned r2' is an independent integer from 0 to 3 at each occurrence. The sum of q2' and r2' is within (CR... 32’ q2’ R33’ r2’ The value in unit ) is 3.

[0462] q2' in each (CR 32’ q2’ R 33’ r2’ The units are preferably integers from 1 to 3, more preferably from 2 to 3, and even more preferably 3.

[0463] R 32 Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 The -Z 3 -SiR 34 n2 R 35 3－n2 The meaning of R above is the same as above. 32’ The records are the same.

[0464] The above R 33 Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0465] The above R 33 In this context, the monovalent organic group is preferably C. 1－20 Alkyl or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (In the formula, s is an integer from 1 to 6, preferably an integer from 2 to 4; t1 is 1 or 0, preferably 0; 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 C. 1－20 Alkyl groups, more preferably C4 1－6 Alkyl groups, particularly preferably methyl groups.

[0466] In one approach, R 33 It is a hydroxyl group.

[0467] In another way, R 33 It is a monovalent organic group, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0468] In each occurrence of p2, each occurrence of q2, and each occurrence of r2 is an independent integer from 0 to 3. Furthermore, the sum of p2, q2, and r2 is an independent integer from 0 to 3 in each (CR) 31 p2 R 32 q2 R 33 r2 The value in unit ) is 3.

[0469] In one mode, p2 is 0.

[0470] In one approach, p2 in each (CR) 31 p2 R 32 q2 R 33 r2 Each of the units is an integer from 1 to 3, an integer from 2 to 3, or 3. In the preferred embodiment, p2 is 3.

[0471] In one approach, q2 is in each (CR) 31 p2 R 32 q2 R 33 r2 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0472] In one mode, p2 is 0, and q2 is in each (CR) 31 p2 R 32 q2 R 33 r2 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0473] The above R e1 Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 The -Z 3 -SiR 34 n2 R 35 3－n2 The meaning of R above is the same as above. 32’ The records are the same.

[0474] The above R f1 Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0475] The above R f1 In this context, the monovalent organic group is preferably C. 1－20 Alkyl or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (In the formula, s is an integer from 1 to 6, preferably an integer from 2 to 4; t1 is 1 or 0, preferably 0; 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 C. 1－20 Alkyl groups, more preferably C4 1－6 Alkyl groups, particularly preferably methyl groups.

[0476] In one approach, R f1 It is a hydroxyl group.

[0477] In another way, R f1 It is a monovalent organic group, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0478] In the above examples, k2, l2, and m2 are each independently an integer from 0 to 3 at each occurrence. Furthermore, the sum of k2, l2, and m2 is within (CR... d1 k2 R e1 l2 R f1 m2 The value in unit ) is 3.

[0479] In equations (1) and (2) above, R Si In the case of the group shown in formula (S4), it is preferable that at least two Si atoms bonded with hydroxyl or hydrolyzable groups are present at the end portions of formulas (1) and (2).

[0480] In one approach, R Si When n2 is a group as shown in formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR). 34 n2 R 35 3－n2 There are two or more units in each of the end portions of equations (1) and (2), for example, there are 2 to 27 units, preferably 2 to 9 units, more preferably 2 to 6 units, even more preferably 2 to 3 units, and particularly preferably 3 units.

[0481] In the preferred embodiment, R exists in equation (S4). 32’In the case of at least one, preferably all R 32’ In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0482] In the preferred embodiment, R exists in equation (S4). 32 In the case of at least one, preferably all R 32 In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0483] In the preferred embodiment, R exists in equation (S4). e1 In the case of at least one, preferably all R a1 In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0484] In the preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0485] The above R g1 and R h1 Each occurrence is independently represented by -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 l2 R f1 m2 Among them, R 11 R 12 R a1 R b2 R c1 R d1 R e1 R f1 The meanings of n1, k1, l1, m1, k2, l2, and m2 are the same as those described above.

[0486] In the preferred method, R g1 and R h1 Each independently is -Z 4 -SiR 11 n1 R 12 3－n1 .

[0487] The above Z 4 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 4 The right side of the structure and (SiR) 11 n1 R 12 3－n1 ) bond.

[0488] In one approach, Z 4 It is an oxygen atom.

[0489] In one approach, Z 4 It is a divalent organic group.

[0490] The above Z 4 C is preferred 1－6 Alkylene, -(CH2) z5” -O-(CH2) z6” -(where 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” -Phenylidene-(CH2) z8” —(In the formula, z7” is an integer from 0 to 6, for example, an integer from 1 to 6; z8” is an integer from 0 to 6, for example, an integer from 1 to 6). The above C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted.

[0491] In the preferred method, Z 4 C 1－6 Alkylene or -(CH2) z7” -Phenylidene-(CH2) z8” -, preferably -phenylene-(CH2) z8” - In Z 3 When the above-mentioned groups are present, the lightfastness, especially the UV resistance, can be further improved.

[0492] In other preferred embodiments, the above Z 4 C 1－3 Alkylene. In one manner, Z 4 It can be -CH2CH2CH2-. In another way, Z 4 It can be -CH2CH2-.

[0493] In one approach, R SiThese are groups represented by formulas (S2), (S3), (S4), or (S5). These compounds can form surface-treated layers with high surface slip properties.

[0494] In one approach, R Si These compounds are groups represented by formulas (S3), (S4), or (S5). These compounds have multiple hydrolyzable groups at one end, thus enabling strong adhesion to the substrate and the formation of a surface treatment layer with high wear resistance.

[0495] In one approach, R Si These compounds have groups represented by formula (S3) or (S4). These compounds have multiple hydrolyzable groups branching from a Si or C atom at one end, thus enabling the formation of surface treatment layers with higher wear resistance.

[0496] In one approach, R Si The group is represented by formula (S1).

[0497] In one approach, R Si It is the group shown in formula (S2).

[0498] In one approach, R Si It is the group shown in formula (S3).

[0499] In one approach, R Si It is the group shown in formula (S4).

[0500] In one approach, R Si It is the group shown in formula (S5).

[0501] In equations (1) and (2) above, X A This can be understood as referring to the fluoropolyether portion (R) that primarily provides water repellency and surface lubrication. F1 and R F2 ) and the portion that provides bonding energy with the substrate (R Si The connecting part of the link. Therefore, as long as the compounds shown in formulas (1) and (2) can exist stably, the X A It can be a single bond or any group.

[0502] In equation (1) above, α is an integer from 1 to 9, and β is an integer from 1 to 9. These α and β can be determined according to X. A The valence changes accordingly. The sum of α and β and X A The valences are the same. For example, in X A When the organic group is decavalent, the sum of α and β is 10; 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. Furthermore, in X... AWhen the organic group is divalent, α and β are 1.

[0503] In equation (2) above, γ is an integer from 1 to 9. γ can be determined based on X. A The valence changes with X. That is, γ changes from X. A The value after subtracting 1 from the valence.

[0504] X A Each is independently a single bond or a 2- to 10-valent organic group;

[0505] The above X A The 2- to 10-valent organic groups are preferably 2- to 8-valent organic groups. In one embodiment, the 2- to 10-valent organic groups are preferably 2- to 4-valent organic groups, more preferably 2-valent organic groups. In another embodiment, the 2- to 10-valent organic groups are preferably 3- to 8-valent organic groups, more preferably 3- to 6-valent organic groups.

[0506] In one manner, X A It is a single bond or a divalent organic group, with α = 1 and β = 1.

[0507] In one manner, X A It is a single bond or a divalent organic group, and γ is 1.

[0508] In one manner, X A It consists of 3 to 6 valent organic groups, with α being 1 and β being 2 to 5.

[0509] In one manner, X A It consists of 3- to 6-valent organic groups, with γ ranging from 2 to 5.

[0510] In one manner, X A It is a trivalent organic group, with α = 1 and β = 2.

[0511] In one manner, X A It is a trivalent organic group, and γ is 2.

[0512] In X A In the case of a single bond or a divalent organic group, formulas (1) and (2) are represented by the following formulas (1') and (2').

[0513] R F1 -X A -R Si (1')

[0514] R Si -X A -R F2 -X A -R Si (2')

[0515] In one manner, XA It is a single key.

[0516] In another way, X A It is a divalent organic group.

[0517] In one way, as X A For example, single keys or the following formulas can be listed:

[0518] -(R 51 ) p5 -(X 51 ) q5 - The divalent organic group shown.

[0519] [In the formula, R] 51 Indicates a single bond, -(CH2) s5 -or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s5 -,

[0520] 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.

[0521] X 51 Represents -(X) 52 ) 15 -,

[0522] X 52 Each occurrence independently represents a combination of -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -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 - group,

[0523] R 53 Each occurrence independently represents phenyl, C 1-6 Alkyl or C 1-6 Alkoxy, preferably phenyl or C 1-6 Alkyl, more preferably methyl,

[0524] R 54 Each occurrence independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably methyl),

[0525] m5 is an integer from 1 to 100 at each occurrence, preferably an integer from 1 to 20.

[0526] n5 is an integer from 1 to 20 at each occurrence, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0527] l5 is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0528] p5 is either 0 or 1.

[0529] q5 is either 0 or 1.

[0530] Where at least one of p5 and q5 is 1, and the order of the repeating units labeled p5 or q5 and enclosed in parentheses is arbitrary.

[0531] Among them, X A (typically X) A The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, X A It is not replaced by these groups.

[0532] In the preferred embodiment, the above X A Each independently is -(R) 51 ) p5 -(X) 51 ) q5 -R 52 -. R 52 Indicates a single bond, -(CH2) t5 - or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). t5 - t5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. Wherein, R 52 (typically R) 52 The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, R 56 It is not replaced by these groups.

[0533] The above X is preferred A Each can be independently:

[0534] single bond,

[0535] C 1－20 Alkylene

[0536] -R 51 -X 53 -R 52 -,or

[0537] -X 54 -R 5 -.

[0538] [In the formula, R] 51 and R 52 The meaning is the same as above.

[0539] X 53 express:

[0540] -O-、

[0541] -S-、

[0542] -C(O)O-,

[0543] -CONR 54 -、

[0544] -O-CONR 54 -、

[0545] -Si(R) 53 )2-、

[0546] -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、

[0547] -O-(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、

[0548] -O-(CH2) u5 -Si(R) 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-、

[0549] -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-,

[0550] -CONR 54 -(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、

[0551] -CONR 54 -(CH2) u5 -N(R) 54)-,or

[0552] -CONR 54 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 53 )2-,

[0553] (where R is in the formula) 53 R 54 The meanings of m5 and m5 are the same as those mentioned above.

[0554] u5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3.

[0555] X 54 express:

[0556] -S-、

[0557] -C(O)O-,

[0558] -CONR 54 -、

[0559] -O-CONR 54 -、

[0560] -CONR 54 -(CH2) u5 -(Si(R) 54 )2O) m5 -Si(R) 54 )2-、

[0561] -CONR 54 -(CH2) u5 -N(R) 54 )-,or

[0562] -CONR 54 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 54 )2-,

[0563] (The meanings of each symbol in the formula are the same as above.)

[0564] More preferably, the above-mentioned X A Each independently is:

[0565] single bond,

[0566] C 1－20 Alkylene

[0567] -(CH2) s5 -X 53 -;

[0568] -(CH2) s5 -X 53 -(CH2)t5 -.

[0569] -X 54 -,or

[0570] -X 54 -(CH2) t5 -.

[0571] [In the formula, X] 53 X 54 The meanings of s5 and t5 are the same as described above.

[0572] More preferably, the above-mentioned X A Each independently is:

[0573] single bond,

[0574] C 1－20 Alkylene

[0575] -(CH2) s5 -X 53 -(CH2) t5 -,or

[0576] -X 54 -(CH2) t5 -.

[0577] [In the formula, the meanings of each symbol are the same as above.]

[0578] In the preferred embodiment, the above X A Each can be independently:

[0579] single bond,

[0580] C 1－20 Alkylene

[0581] -(CH2) s5 -X 53 -,or

[0582] -(CH2) s5 -X 53 -(CH2) t5 -.

[0583] [In the formula, X] 53 -O-, -CONR 54 - or - O-CONR 54 -,

[0584] R 54 Each occurrence independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 alkyl,

[0585] s5 is an integer from 1 to 20.

[0586] t5 is an integer from 1 to 20.

[0587] In the preferred embodiment, the above X A Each can be independently:

[0588] -(CH2) s5 -O-(CH2) t5 -;

[0589] -CONR 54 -(CH2) t5 -.

[0590] [In the formula, R] 54 Each occurrence independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 alkyl,

[0591] s5 is an integer from 1 to 20.

[0592] t5 is an integer from 1 to 20.

[0593] In one manner, the aforementioned X A Each independently is:

[0594] single bond,

[0595] C 1－20 Alkylene

[0596] -(CH2) s5 -O-(CH2) t5 -、

[0597] -(CH2) s5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-(CH2) t5 -、

[0598] -(CH2) s5 -O-(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-(CH2) t5 -,or

[0599] -(CH2) s5 -O-(CH2) t5 -Si(R) 53 )2-(CH2) u5 -Si(R) 53 )2-(C v H 2v )-.

[0600] [In the formula, R] 53 The meanings of m5, s5, t5, and u5 are the same as described above, and v5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3.

[0601] In the above formula, -(C v H 2v - can be a straight chain or a branched chain, for example, it can be -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0602] The above X A They can be independently selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 Fluoroalkyl (preferably C) 1－3 One or more substituents are substituted in the perfluoroalkyl group. In one manner, X A It is not a substitute.

[0603] In addition, the above X A The various left sides and R F1 Or R F2 Combined, the right side with R Si Combine.

[0604] In one manner, X A They can be -O-C independently. 1－6 Groups other than alkylene groups.

[0605] In another way, as X A For example, the following groups can be listed.

[0606]

[0607]

[0608] [In the formula, R] 41 Each is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C14 group. 1－6 Alkoxy, preferably methyl;

[0609] D is selected from:

[0610] -CH2O(CH2)2-,

[0611] -CH2O(CH2)3-,

[0612] -CF2O(CH2)3-,

[0613] -(CH2)2-,

[0614] -(CH2)3-,

[0615] -(CH2)4-,

[0616] -CONH-(CH2)3-,

[0617] -CON(CH3)-(CH2)3-,

[0618] -CON(Ph)-(CH2)3- (where Ph represents phenyl), and

[0619] Groups in

[0620] (where R is in the formula) 42 Each independently represents a hydrogen atom and a carbon atom. 1－6 alkyl or C 1－6 The alkoxy group is preferably represented by methyl or methoxy, more preferably by methyl.

[0621] E is -(CH2) n - (n is an integer from 2 to 6),

[0622] D and R of the molecular backbone F1 Or R F2 Combining E and R Si Combine.

[0623] As for the above X A Specific examples can be listed as follows:

[0624] single bond,

[0625] -CH2OCH2-,

[0626] -CH2O(CH2)2-,

[0627] -CH2O(CH2)3-,

[0628] -CH2O(CH2)4-,

[0629] -CH2O(CH2)5-,

[0630] -CH2O(CH2)6-,

[0631] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0632] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0633] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[0634] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、

[0635] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-

[0636] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-

[0637] -CH2OCF2CHFOCF2-、

[0638] -CH2OCF2CHFOCF2CF2-、

[0639] -CH2OCF2CHFOCF2CF2CF2-、

[0640] -CH2OCH2CF2CF2OCF2-、

[0641] -CH2OCH2CF2CF2OCF2CF2-、

[0642] -CH2OCH2CF2CF2OCF2CF2CF2-、

[0643] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[0644] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[0645] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[0646] -CH2OCH2CHFCF2OCF2-、

[0647] -CH2OCH2CHFCF2OCF2CF2-、

[0648] -CH2OCH2CHFCF2OCF2CF2CF2-、

[0649] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[0650] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[0651] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[0652] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0653] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[0654] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、

[0655] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、

[0656] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[0657] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、

[0658] -(CH2)2-Si(CH3)2-(CH2)2-、

[0659] -CH2-

[0660] -(CH2)2-、

[0661] -(CH2)3-、

[0662] -(CH2)4-、

[0663] -(CH2)5-、

[0664] -(CH2)6-、

[0665] -CO-、

[0666] -CONH-

[0667] -CONH-CH2-

[0668] -CONH-(CH2)2-、

[0669] -CONH-(CH2)3-、

[0670] -CONH-(CH2)4-、

[0671] -CONH-(CH2)5-、

[0672] -CONH-(CH2)6-,

[0673] -CON(CH3)-CH2-,

[0674] -CON(CH3)-(CH2)2-,

[0675] -CON(CH3)-(CH2)3-,

[0676] -CON(CH3)-(CH2)4-,

[0677] -CON(CH3)-(CH2)5-,

[0678] -CON(CH3)-(CH2)6-,

[0679] -CON(Ph)-CH2- (where Ph represents phenyl),

[0680] -CON(Ph)-(CH2)2- (where Ph represents phenyl),

[0681] -CON(Ph)-(CH2)3- (where Ph represents phenyl),

[0682] -CON(Ph)-(CH2)4- (where Ph represents phenyl),

[0683] -CON(Ph)-(CH2)5- (where Ph represents phenyl),

[0684] -CON(Ph)-(CH2)6- (where Ph represents phenyl),

[0685] -CONH-(CH2)2NH(CH2)3-,

[0686] -CONH-(CH2)6NH(CH2)3-,

[0687] -CH2O-CONH-(CH2)3-,

[0688] -CH2O-CONH-(CH2)6-,

[0689] -S-(CH2)3-,

[0690] -(CH2)2S(CH2)3-,

[0691] -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0692] -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0693] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[0694] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[0695] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-,

[0696] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-,

[0697] -C(O)O-(CH2)3-,

[0698] -C(O)O-(CH2)6-,

[0699] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2,

[0700] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-,

[0701] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3,

[0702] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[0703] -OCH2-,

[0704] -O(CH2)3-,

[0705] -OCFHCF2-,

[0706] and the like.

[0707] In another aspect, X A are each independently a group of the formula: -(R 16 ) x1 -(CFR 17 )y1 -(CH2) z1 - The group shown. In the formula, x1, y1 and z1 are independent integers from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0708] In the above formula, R 16 Each occurrence is independently represented by an oxygen atom, a phenylene group, an imidazolyl group, or a -NR group. 18 -(where R) 18 (Represents a hydrogen atom or an organic group) or a divalent organic group. R is preferred. 18 It is an oxygen atom or a divalent polar group.

[0709] There are no particular limitations on the aforementioned "divalent polar groups," and examples include -C(O)- and -C(=NR). 19 )- and -C(O)NR 19 -(In these formulas, R) 19 (Indicates 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, which may be substituted with one or more fluorine atoms.

[0710] In the above formula, R 17 Each occurrence is independently represented by 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 a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0711] In yet another way, as X A Examples of such groups can be listed below.

[0712]

[0713] [In the formula, R] 41 Each is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C14 group. 1－6 Alkoxy, preferably methyl;

[0714] Each X A In the base, any number of T are R with respect to the molecular backbone. F1 Or R F2 The following groups are combined:

[0715] -CH2O(CH2)2-,

[0716] -CH2O(CH2)3-,

[0717] -CF2O(CH2)3-,

[0718] -(CH2)2-,

[0719] -(CH2)3-,

[0720] -(CH2)4-,

[0721] -CONH-(CH2)3-,

[0722] -CON(CH3)-(CH2)3-,

[0723] -CON(Ph)-(CH2)3- (where Ph represents phenyl), or

[0724]

[0725] [In the formula, R] 42 Each independently represents a hydrogen atom and a carbon atom. 1－6 alkyl or C 1－6 The alkoxy group is preferably represented by methyl or methoxy, and more preferably by methyl.

[0726] The other Ts and Rs of the molecular backbone Si In combination, when present, the remaining Ts are independently methyl, phenyl, and C, respectively. 1－6 Alkyl groups, free radical scavenging groups, or ultraviolet-absorbing groups.

[0727] There are no particular limitations on free radical scavenging groups, as long as they can capture free radicals generated by light irradiation. Examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate esters, crotonic acid esters, malondiamide esters, organic acrylates, hindered amines, hindered phenols, or triazines.

[0728] There are no particular limitations on ultraviolet absorbing groups as long as they are capable of absorbing ultraviolet light. Examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxaloylteaniline, benzoxazinones, and benzoxazoles.

[0729] In preferred embodiments, examples of preferred free radical scavenging groups or ultraviolet absorbing groups include:

[0730]

[0731] In this method, X A Each can be an organic group with a 3 to 10 valence.

[0732] In yet another way, as X A Examples can be listed below for the following groups:

[0733]

[0734] [In the formula, R] 25 R 26 and R 27 Each is an independent 2- to 6-valent organic group.

[0735] R 25 With at least one R F1 Combined, R 26 and R 27 With at least one R Si Combine.

[0736] In one approach, the aforementioned R 25 For single bond, C 1－20 Alkylene, C 3－20 Cycloalkylene, C 5－20 Alpha-aryl, -R 57 -X 58 -R 59 -、-X 58 -R 59 - or -R 57 -X 58 - The above R 57 and R 59 Each independently represents a single bond and a C bond. 1－20 Alkylene, C 3－20 Cycloalkyl or C 5－20 Alpha-aryl. The above X 58 It can be -O-, -S-, -CO-, -O-CO-, or -COO-.

[0737] In one approach, the aforementioned R 26 and R 27 Each group is independently a hydrocarbon group, or has at least one atom selected from N, O, and S at the end or in the main chain of a hydrocarbon, preferably C. 1－6 Alkyl, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-etc. Among them, R 36 Each is 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 It is N, O, or S, preferably N or O. R 38 -R 45 -R 46 -R 45 -、-R 46 -R 45 - or -R 45 -R 46—. Among them, R 45 Each is an alkyl group having 1 to 6 carbon atoms. R 46 It can be N, O, or S, with O being the preferred choice.

[0738] In this method, X A Each can be an organic group with a 3 to 10 valence.

[0739] In yet another way, as X A Examples can be listed below, including the following groups:

[0740]

[0741] [In the formula, X] a It is a single bond or a divalent organic group.

[0742] The above X a It is a single bond or divalent linker directly bonded to the isocyanuric acid ring. As X a Preferably, it is a single bond, an alkylene group, or a divalent group containing at least one type of bond selected from ether bonds, ester bonds, amide bonds, and thioether bonds; more preferably, it is a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one type of bond selected from ether bonds, ester bonds, amide bonds, and thioether bonds.

[0743] As X a More preferably, it is the following formula:

[0744] -(CX) 121 X 122 ) x1 -(X) a1 ) y1 -(CX) 123 X 124 ) z1 - The group shown.

[0745] (where X) 121 ~X 124 They are independently H, F, OH or -OSi (OR) 121 )3 (where R is 3) 121 Each is an alkyl group having 1 to 4 carbon atoms.

[0746] The above X a1 The bonds are -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 connected to CX). 121 X 122 (combined),

[0747] x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.

[0748] As for the above X a1 Preferably, it is -O- or -C(=O)O-.

[0749] As for the above X a The following formula is particularly preferred:

[0750] -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - The group shown

[0751] (In the formula, 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.)

[0752] -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - The group shown

[0753] (In the formula, 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.)

[0754] -(CF2) m17 -(CH2) m18 - The group shown

[0755] (In the formula, m17 is an integer from 1 to 3, and m18 is an integer from 1 to 3.)

[0756] -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - The group shown, or

[0757] (In the formula, 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.)

[0758] -(CH2) m22 - The group shown.

[0759] (In the formula, m22 is an integer from 1 to 3.)

[0760] As for the above X a There are no specific limitations, but the following can be listed: -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 independent integers from 0 to 4), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2-, etc.

[0761] In this method, X A Each can be a divalent or trivalent organic group.

[0762] The fluorinated silane compounds shown in formula (1) or formula (2) above are not particularly limited and may have a content of 5 × 10 2 ~1×10 5 The average molecular weight. Within this range, from the viewpoint of wear durability, an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, is preferred. Herein, the above-mentioned "average molecular weight" is the exponential average molecular weight, and "average molecular weight" is determined by... 19 Values ​​measured by F-NMR.

[0763] In one embodiment, the fluorinated silane compound in the surface treatment agent of the present invention is a compound represented by formula (1).

[0764] In another embodiment, the fluorinated silane compound in the surface treatment agent of the present invention is the compound shown in formula (2).

[0765] In another embodiment, the fluorinated silane compound in the surface treatment agent of the present invention is the compound shown in formula (1) and the compound shown in formula (2).

[0766] In the surface treatment agent of the present invention, the compound shown in formula (2) is preferably 0.1 mol% to 35 mol% relative to the total of the compounds shown in formula (1) and formula (2). The lower limit of the content of the compound shown in formula (2) relative to the total of the compounds shown in formula (1) and formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, even more preferably 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, particularly preferably 5 mol%. The upper limit of the content of the compound shown in formula (2) relative to the total of the compounds shown in formula (1) and formula (2) is preferably 35 mol%, more preferably 30 mol%, even more preferably 20 mol%, even more preferably 15 mol% or 10 mol%. Relative to the total of the compounds shown in formula (1) and formula (2), the compound shown in formula (2) is preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, further preferably 0.2 mol% to 10 mol%, even more preferably 0.5 mol% to 10 mol%, particularly preferably 1 mol% to 10 mol%, for example 2 mol% to 10 mol% or 5 mol% to 10 mol%. By placing the compound shown in formula (2) within such a range, wear durability can be further improved.

[0767] In one embodiment, the surface treatment agent of the present invention contains two or more fluorinated silane compounds of formula (1) or (2). By containing multiple fluorinated silane compounds, friction durability can be further improved.

[0768] In one embodiment, the surface treatment agent of the present invention contains R Si Two or more fluorosilane compounds of formula (1) or (2) are selected from formulas (S1), (S2), (S3), (S4), and (S5) and are distinct from each other. This is achieved by containing different R groups. Si Fluorinated silane compounds can further improve friction durability.

[0769] In one embodiment, the surface treatment agent of the present invention contains R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) that are groups selected from formulas (S3), (S4), and (S5). By simultaneously using R... Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) whose groups are selected from formulas (S3), (S4) and (S5) can further improve friction durability.

[0770] In one embodiment, the surface treatment agent of the present invention contains R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) are selected from groups of formulas (S3) and (S4). By simultaneously using R... Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) with groups selected from formula (S3) and (S4) can further improve friction durability.

[0771] In one embodiment, the surface treatment agent of the present invention contains R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) with the group shown in formula (S3). By simultaneously using R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S3) can further improve friction durability.

[0772] In one embodiment, the surface treatment agent of the present invention contains R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) with the group shown in formula (S4). By simultaneously using R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S1), and R Si Fluorosilane compounds of formula (1) or (2) with groups represented by formula (S4) can further improve friction durability.

[0773] The compound shown in formula (1) or (2) above can be obtained, for example, by methods known to the public, such as those described in International Publication No. 97 / 07155, Japanese Patent Application Publication No. 2008-534696, Japanese Patent Application Publication No. 2014-218639, and Japanese Patent Application Publication No. 2017-82194.

[0774] The content of the compound shown in formula (1) or (2) above is preferably 0.01 to 50.0% by mass relative to the total content of the surface treatment agent, more preferably 0.1 to 30.0% by mass, even more preferably 1.0 to 25.0% by mass, and particularly preferably 5.0 to 20.0% by mass. By keeping the content of the above-mentioned fluorinated silane compound within the above range, higher water and oil repellency can be obtained.

[0775] The surface treatment agent of the present invention may contain solvents, (non-reactive) fluorinated polyether compounds which can be understood as fluorinated oils, preferably perfluorinated (poly)ether compounds (hereinafter collectively referred to as "fluorinated oils"), (non-reactive) organosilicon compounds which can be understood as silicone oils (hereinafter referred to as "silicone oils"), alcohols, compatibilizers, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.

[0776] Examples of solvents mentioned above include: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, acetic acid cellosol, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, and ethyl acetoacetate. Esters such as amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; and ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and propylene glycol monomethyl ether acetate. Diol ethers such as propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, and tert-pentanol; diols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and methyl cellosolve. Solvents, isopropyl solvents, butyl solvents, diethylene glycol monomethyl ether and other ether alcohols; diethylene glycol monoethyl ether acetate; fluorinated solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), ZEORORAH, HFE7100, HFE7200, HFE7300, etc. Alternatively, two or more of these mixed solvents can be listed.

[0777] As a fluorinated oil, there are no particular limitations, for example, the following compounds (perfluoro(poly)ether compounds) can be listed as general formula (3).

[0778] Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’-(OCF2) d’ -Rf 6 …(3)

[0779] In the formula, Rf 5 This indicates an alkyl group (preferably C16) with 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. 1－16 perfluoroalkyl), Rf 6 This refers to an alkyl group (preferably C16) with 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. 1－16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0780] a', b', c', and d' represent the number of four repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are independent integers ranging from 0 to 300. Furthermore, the sum of a', b', c', and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of the repeating units indicated by subscripts a', b', c', or d' and enclosed in parentheses is arbitrary in the formula. In these repeating units, -(OC4F8)- can be any one 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))-, preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. -(OC2F4)- can be either -(OCF2CF2)- or (OCF(CF3))-, with -(OCF2CF2)- being preferred.

[0781] As examples of perfluoro(poly)ether compounds represented by the above general formula (3), compounds represented by any of the following general formulas (3a) and (3b) (or mixtures of one or more) can be listed.

[0782] Rf 5 -(OCF2CF2CF2) b” -Rf 6 …(3a)

[0783] Rf 5-(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 …(3b)

[0784] In these formulas, Rf 5 and Rf 6 As described above; in equation (3a), b” is an integer greater than 1 and less than 100; in equation (3b), a” and b” are each independently an integer greater than 0 and less than 30, and c” and d” are each independently an integer greater than 1 and less than 300. The order of the repeated units marked with subscripts a”, b”, c”, and d” and enclosed in parentheses is arbitrary in the equation.

[0785] Furthermore, from other perspectives, fluorinated oils can be classified using the general formula Rf. 3 -F(where Rf) 3 C 5－16 Compounds shown as perfluoroalkyl groups. Alternatively, they can be trifluorochloroolidinium oligomers.

[0786] The aforementioned fluorinated oils can have an average molecular weight of 500–10,000. The molecular weight of fluorinated oils can be determined using GPC.

[0787] The fluorinated oil may contain, for example, 0.01 to 50% by mass, preferably 0.1 to 30% by mass, and for example, 1 to 15% by mass, relative to the surface treatment agent of the present invention.

[0788] In one embodiment, the surface treatment agent of the present invention is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means completely free of fluorinated oil, or may contain trace amounts of fluorinated oil.

[0789] In one approach, the average molecular weight of the fluorinated oil can be greater than that of the fluorinated silane compound. By setting such an average molecular weight, especially when the surface treatment layer is formed using vacuum evaporation, superior wear durability and surface lubrication can be obtained.

[0790] In one approach, the average molecular weight of the fluorinated oil can be made smaller than the average molecular weight of the fluorinated silane compound. By setting such an average molecular weight, it is possible to suppress the decrease in transparency of the surface treatment layer obtained from the compound and to form a cured product with high wear resistance and high surface lubricity.

[0791] Fluorinated oils help improve the surface lubricity of layers formed by the surface treatment agents of this invention.

[0792] As the aforementioned silicone oil, for example, linear or cyclic silicone oils with siloxane bonds of 2,000 or less can be used. Linear silicone oils can be so-called ordinary silicone oils and modified silicone oils. Examples of ordinary silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include silicone oils obtained by modifying ordinary silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, or alcohol groups. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0793] In the surface treatment agent of the present invention, relative to the total of 100 parts by mass of the fluorinated silane compounds of the present invention (or the total of two or more, the same below), the silicone oil may contain, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass.

[0794] Silicone oil helps improve the surface lubrication of surface treatment layers.

[0795] Examples of alcohols mentioned above include non-fluorinated alcohols with 1 to 6 carbon atoms, such as methanol, ethanol, isopropanol, and tert-butanol. Adding these alcohols to surface treatment agents can improve the stability of the agents and enhance the compatibility between fluorinated silane compounds and solvents.

[0796] Examples of compatibilizers include fluorinated alcohols such as 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, with preferred fluorinated alcohols having a CF2H terminus, fluorinated aryl alcohols such as 1,3-bis(trifluoromethyl)benzene, and preferably fluorinated benzene.

[0797] Examples of catalysts mentioned above include acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), and transition metals (such as Ti, Ni, Sn, etc.).

[0798] The catalyst promotes the hydrolysis and dehydration condensation of the fluorinated silane compounds of the present invention, and promotes the formation of the layer formed by the surface treatment agent of the present invention.

[0799] Other components, besides those mentioned above, may include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, methyltriacetoxysilane, etc.

[0800] The surface treatment agent of the present invention can be impregnated in a porous material, such as a porous ceramic material, metal fiber, or a material such as steel wool fixed into a cotton-like form, to form granules. These granules can be used, for example, for vacuum evaporation.

[0801] In addition to the above-mentioned components, the surface treatment agent of the present invention may also contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.

[0802] The thickness of the aforementioned surface treatment layer is not particularly limited. In the case of optical components, from the viewpoints of optical performance, surface lubricity, friction durability, and anti-fouling properties, the thickness of the aforementioned layer is preferably in the range of 1–50 nm, 1–30 nm, and more preferably 1–15 nm.

[0803] The aforementioned surface treatment layer can be formed, for example, by forming a layer of the aforementioned surface treatment agent on the aforementioned intermediate layer and performing post-treatment on the layer as needed.

[0804] The formation of the aforementioned surface treatment agent layer can be achieved by applying the surface treatment agent to the surface of the intermediate layer in a manner that covers the surface. There are no particular limitations on the covering method. For example, wet covering and dry covering methods can be used.

[0805] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0806] Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition) include resistance heating, high-frequency heating using electron beams, microwaves, etc., ion beams, and similar methods. Specific examples of CVD methods include plasma CVD, optical CVD, thermal CVD, and similar methods.

[0807] Alternatively, atmospheric pressure plasma method can be used for coverage.

[0808] When using the wet coating method, the above-mentioned surface treatment agent can be applied to the intermediate layer after being diluted with a solvent. From the viewpoint of the stability of the above-mentioned surface treatment agent and the volatility of the solvent, the following solvents are preferred: perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F... 13CH2CH3 (e.g., ASAHIKLIN AC-6000 manufactured by Asahi Glass Co., Ltd., a registered trademark); 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., ZEORORA H manufactured by ZEON Corporation, a registered trademark); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd., a registered trademark); perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd., a registered trademark). Alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl groups can be straight-chain or branched) such as 7100), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Corporation), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Corporation), or CF3CH2OCF2CHF2 (e.g., ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or in mixtures of two or more. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0809] When using the dry coating method, the above-mentioned surface treatment agent can be supplied directly to the dry coating method, or it can be supplied to the dry coating method after being diluted with the above-mentioned solvent.

[0810] The formation of the aforementioned surface treatment agent layer is preferably carried out in such a manner that the surface treatment agent is present in the layer together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of using the wet coating method, the aforementioned surface treatment agent can be diluted with a solvent, and the catalyst can be added to the diluted solution of the aforementioned surface treatment agent before it is applied to the surface of the intermediate layer. In the case of using the dry coating method, the aforementioned surface treatment agent with added catalyst can be directly vapor-deposited (usually vacuum vapor-deposited), or vapor-deposited (usually vacuum vapor-deposited) using particulate material of the aforementioned surface treatment agent with added catalyst impregnated in a porous metal such as iron or copper.

[0811] The catalyst can be any suitable acid or base. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0812] As described above, a layer derived from the aforementioned surface treatment agent is formed on the surface of the intermediate layer to manufacture the article of the present invention. The resulting surface treatment layer exhibits high friction durability. Furthermore, in addition to high friction durability, the layer, depending on the composition of the surface treatment agent used, can also possess properties such as water repellency, oil repellency, stain resistance (e.g., preventing the adhesion of fingerprints and other dirt), water resistance (preventing water from penetrating electronic components, etc.), and surface slip properties (or lubrication, such as the ability to wipe away fingerprints and other dirt, and excellent tactile feel for fingers), making it suitable for use as a functional film.

[0813] The article of the present invention can also be an optical material having the above-described surface treatment layer on its outermost layer.

[0814] The articles of this invention can be optical components, but are not particularly limited thereto. Examples of optical components include: lenses for eyeglasses, etc.; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panels for devices such as portable telephones and portable information terminals; disc surfaces for Blu-ray discs, DVD discs, CD-Rs, MO discs, etc.; optical fibers; and the display surfaces of clocks, etc.

[0815] In addition, the articles of the present invention can also be medical devices or medical materials.

[0816] The articles of the present invention have high friction durability and high weather resistance by having an intermediate layer containing a Ce layer on a substrate, and having a surface treatment layer thereon formed by a surface treatment agent containing a fluorinated silane compound.

[0817] The articles of the present invention have been described in detail above. However, the articles and methods of manufacturing the articles of the present invention are not limited to the descriptions above.

[0818] Example

[0819] The articles of the present invention will be described below in the embodiments, but the present invention is not limited to the following embodiments. In addition, in this embodiment, the chemical formulas shown below all represent average compositions, and the order of the repeating units constituting the fluorinated polyether ((CF2CF2CF2O), (CF(CF3)CF2O), (CF2CF2O), (CF2O), etc.) is arbitrary.

[0820] As the glass substrate, chemically strengthened and surface-polished Gorilla Glass 5 (manufactured by Corning Incorporated) with a thickness of 0.8 mm and dimensions of 66.0 mm × 142.0 mm was used. After forming an intermediate layer on the glass substrate, a surface treatment layer was formed on the intermediate layer to obtain a glass substrate with a surface treatment layer. Details are as follows.

[0821] (Vapor-deposited materials)

[0822] For the individual SiO2 and Ta2O5 vapor deposition materials, vapor deposition materials manufactured by Canon Optronics were purchased and used; for CeO2, vapor deposition materials manufactured by Sanwa Grinding & Industrial Co., Ltd. were purchased and used. In addition, vapor deposition materials with Si to Ce molar ratios of 95:5 and 90:10 were prepared separately. The Si to Ce molar ratio was determined by X-ray fluorescence (XRF) analysis.

[0823] (Formation of the intermediate layer)

[0824] The intermediate layer was formed by electron beam evaporation (Examples 1-7, Comparative Examples 1, 3 and 4) or sputtering (Comparative Example 2).

[0825] Electron beam evaporation is performed in the following manner.

[0826] The vacuum evaporation apparatus is equipped with individual SiO2, individual CeO2, individual Ta2O5, or both SiO2 and CeO2. The vacuum evaporation apparatus is then vented to a pressure of 3.0 × 10⁻⁶. －3 Pa or less. Then, on Gorilla Glass 5 (manufactured by Corning Incorporated), conditions are set for each embodiment to form a film by forming a single layer of film-forming material 1 as shown in Table 1 below, or by stacking layers of film-forming material 1 and film-forming material 2, thereby forming an intermediate layer film.

[0827] The sputtering method is performed as described below.

[0828] A silicon and tantalum target were set in a DC sputtering apparatus. While introducing a mixture of argon and oxygen into the chamber, a 40 nm thick intermediate layer composed of a composite oxide of silicon and tantalum was formed with a film formation ratio (Si / Ta) of 9 / 1.

[0829] [Table 1]

[0830]

[0831] (Preparation of surface treatment agents)

[0832] The following fluorinated polyether compounds (A) or (B) were diluted with HFE7200 to reach 20% by mass. In Examples 1-4, 6 and 7 and Comparative Examples 1-3, compound (A) containing fluorinated polyether groups was used, and in Example 5 and Comparative Example 4, compound (B) containing fluorinated polyether groups was used.

[0833] • Compounds containing fluorinated polyether groups (A)

[0834] CF3CF2CF2O(CF2CF2CF2O) 23 CF2CF2CONHCH2C(CH2CH2CH2Si(OCH3)3)3

[0835] • Compounds containing fluorinated polyether groups (B)

[0836]

[0837] (Formation of the surface treatment layer)

[0838] The surface treatment layer was formed using an apparatus capable of resistance heating vapor deposition. Specifically, 0.09 g of surface treatment agent was filled into the resistance heating boat within the vacuum vapor deposition apparatus, and the vacuum vapor deposition apparatus was evacuated to a pressure of 3.0 × 10⁻⁶. －3 Pa below. Then, the resistance heating boat is heated to a certain temperature, thereby depositing a film on the glass on which the above-mentioned intermediate layer is formed. Then, the glass with the deposited film is left to stand in an atmosphere at 150°C for 30 minutes, and then cooled to room temperature to form a surface treatment layer on the glass, thus obtaining the glass substrate with the surface treatment layer of Examples 1 to 7 and Comparative Examples 1 to 4.

[0839] (Friction test)

[0840] (Friction Test A)

[0841] Using a friction tester (manufactured by Shin-To Science Co., Ltd.), the static contact angle (°) of water on the surfaces of the glass substrates of Examples 1-9 and Comparative Examples 1-4 was measured after every 2500 rubs under the following conditions. The test was stopped when the measured value of the static contact angle of water fell below 100°, or when the number of rubs changed by 20,000. The test environment conditions were 25°C and 40% RH. The static contact angle of water was measured using the method described below. The results are shown in Table 1 below.

[0842] Eraser: Raber Eraser (manufactured by Minoan);

[0843] Grounding area:

[0844] Travel distance (one way): 30mm;

[0845] Movement speed: 2,400 mm / min;

[0846] load:

[0847] (Friction Test B)

[0848] The glass substrates of Examples 1-9 and Comparative Examples 1-4 were arranged horizontally, and the following friction element was brought into contact with the surface of the surface treatment layer (the contact surface is a circle with a diameter of 1 cm). A load of 5 N was applied, and then, under the applied load, the friction element was reciprocated at a speed of 40 mm / s. The static contact angle of water (°) was measured after every 1000 friction cycles. The test was stopped when the measured value of the static contact angle of water became less than 90°. The static contact angle of water was measured using the method described below.

[0849] Friction components

[0850] Cover the surface (1 cm in diameter) of the silicone rubber processed article shown below with cotton soaked in artificial sweat with the composition shown below, and use it as a friction element.

[0851] Composition of artificial sweat:

[0852] Anhydrous disodium hydrogen phosphate: 2g;

[0853] Sodium chloride: 20g;

[0854] 85% lactic acid: 2g;

[0855] Histidine hydrochloride: 5g;

[0856] Distilled water: 1 kg.

[0857] Silicone rubber processed products:

[0858] The silicone rubber plug SR-51 made by TIGERS POLYMER is processed into a cylindrical shape with a diameter of 1cm and a thickness of 1cm.

[0859] (Enhancing weather resistance testing and evaluation)

[0860] For the glass substrates of Example 5 and Comparative Example 4, a weathering resistance test was conducted by irradiation with a xenon lamp. The xenon lamp used was a Suga testing machine manufacturer, with an irradiance of 180 W / m² at 300–400 nm. 2 The xenon lamp irradiation was performed continuously, but when determining the static contact angle of water, the glass substrate was temporarily removed. The surface treatment layer was wiped five times with KIMWIPES (trade name, manufactured by Kimberly-Clark Corporation) that had fully absorbed pure water, and then wiped five times with another KIMWIPES that had fully absorbed ethanol. The substrate was then allowed to dry. The static contact angle of water was then measured immediately afterward.

[0861] First, as an initial evaluation, the static contact angle of water was measured on the glass substrate after the surface treatment layer was formed, before xenon lamp irradiation (irradiation time 0 hours). Then, the static contact angle of water was measured on the surface treatment layer after xenon lamp irradiation for a specified time. Evaluation was conducted from the start of xenon lamp irradiation until the static contact angle of water was less than 90 degrees, or until the cumulative irradiation time reached 1858 hours. The results are shown in Table 2.

[0862] (Static contact angle measurement)

[0863] Regarding the static contact angle of water, in friction tests A and B, 2 μL of pure water droplets were dropped in each test. The contact angle of the water at 5 points was measured using a contact angle meter (Kyowa Interface Chemical Co., Ltd.: DropMaster701 automatic contact angle meter), and the average value was recorded.

[0864] [Table 2]

[0865]

[0866] [Table 3]

[0867]

[0868] Industrial availability

[0869] The articles of the present invention are suitable for a wide variety of uses, such as for use as optical components.

Claims

1. An article having a substrate, an intermediate layer, and a surface treatment layer, characterized in that: The intermediate layer is located on the substrate. The surface treatment layer is located on the intermediate layer in contact with it, and is formed of a surface treatment agent containing a fluorinated silane compound. The intermediate layer includes a Ce-containing layer. The Ce-containing layer also contains Si. In the Ce-containing layer, the molar ratio of Si to Ce is 40:60 to 99:

1. The intermediate layer is a film formed by sputtering, ion beam assisted deposition, vacuum evaporation, chemical vapor deposition, or atomic layer deposition. The thickness of the intermediate layer is less than 120 nm.

2. The article as described in claim 1, characterized in that: The Ce-containing layer comprises a composite oxide containing Si and Ce.

3. The article as described in claim 1, characterized in that: In the Ce-containing layer, the molar ratio of Si to Ce is 40:60 to 98:

2.

4. The article as described in claim 1, characterized in that: The intermediate layer also contains alkali metals or alkaline earth metals.

5. The article as described in claim 4, characterized in that: The concentration of the alkali metal and alkaline earth metal in the intermediate layer is 0.1–30 mol%.

6. The article as claimed in claim 1, characterized in that: The thickness of the Ce-containing layer is 0.1–100 nm.

7. The article as claimed in claim 1, characterized in that: The intermediate layer is composed of a Ce-containing layer.

8. The article as claimed in claim 1, characterized in that: The intermediate layer further includes a silicon oxide layer on top of the Ce-containing layer.

9. The article as claimed in claim 8, characterized in that: The thickness of the silicon oxide layer is 0.1 nm to 100 nm.

10. The article as claimed in claim 1, characterized in that: The fluorinated silane compound is at least one compound containing a fluorinated polyether group, as shown in formula (1) or (2): In equations (1) and (2): R F1 Rf, independently 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 Each is independently a C that is substituted with one or more fluorine atoms or is not substituted. 1－16 alkyl; Rf 2 C atoms that are substituted with one or more fluorine atoms or are not substituted 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R Si Each of these is a monovalent group, independently containing a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group other than a hydrolyzable group; The hydrolyzable group is selected from -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j In these formulas, R, -NCO, and halogens, are... j C indicates substitution or non-substitution. 1－4 alkyl, At least 1 R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; X A Each is an independent single bond or an organic group with a valence of 2 to 10. α is an integer from 1 to 9; β is an integer from 1 to 9; γ can be an integer from 1 to 9, each independently.

11. The article as claimed in claim 10, characterized in that: R F Each of the following groups can be independently represented: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - In the formula, R Fa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each an independent integer from 0 to 200. The sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

12. The article as claimed in claim 11, characterized in that: Rf 1 C, each independently 1－16 Perfluoroalkyl Rf 2 C, each independently 1－6 Perfluoroalkylene, R Fa It is a fluorine atom.

13. The article as claimed in claim 10, characterized in that: R F Each occurrence is independently represented by a group as shown in formula (f1), (f2), (f3), (f4), (f5), or (f6): -(OC3F6) d -(OC2F4) e - (f1) In equation (f1), d is an integer from 1 to 200, and e is 0 or 1. -(OC4F8) c -(OC3F6) d -(OC2F4) e - (OCF2) f - (f2) In equation (f2), c and d are independent integers from 0 to 30; e and f are independent integers from 1 to 200; The sum of c, d, e, and f is an integer between 10 and 200; The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula. -(R 6 -R 7 ) g - (f3) In equation (f3), R 6 It is either OCF2 or OC2F4; R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or a combination of two or three groups selected from these groups; g is an integer from 2 to 100. -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) In equation (f4), R 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or combinations of two or three groups independently selected from these groups, R 6’ It is either OCF2 or OC2F4. R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or combinations 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 for ， In the formula, * indicates the bonding position; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) In equation (f5), e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the equation. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) In equation (f6), f is an integer greater than 1 and less than 200, a, b, c, d and e are each an integer greater than 0 and less than 200, and the order of the repeated units marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the equation.

14. The article as claimed in claim 10, characterized in that: R Si The group is represented by the following formula (S1), (S2), (S3), (S4), or (S5): In equations (S1), (S2), (S3), (S4), and (S5): R 11 Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 12 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; n1 in each (SiR) 11 n1 R 12 3－n1 Each unit contains an independent integer from 0 to 3; X 11 Each occurrence is independently a single bond or a divalent organic group; R 13 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; t is an integer greater than 2 at each occurrence; R 14 Each occurrence is independently represented by a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 ; R 15 Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 1 to 6 carbon atoms; R a1 Each occurrence is independently represented by -Z. 1 -SiR 21 p1 R 22 q1 R 23 r1 ; Z 1 Each occurrence is independently represented by an oxygen atom or a divalent organic group; R 21 Each occurrence is independently represented by -Z. 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ; R 22 Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 23 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; p1 is an integer from 0 to 3 independently at each occurrence; q1 is an integer from 0 to 3 at each occurrence; r1 is an integer from 0 to 3 independently at each occurrence; The sum of p1, q1, and r1 in SiR 21 p1 R 22 q1 R 23 r1 The unit is 3; Z 1’ Each occurrence is independently represented by an oxygen atom or a divalent organic group; R 21’ Each occurrence is independently represented by -Z. 1” -SiR 22” q1” R 23” r1” ; R 22’ Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 23’ Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; p1' is an integer from 0 to 3, which appears independently at each location; q1' is an integer from 0 to 3 independently at each occurrence; r1' is an integer from 0 to 3 independently at each occurrence; The sum of p1', q1', and r1' in SiR 21’ p1’ R 22’ q1’ R 23’ r1’ The unit is 3; Z 1” Each occurrence is independently represented by an oxygen atom or a divalent organic group; R 22” Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 23” Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; q1” is an integer from 0 to 3, which appears independently at each occurrence; r1” is an integer from 0 to 3, which appears independently at each occurrence; The sum of q1” and r1” in SiR 22” q1” R 23” r1” The unit is 3; R b1 Each occurrence is independently a hydroxyl group or a hydrolyzable group; R c1 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; k1 is an independent integer from 0 to 3 at each occurrence; l1 is an integer from 0 to 3 independently at each occurrence; m1 is an integer from 0 to 3 at each occurrence; The sum of k1, l1, and m1 in SiR a1 k1 R b1 l1 R c1 m1 The unit is 3; R d1 Each occurrence is independently represented by -Z. 2 -CR 31 p2 R 32 q2 R 33 r2 ; Z 2 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group; R 31 Each occurrence is independently represented by -Z. 2’ -CR 32’ q2’ R 33’ r2’ ; R 32 Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 ; R 33 Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is an integer from 0 to 3 independently at each occurrence; q2 is an integer from 0 to 3 independently at each occurrence; r2 is an integer from 0 to 3 independently at each occurrence; The sum of p2, q2, and r2 in SiR 31 p2 R 32 q2 R 33 r2 The unit is 3; Z 2’ Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group; R 32’ Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 ; R 33’ Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is an integer from 0 to 3 independently at each occurrence; r2' is an integer from 0 to 3 independently at each occurrence; The sum of q2' and r2' in SiR 32’ q2’ R 33’ r2’ The unit is 3; Z 3 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group; R 34 Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 35 Each occurrence is independently represented by a hydrogen atom or a monovalent organic group; n2 is an integer from 0 to 3 independently at each occurrence; R e1 Each occurrence is independently represented by -Z. 3 -SiR 34 n2 R 35 3－n2 ; R f1 Each occurrence is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 is an integer from 0 to 3 independently at each occurrence; l2 is an integer from 0 to 3 independently at each occurrence; m2 is an integer from 0 to 3 at each occurrence; The sum of k2, l2, and m2 in CR d1 k2 R e1 l2 R f1 m2 The unit is 3; R g1 and R h1 Each occurrence is independently represented by -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 l2 R f1 m2 ; Z 4 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group; The hydrolyzable group is selected from -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j In these formulas, R, -NCO, and halogens, are... j C indicates substitution or non-substitution. 1－4 alkyl, In formulas (S1), (S2), (S3), (S4) and (S5), there is at least one Si atom bonded with a hydroxyl group or a hydrolyzable group.

15. The article as claimed in claim 10, characterized in that: X A Each can be an independent single bond or a divalent organic group. α, β and γ are 1.

16. The article as claimed in claim 10, characterized in that: X A Each is an independent trivalent organic group. α is 1 and β is 2, or α is 2 and β is 1. γ is 2.

17. The article as claimed in claim 1, characterized in that: The substrate is a glass substrate.

18. The article as claimed in claim 1, characterized in that: The substrate is a glass substrate. The thickness of the Ce-containing layer is 1.0–50 nm. The fluorinated silane compound is at least one compound containing a fluorinated polyether group, as shown in formula (1): In formula (1): R F1 Rf, each independently 1 -R F -O q -; Rf 1 C independently 1－3 Perfluoroalkyl; R F Each of these groups is independently represented by the following formula (f1): -(OC3F6) d -(OC2F4) e - (f1) In equation (f1), d is an integer from 10 to 200, and e is 1; q is 0 independently; R Si Independently for -SiR 11 3 or -CR e1 3; Formula – SiR 11 3. -CR e1 3 in: R 11 Each occurrence is independently represented by -OR j ; R j C 1－4 alkyl; R e1 Each occurrence is independently represented by -Z. 3 -SiR 34 3; Z 3 It is -CH2CH2CH2-; R 34 Each occurrence is independently represented by -OR j ; X A Each is independently -CONH-(CH2) t5 - or the group shown in the following formula: ， In the formula, X a For -(CH2) m22 -, where m22 is an integer from 1 to 3, Formula: CONH-(CH2) t5 In this context, t5 is an integer from 1 to 20; α is 1; β is 1 or 2.

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