Antifouling material

Abstract

The present invention provides a product which comprises: a base material; an intermediate layer positioned upon the base material; and a surface treatment layer which is positioned upon the intermediate layer and is formed from a surface treatment agent which contains a fluorine-containing silane compound, wherein the base material is a ceramic glass which contains a petalite crystalline phase and a lithium silicate crystalline phase, and the intermediate layer contains a first layer of aluminum oxide and silicon oxide and a second layer of silicon oxide which is positioned upon the first layer.

Description

[Technical Field]

[0001] This disclosure relates to compounds containing fluoropolyether groups. [Background technology]

[0002] Certain fluorine-containing silane compounds are known to provide excellent water repellency, oil repellency, and stain resistance when used for surface treatment of substrates. Layers obtained from surface treatment agents containing fluorine-containing silane compounds (hereinafter also referred to as "surface treatment layers") are applied as so-called functional thin films to a wide variety of substrates, such as glass, plastics, fibers, sanitary products, and building materials (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-218639 [Patent Document 2] Japanese Patent Publication No. 2017-082194 [Overview of the project] [Problems that the invention aims to solve]

[0004] While the fluorine-containing silane compounds described in Patent Document 1 or Patent Document 2 can provide a surface treatment layer with excellent functionality, there is a need for a surface treatment layer with even higher friction resistance.

[0005] This disclosure aims to provide articles having a surface treatment layer with higher friction resistance. [Means for solving the problem]

[0006] This disclosure includes the following aspects: [1] Substrate and An intermediate layer located on the aforementioned substrate, A surface treatment layer located on the aforementioned intermediate layer, formed from a surface treatment agent containing a fluorine-containing silane compound, An article having, The substrate is a ceramic glass containing a petalite crystalline phase and a lithium silicate crystalline phase. The aforementioned intermediate layer includes a first layer of aluminum oxide and silicon oxide, and a second layer of silicon oxide located above it. Goods. [2] The article according to [1] above, wherein the total mass of the petalite crystalline phase and the lithium silicate crystalline phase in the substrate is greater than the total mass of other crystalline phases present in the ceramic glass. [3] The ceramic glass is composed of the following: SiO2: 55~80% by mass, Al2O3: 2~20% by mass, Li2O: 5~20% by mass, B2O3: 0~10% by mass, Na2O: 0~5% by mass, ZnO: 0~10% by mass, P2O5: 0.5~6% by mass, and ZrO2:0.2~15% by mass The articles described in [1] or [2] above, which contain the following: [4] The ceramic glass further comprises the following components: K2O: 0-4% MgO: 0-8% TiO2: 0-5%, CeO2: 0~0.4%, and SnO2: 0.05~0.5% The article described in [3] above, which contains the following: [5] The article according to any one of the above [1] to [4], wherein the aluminum oxide is Al2O3 and the silicon oxide is SiO2. [6] The article according to any one of the above items [1] to [5], wherein in the first layer, the content of aluminum is 0.5 to 60.0 at% with respect to the total amount of aluminum and silicon. [7] In the first layer, the content of aluminum is 0.7 to 50.5 at% with respect to the total amount of aluminum and silicon. The article according to any one of the above [1] to [6]. [8] The thickness of the intermediate layer is 5 nm to 35 nm. The article according to any one of the above [1] to [7]. [9] The thickness of the intermediate layer is 10 nm to 30 nm. The article according to any one of the above [1] to [8].

[10] The ratio of the thickness of the first layer to the thickness of the second layer is 0.1 to 10. The article according to any one of the above [1] to [9].

[11] The fluorine-containing silane compound is the following formula (1) or (2):

Chemical formula

[10] , which is a fluoropolyether group-containing compound represented by .

[12] Rf 1 In each occurrence, C is independent. 1-16 It is a perfluoroalkyl group, Rf 2 In each occurrence, C is independent. 1-6 It is a perfluoroalkylene group, The articles described in

[11] above.

[13] R F Each occurrence is independent of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In the formula, R Fa In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers between 0 and 200, the sum of a, b, c, d, e, and f is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary within the expression. The articles described in

[11] or

[12] above, which are bases represented by .

[14] R Fa The article described in

[13] above, wherein is a fluorine atom.

[15] R FEach occurrence independently corresponds to the following equations (f1), (f2), (f3), (f4), (f5), or (f6): -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer between 1 and 200, and e is either 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are each independent integers between 0 and 30; e and f are each independent integers between 1 and 200; The sum of c, d, e, and f is an integer between 10 and 200; The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 This is either OCF2 or OC2F4; R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected from these groups; g is an integer between 2 and 100. -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 This is OCF2 or OC2F4, R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. R 6’ This is OCF2 or OC2F4, R 7’ OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. g' is an integer between 2 and 100. R r teeth, [ka] (In the formula, * indicates the bonding position.) That is. The articles described in any one of the above

[11] to

[14] , which are bases represented by [1].

[16] R Si This is expressed by the following formulas (S1), (S2), (S3), (S4), or (S5): [ka] [In formula: R 11 Each instance is independently either a hydroxyl group or a hydrolyzable group; R 12 Each instance is independently either a hydrogen atom or a monovalent organic group; n1 is (SiR 11 n1 R 12 3-n1 Each unit is an independent integer between 0 and 3; X 11 Each instance is independently either a single bond or a divalent organic group; R 13 Each instance is independently either a hydrogen atom or a monovalent organic group; t is an integer greater than or equal to 2, independently in each occurrence; R14 is, in each occurrence independently, a hydrogen atom, a halogen atom or -X 11 -SiR 11 n1 R 12 3-n1 ; R 15 is, in each occurrence independently, a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group having 1 to 6 carbon atoms; R a1 is, in each occurrence independently, -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ; Z 1 is, in each occurrence independently, an oxygen atom or a divalent organic group; R 21 is, in each occurrence independently, -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ; R 22 is, in each occurrence independently, a hydroxyl group or a hydrolyzable group; R 23 is, in each occurrence independently, a hydrogen atom or a monovalent organic group; p1 is, in each occurrence independently, an integer of 0 to 3; q1 is, in each occurrence independently, an integer of 0 to 3; r1 is, in each occurrence independently, an integer of 0 to 3; The sum of p1, q1, and r1 is 3 in the SiR 21 p1 R 22 q1 R 23 r1 unit; Z 1’ is, in each occurrence independently, an oxygen atom or a divalent organic group; R 21’ In each occurrence, -Z is independent. 1” -SiR 22” q1” R 23” r1” and; R 22’ Each instance is independently either a hydroxyl group or a hydrolyzable group; R 23’ Each instance is independently either a hydrogen atom or a monovalent organic group; p1' is an integer between 0 and 3, independently in each occurrence; q1' is an integer between 0 and 3, independently in each occurrence; r1' is an integer between 0 and 3, independently in each occurrence; The sum of p1', q1', and r1' is SiR 21’ p1’ R 22’ q1’ R 23’ r1’ In terms of units, it is 3; Z 1” Each instance is independently either an oxygen atom or a divalent organic group; R 22” Each instance is independently either a hydroxyl group or a hydrolyzable group; R 23” Each instance is independently either a hydrogen atom or a monovalent organic group; q1'' is an integer between 0 and 3, independently in each occurrence; r1" is an integer between 0 and 3, independently of each occurrence; The sum of q1" and r1" is SiR 22” q1” R 23” r1” In terms of units, it is 3; R b1 Each instance is independently either a hydroxyl group or a hydrolyzable group; R c1 Each instance is independently either a hydrogen atom or a monovalent organic group; k1 is an integer between 0 and 3, independently in each occurrence; l1 is an integer between 0 and 3, independently in each occurrence; m1 is an integer between 0 and 3, independently in each occurrence; The sum of k1, l1, and m1 is SiR a1 k1 R b1 l1 R c1 m1 In terms of units, it is 3; R d1 In each occurrence, -Z is independent. 2 -CR 31 p2 R 32 q2 R 33 r2 and; Z 2 Each instance is independently a single bond, an oxygen atom, or a divalent organic group; R 31 In each occurrence, -Z is independent. 2’ -CR 32’ q2’ R 33’ r2’ and; R 32 In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 and; R 33 Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is an integer between 0 and 3, independently in each occurrence; q2 is an integer between 0 and 3, independently in each occurrence; r² is an integer between 0 and 3, independently in each occurrence; The sum of p2, q2, and r2 is SiR 31 p2 R 32 q2 R 33 r2In terms of units, it is 3; Z 2’ Each instance is independently a single bond, an oxygen atom, or a divalent organic group; R 32’ In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 and; R 33’ Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is an integer between 0 and 3, independently in each occurrence; r2' is an integer between 0 and 3, independently in each occurrence; The sum of q2' and r2' is SiR 32’ q2’ R 33’ r2’ In terms of units, it is 3; Z 3 Each instance is independently a single bond, an oxygen atom, or a divalent organic group; R 34 Each instance is independently either a hydroxyl group or a hydrolyzable group; R 35 Each instance is independently either a hydrogen atom or a monovalent organic group; n² is an integer between 0 and 3, independently in each occurrence; R e1 In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 and; R f1 Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 is an integer between 0 and 3, independently in each occurrence; l2 is an integer between 0 and 3, independently in each occurrence; m2 is an integer between 0 and 3, independently in each occurrence; The sum of k2, l2, and m2 is CR d1 k2 R e1 l2 R f1 m2 In terms of units, it is 3; R g1 and R h1 In each occurrence, -Z is independent. 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 and; Z 4 Each instance is independently a single bond, an oxygen atom, or a divalent organic group; However, in formulas (S1), (S2), (S3), (S4), and (S5), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded. The articles described in any one of the above

[11] to

[15] , which are bases represented by [1].

[17] R Si The article is one of the articles described in any one of the above paragraphs

[11] to

[16] , which is formula (S3), (S4), or (S5).

[18] R Si The article is one of the articles described in any one of the above paragraphs

[11] to

[17] , which is formula (S3) or (S4).

[19] The articles described in any one of the above paragraphs

[11] to

[18] , wherein α, β, and γ are 1.

[20] X A These are, independently, trivalent organic groups. Is α 1 and β 2, or is α 2 and β 1? γ is 2. The articles listed in any one of the above items

[11] to

[18] . [Effects of the Invention]

[0007] According to this disclosure, it is possible to provide an article having a surface treatment layer with better friction resistance. [Modes for carrying out the invention]

[0008] The articles disclosed herein are Substrate and An intermediate layer located on the aforementioned substrate, A surface treatment layer located on the aforementioned intermediate layer, formed from a surface treatment agent containing a fluorine-containing silane compound, An article having, The substrate is a ceramic glass containing a petalite crystalline phase and a lithium silicate crystalline phase. The aforementioned intermediate layer includes a first layer of aluminum oxide and silicon oxide, and a second layer of silicon oxide located above it.

[0009] (base material) The above-mentioned substrate is a ceramic glass containing a petalite crystalline phase and a lithium silicate crystalline phase.

[0010] The above ceramic glass has petalite and lithium silicate as primary crystalline phases.

[0011] The above petalite, i.e., LiAlSi4O 10 It is a monoclinic crystal with a layered, three-dimensional skeletal structure having folded Si2O5 layers linked by Li and Al tetrahedra.

[0012] The content of the petalite crystalline phase in the ceramic glass is preferably 20 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 40 to 60% by mass.

[0013] The above lithium silicate crystalline phase may be lithium disilicate or lithium metasilicate. Lithium disilicate, i.e., Li2Si2O5, is orthorhombic, based on a wavy sheet of {Si2O5} tetrahedral arrays. Lithium metasilicate, i.e., Li2SiO3, has orthorhombic symmetry, with (Si2O6) chains running parallel to the c-axis and integrally linked by lithium ions.

[0014] The content of the lithium silicate crystalline phase in the above ceramic glass is preferably 20 to 60% by mass, more preferably 20 to 55% by mass, and even more preferably 20 to 50% by mass.

[0015] In a preferred embodiment, the ceramic glass contains 20-70% by mass of a petalite crystalline phase and 20-60% by mass of a lithium silicate crystalline phase, preferably 45-70% by mass of a petalite crystalline phase and 20-50% by mass of a lithium silicate crystalline phase, more preferably 40-60% by mass of a petalite crystalline phase and 20-50% by mass of a lithium silicate crystalline phase.

[0016] The content of each crystalline phase described above can be determined according to methods conforming to JIS R 3101, JIS R 3105, JIS M 8851, JIS M 8852, JIS M 8853, or JIS R 9301, or other techniques commonly used in the glass field. Specifically, it can be determined according to the method conforming to JIS R 3101.

[0017] The crystalline phase of the above ceramic glass contains petalite and lithium silicate, but may also contain small amounts of β-spodumene ss, β-quartz ss, lithium phosphate, cristobalite, and rutile as part of the phase.

[0018] In one embodiment, the total mass of the petalite crystalline phase and the lithium silicate crystalline phase is greater than the total mass of other crystalline phases present in the ceramic glass.

[0019] Two types of ceramic glass containing lithium disilicate exist. The first type of lithium disilicate ceramic glass includes those doped with ceria and precious metals such as silver. The second type of lithium disilicate ceramic glass includes those nucleated by the addition of P2O5, where the nucleating phase is Li3PO4.

[0020] The above ceramic glass contains SiO2, Al2O3 and Li2O, and may further contain alkali salts such as Na2O, K2O, Rb2O or Cs2O, as well as P2O5 and ZrO2. Furthermore, the above ceramic glass may contain B2O3, MgO, ZnO, TiO2, CeO2, SnO, SnO2, AgO, CuO, Cu2O, As2O3, Sb2O3, MnO, Nb2O5, MoO3, Ta2O5, WO3, Y2O3, La2O3, HfO2, CdO, Fe2O3, CeO 2、 It may contain halogens, SnCO3, and SnC2O2. Furthermore, the ceramic glass is substantially composed of the above components, but may contain unavoidable trace components. Trace components are not limited to, but include, for example, Na, Ti, Mn, Zn, Nb, Mo, Ta, Zr, W, Y, La, Hf, Cd, Sn, Fe, Ce, As, Sb, and their oxides, sulfur compounds such as sulfuric acid, and halogens.

[0021] The ceramic glass described above may be ion-exchangeable by methods widely known in the art. In a typical ion exchange process, relatively small metal ions in the layers near the outer surface of the ceramic glass are replaced by relatively large metal ions of the same valence. The replacement of relatively small metal ions by relatively large metal ions generates compressive stress within the layers of the ceramic glass. In one embodiment, these metal ions are monovalent alkali metal ions (e.g., Na + , K + , Rb + , Cs + (etc.) In another embodiment, the above metal ion is another monovalent ion (Ag + , Tl + Cu +(etc.)

[0022] The content of each component listed below can be determined according to methods conforming to JIS R 3101, JIS R 3105, JIS M 8851, JIS M 8852, JIS M 8853, or JIS R 9301, or other techniques commonly used in the glass industry. Specifically, it can be determined according to the method conforming to JIS R 3101.

[0023] In one embodiment, the ceramic glass comprises the following components: SiO2: 55~80% by mass, Al2O3: 2~20% by mass, Li2O: 5~20% by mass, B2O3: 0~10% by mass, Na2O: 0~5% by mass, ZnO: 0~10% by mass, P2O5: 0.5~6% by mass, and ZrO2:0.2~15% by mass It contains [the specified ingredient]. Here, 0% by mass means that the ingredient is not present. The same applies below.

[0024] In one embodiment, the ceramic glass further comprises the following components: K2O: 0-4% MgO: 0-8% TiO2: 0-5%, CeO2: 0-0.4%, and SnO2: 0.05~0.5% It contains.

[0025] In one embodiment, the ceramic glass comprises the following components: SiO2: 69-80%, Al2O3: 6-9% Li2O: 10-14%, B2O3: 0-2% P2O5: 1.5~2.5%, and ZrO2: 2-4% It contains.

[0026] In one embodiment, the ceramic glass comprises the following components: SiO2: 69-80%, Al2O3: 6-9% Li2O: 10-14%, Na2O: 1-2%, K2O: 1-2%, B2O3: 0-12% P2O5: 1.5~2.5%, and ZrO2: 2-4% It contains.

[0027] In one embodiment, the ceramic glass comprises the following components: SiO2: 65-80%, Al2O3: 5-16% Li2O: 8-15%, Na2O: 0-3%, K2O: 0-3% B2O3: 0-6% ZnO: 0-2%, P2O5: 0.5-4%, and ZrO2: 0.2~6% It contains.

[0028] In one embodiment, the ceramic glass comprises the following components: SiO2: 60-80%, Al2O3: 5-20% Li2O: 5-20%, Na2O: 0-3%, K2O: 0-3% B2O3: 0-6% ZnO: 0-4%, P2O5: 0.5-4%, and ZrO2: 0.2-8% It contains.

[0029] In one embodiment, the total content of P2O5 and ZrO2 in the ceramic glass is greater than 3% by mass.

[0030] In one embodiment, the amount of K atoms present on the surface layer of the ceramic glass is 0.1 to 1.0 at%, preferably 0.2 to 0.6 at%.

[0031] In one embodiment, the amount of Zr atoms present on the surface layer of the ceramic glass is 0.5 to 2.0 at%, preferably 0.7 to 1.5 at%, and more preferably 0.7 to 1.1 at%.

[0032] In one embodiment, the amount of Al atoms present on the surface layer of the ceramic glass is 1.0 to 10.0 at%, preferably 2.0 to 8.0 at%, and more preferably 2.5 to 5.0 at%.

[0033] In a preferred embodiment, the amount of K atoms in the surface layer of the ceramic glass is 0.1 to 1.0 at%, preferably 0.2 to 0.6 at%, the amount of Zr atoms is 0.5 to 2.0 at%, preferably 0.7 to 1.5 at%, more preferably 0.7 to 1.1 at%, and the amount of Al atoms is 1.0 to 10.0 at%, preferably 2.0 to 8.0 at%, more preferably 2.5 to 5.0 at%.

[0034] Here, the surface layer of the ceramic glass refers to the portion including the surface in contact with the intermediate layer, and the layer portion up to the depth measured by the XPS analysis described below.

[0035] The atomic content in the surface layer of the above ceramic glass is measured by XPS analysis (X-ray photoelectron spectroscopy). The XPS analysis can be performed under the following conditions, using Ar ions for sputtering. By observing the peak areas of C1s, O1s, F1s, Si2p orbitals, and appropriate orbitals of metal atoms using the following apparatus and measurement conditions, the composition of the ceramic glass can be determined by calculating the atomic ratios of carbon, oxygen, fluorine, silicon, and metal atoms. Examples of appropriate orbitals for metal atoms include the 1s orbital for atomic number 5 (B), the 2p orbital for atomic numbers 13-14 and 21-31 (Al-Si, Sc-Ga), the 3d orbital for atomic numbers 32-33 and 39-52 (Ge-As, Y-Te), and the 4f orbital for atomic numbers 72-83 (Hf-Bi). Equipment: ULVAC-PHI PHI5000VersaProbeII X-ray source: Colored AlKα radiation (25W) Photoelectron detection area: 1400 μm × 300 μm Photoelectron detection angle: 45 degrees Pass energy: 23.5 eV

[0036] (Middle class) The above-mentioned intermediate layer is located on the above-mentioned substrate and includes a first layer of aluminum oxide and silicon oxide, and a second layer of silicon oxide located above it. "Located on the substrate" means that the intermediate layer is in contact with the substrate.

[0037] The above aluminum oxide is typically Al x O y (x and y are any integers). Aluminum oxide is typically Al2O3, but may contain subtle amounts of aluminum oxide with different chemical ratios.

[0038] The silicon dioxide mentioned above is typically Si x O y (x and y are arbitrary integers). Silicon oxide is typically SiO2, but may contain subtle amounts of silicon oxide with different chemical ratios.

[0039] The first layer described above is placed in direct contact with the substrate and contains aluminum oxide and silicon oxide.

[0040] The first layer described above consists substantially of aluminum oxide and silicon oxide. Here, "substantially" means that the presence of trace amounts of other components, such as components that are unavoidable in the manufacturing process or components that cannot be separated, is permitted. The first layer preferably contains 99.5% by mass or more, preferably 99.9% by mass or more, and more preferably 100% aluminum oxide and silicon oxide.

[0041] In a preferred embodiment, the aluminum content in the first layer is 0.5 to 60.0 at%, preferably 0.7 to 50.5 at%, and more preferably 1.5 to 35.5 at%, relative to the total amount of aluminum and silicon. By setting the aluminum content within the above range, the frictional durability of the laminate is improved.

[0042] In a preferred embodiment, the aluminum content in the first layer, among all elements (i.e., Al, F, C, Si, and O), is 0.1 to 30 at%, preferably 0.4 to 20 at%, and more preferably 0.5 to 10 at%. By setting the aluminum content within the above range, the frictional durability of the laminate is improved.

[0043] Here, the aluminum content in the first layer is measured by XPS analysis (X-ray photoelectron spectroscopy).

[0044] The atomic content in each layer can be measured by depth profiling using XPS analysis. For XPS analysis, a monochromatic AlKα X-ray source is used at 25W, the photoelectron detection area is 1400 μm × 300 μm, the photoelectron detection angle is 45 degrees, and the pass energy is 23.5 eV. Ar ions can be used as sputtering ions. The surface layer of the laminate is etched from 1 to 100 nm by sputtering with Ar ions, and the peak areas of the appropriate orbitals of C1s, O1s, F1s, Si2p orbitals, and metal atoms are observed at each etching depth. By calculating the atomic ratios of carbon, oxygen, fluorine, silicon, and metal atoms, the composition in each layer can be determined. Suitable orbitals for metal atoms include, for example, the 1s orbital for atomic number 5 (B), the 2p orbital for atomic numbers 13-14 and 21-31 (Al-Si, Sc-Ga), the 3d orbital for atomic numbers 32-33 and 39-52 (Ge-As, Y-Te), and the 4f orbital for atomic numbers 72-83 (Hf-Bi). Equipment: ULVAC-PHI PHI5000VersaProbeII X-ray source: Colored AlKα radiation (25W) Photoelectron detection area: 1400 μm × 300 μm Photoelectron detection angle: 45 degrees Pass energy: 23.5 eV Ar acceleration voltage: 3kV Sputter time: 14-21 seconds

[0045] In one embodiment, the difference in aluminum content between the surface of the first layer in contact with the substrate and the surface in contact with the second layer is preferably within 1.0 at%, more preferably within 0.5 at%, and even more preferably within 0.1 at%. That is, there is little or no concentration gradient of aluminum content from the surface of the first layer in contact with the substrate to the surface in contact with the second layer.

[0046] The concentration gradient of the aluminum content in the first layer described above can be calculated from the etching rate obtained by etching the surface of the article from the surface treatment layer side using an argon cluster ion beam (Ar-GCIB), measuring the atomic concentration by X-ray photoelectron spectroscopy (XPS analysis), and repeating this operation.

[0047] The second layer described above is placed in direct contact with the first layer described above and contains silicon dioxide.

[0048] The second layer described above consists substantially of silicon dioxide. Here, "substantially" means that the presence of trace amounts of other components, such as components that are unavoidable in the manufacturing process or components that cannot be separated, is permitted. The second layer preferably contains 99.5% by mass or more, preferably 99.9% by mass or more, and more preferably 100% silicon dioxide.

[0049] The thickness of the intermediate layer is preferably 5 nm to 35 nm, more preferably 10 nm to 30 nm. By setting the thickness of the intermediate layer within this range, the frictional durability of the surface treatment layer is improved.

[0050] The thickness of the first layer is preferably 1 nm to 30 nm, more preferably 3 nm to 20 nm, and even more preferably 5 nm to 10 nm. By setting the thickness of the first layer within the above range, the frictional durability of the surface treatment layer is improved.

[0051] The thickness of the second layer is preferably 1 nm to 30 nm, more preferably 5 nm to 25 nm, and even more preferably 8 nm to 20 nm. By setting the thickness of the second layer within the above range, the frictional durability of the surface treatment layer is improved.

[0052] The ratio of the thickness of the first layer to the thickness of the second layer is preferably 0.1 to 10, more preferably 0.2 to 5.0, and even more preferably 0.3 to 1.0. By setting the ratio of the thickness of the first layer to the thickness of the second layer within the above range, the frictional durability of the surface treatment layer is improved.

[0053] The thicknesses of the intermediate layer, first layer, and second layer can be calculated from the etching rate obtained by etching the surface of the article from the surface treatment layer side using an argon cluster ion beam (Ar-GCIB), measuring the atomic concentration by X-ray photoelectron spectroscopy (XPS analysis), and repeating this operation.

[0054] The method for forming each of the above layers is not particularly limited as long as it is a method that can form a layer of metal oxide on the substrate, but vapor deposition methods such as physical vapor deposition (PVD) and chemical vapor deposition (CVD) can be used. The PVD method is not particularly limited, but examples include vacuum deposition and sputtering. Specific examples of vacuum deposition methods include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma CVD, optical CVD, thermal CVD, and similar methods. Among these, the PVD method is preferred, with resistance heating deposition or electron beam deposition being particularly preferred, and electron beam deposition being more preferred. By using the PVD method, a surface treatment layer with higher friction resistance can be obtained.

[0055] In one embodiment, a pretreatment, such as a cleaning treatment, may be performed before forming the surface treatment layer on the intermediate layer. By performing the pretreatment, the adhesion between the intermediate layer and the surface treatment layer is improved, and higher frictional durability can be obtained.

[0056] (Surface treatment layer) The above-mentioned surface treatment layer is located on the above-mentioned intermediate layer and is formed from a surface treatment agent containing a fluorine-containing silane compound. "Located on the intermediate layer" means that the surface treatment layer is in contact with the intermediate layer.

[0057] The above fluorine-containing silane compounds are defined by the following formula (1) or (2): [ka] [In formula: RF1 Each occurrence is independent of Rf 1 -R F -O q -and; R F2 -Rf 2 p -R F -O q -and; Rf 1 C may be independently substituted with one or more fluorine atoms in each occurrence. 1-16 It is an alkyl group; Rf 2 C may be substituted with one or more fluorine atoms. 1-6 It is an alkylene group; R F Each occurrence is independently a divalent fluoropolyether group; p is either 0 or 1; q is either 0 or 1 in each occurrence, independently; R Si Each instance independently contains a monovalent group comprising a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a Si atom to which a monovalent organic group is bonded; at least one R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; X A Each of these is independently a single bond or a 2-10 valent organic group; α is an integer between 1 and 9; β is an integer between 1 and 9; Each of the γ values ​​is an independent integer between 1 and 9. It is at least one fluorine-containing silane compound represented by [formula].

[0058] In the above equation (1), R F1 Each occurrence is independent of Rf 1 -R F -O q - is

[0059] In equation (2) above, RF2 -Rf 2 p -R F -O q - is

[0060] In the above formula, Rf 1 C may be independently substituted with one or more fluorine atoms in each occurrence. 1-16 It is an alkyl group.

[0061] C may be substituted with one or more fluorine atoms as described above. 1-16 "C" in alkyl groups 1-16 The alkyl group may be linear or branched, preferably linear or branched C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group, more preferably a linear C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0062] The above Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1-16 It is an alkyl group, more preferably CF2H-C 1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0063] C above 1-16 The perfluoroalkyl group may be linear or branched, preferably linear or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 Perfluoroalkyl groups, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0064] In the above formula, Rf 2 C may be substituted with one or more fluorine atoms.1-6 It is an alkylene group.

[0065] C may be substituted with one or more fluorine atoms as described above. 1-6 "C" in the alkylene group 1-6 The alkylene group may be linear or branched, preferably linear or branched C 1-3 An alkylene group, more preferably a linear C group 1-3 It is an alkylene group.

[0066] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1-6 It is an alkylene group, and more C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0067] C above 1-6 The perfluoroalkylene group may be linear or branched, preferably linear or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 The perfluoroalkylene group is specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0068] In the above formula, p is either 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0069] In the above equation, q is either 0 or 1 independently in each occurrence. In one embodiment, q is 0. In another embodiment, q is 1.

[0070] In the above equations (1) and (2), R F Each instance is independently a divalent fluoropolyether group.

[0071] R F Preferably, the following: -(OCh1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 - [In formula: R Fa In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom. h1 is an integer between 1 and 6. h2 is an integer between 4 and 8. h3 is a non-negative integer, h4 is a non-negative integer, However, the combination of h3 and h4 is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of existence of each repeating unit enclosed in parentheses with h3 and h4 is arbitrary in the formula. It may contain a group represented by .

[0072] In one embodiment, R F It can be linear or branched. F Preferably, the formula is: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers between 0 and 200, and the sum of a, b, c, d, e, and f is 1 or greater. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression. However, all R Fa If is a hydrogen atom or a chlorine atom, then at least one of a, b, c, e, and f is 1 or more. It is a base represented by .

[0073] R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom. However, all R Fa If is a hydrogen atom or a chlorine atom, then at least one of a, b, c, e, and f is 1 or more.

[0074] a, b, c, d, e, and f may preferably be independent integers between 0 and 100.

[0075] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0076] These repeating units may be linear or branched. For example, -(OC6F 12 )- may also be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10)- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(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, in the above formula, R Fa (where is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0077] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, wear resistance, etc., of the surface treatment layer can be improved.

[0078] In one embodiment, the repeating unit is branched and chain-like. By making the repeating unit branched and chain-like, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0079] In one embodiment, R F This may include a ring structure.

[0080] The above ring structure may be a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring. [ka] [In the formula, * indicates a bonding position.]

[0081] The above ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0082] The repeating units having a ring structure may preferably be the following units. [ka] [In the formula, * indicates a bonding position.]

[0083] In one embodiment, R F Each occurrence of is independently represented by one of the following equations (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer between 1 and 200, and e is either 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are independent integers between 0 and 30, and e and f are independent integers between 1 and 200.] The sum of c, d, e, and f is 2 or greater. The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 This is OCF2 or OC2F4, R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. -(R 6 -R 7 ) g -R r -(R 7’-R 6’ ) g’ - (f4) [In the formula, R 6 This is OCF2 or OC2F4, R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. R 6’ This is OCF2 or OC2F4, R 7’ OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. g' is an integer between 2 and 100. R r teeth, [ka] (In the formula, * indicates the bonding position.) That is. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer between 1 and 200, a, b, c, d, and f are each independent integers between 0 and 200, and the order of existence of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d-(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer between 1 and 200, a, b, c, d, and e are each independent integers between 0 and 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0084] In the above formula (f1), d is preferably an integer between 5 and 200, more preferably between 10 and 100, and even more preferably between 15 and 50, for example between 25 and 35. In the above formula (f1), OC3F6 is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). In the above formula (f1), (OC2F4) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0085] In the above formula (f2), e and f are each an integer, preferably between 5 and 200, more preferably between 10 and 200. The sum of c, d, e, and f is preferably 5 or greater, more preferably 10 or greater, and may be, for example, 15 or greater or 20 or greater. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f - is the base represented by -. In another embodiment, formula (f2) is -(OC2F4) e -(OCF2) f It may also be represented as a base by -.

[0086] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably, a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 is not particularly limited, but examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, and -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The chain may be either linear or branched, and is preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g - is

[0087] In the above equation (f4), R 6 , R 7 And g have the same meaning as described in the above formula (f3) and have the same characteristics. 6’ , R 7’ and g' are R as described in formula (f3) above, respectively. 6 , R 7 And g are synonymous and have similar characteristics. r Preferably, [ka] [In the formula, * indicates a bonding position.] and, more [ka] [In the formula, * indicates a bonding position.] That is the case.

[0088] In the above formula (f5), e is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0089] In the above formula (f6), f is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0090] In one embodiment, the above R F This is the group represented by the above formula (f1).

[0091] In one embodiment, the above R F This is the group represented by the above formula (f2).

[0092] In one embodiment, the above R F This is the group represented by the above formula (f3).

[0093] In one embodiment, the above R F This is the group represented by the above formula (f4).

[0094] In one embodiment, the above R F This is the group represented by the above formula (f5).

[0095] In one embodiment, the above R F This is the group represented by the above formula (f6).

[0096] 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 setting the e / f ratio to 10 or less, the slipperiness, wear resistance, and chemical resistance (e.g., resistance to artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the better the slipperiness and wear resistance of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The larger the e / f ratio, the better the stability of the compound.

[0097] In the above fluorine-containing silane compound, R F1 and R F2 The number-average molecular weight of the part 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, 19 The value shall be measured by 1F-NMR.

[0098] In another embodiment, R F1 and R F2 The number-average molecular weight of the part may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.

[0099] In another embodiment, R F1 and R F2 The number-average molecular weight of the part may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0100] In the above equations (1) and (2), R SiEach instance independently contains a monovalent group comprising a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a Si atom to which a monovalent organic group is bonded, and at least one R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded.

[0101] Here, "hydrolyzable group" refers to a group that can undergo hydrolysis, that is, a group that can be removed from the main skeleton of a compound by hydrolysis. Examples of hydrolyzable groups include -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, halogen (in these formulas, R j C is either substituted or non-substituted. 1-4 Examples include (showing an alkyl group).

[0102] In a preferred embodiment, R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded.

[0103] In a preferred embodiment, R Si This is expressed by the following formulas (S1), (S2), (S3), or (S4): [ka] It is a base represented by .

[0104] In the above formula, R 11 Each of these groups is independently either a hydroxyl group or a hydrolyzable group in its respective appearance.

[0105] R 11 Preferably, each occurrence is independently a hydrolyzable group.

[0106] R 11 Preferably, in each occurrence, independently, -OR j , -OCOR j , -ON=CR j 2. -NR j2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0107] In the above formula, R 12 Each instance independently represents either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0108] R 12 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0109] In the above formula, n1 is (SiR 11 n1 R 12 3-n1 Each unit is an independent integer between 0 and 3. However, R Si If the group is represented by formula (S1) or (S2), then the terminal R of formulas (1) and (2) Si In the part (hereinafter also simply referred to as the "terminal part" of equations (1) and (2)), n1 is 1 to 3 (SiR 11 n1 R 12 3-n1There is at least one unit. That is, in such terminal parts, not all n1s are 0 at the same time. In other words, in the terminal parts of formulas (1) and (2), there is at least one Si atom to which a hydroxyl group or hydrolyzable group is bonded.

[0110] n1 is (SiR 11 n1 R 12 3-n1 Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0111] In the above formula, X 11 Each occurrence is independently either a single bond or a divalent organic group. Such a divalent organic group is preferably -R 28 -O x -R 29 -(In the formula, R 28 and R 29 Each instance is independently of a single bond or C 1-20 It is an alkylene group, and x is 0 or 1. 1-20 The alkylene group may be linear or branched, but is preferably linear. 1-20 The alkylene group is preferably C 1-10 Alkylene group, more preferably C 1-6 Alkylene group, more preferably C 1-3 It is an alkylene group.

[0112] In one embodiment, X 11 In each occurrence, -C is independent. 1-6 Alkylene-OC 1-6 Alkilen- or -OC 1-6 It is alkylene-

[0113] In a preferred embodiment, X 11 Each instance independently involves a single bond or a linear chain of carbon atoms. 1-6 An alkylene group, preferably a single bond or a linear C bond. 1-3 Alkylene group, more preferably single bond or linear carbon1-2 An alkylene group, more preferably a linear carbon group. 1-2 It is an alkylene group.

[0114] In the above formula, R 13 Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably C 1-20 It is an alkyl group. 1-20 The alkyl group may be linear or branched, but is preferably linear.

[0115] In a preferred embodiment, R 13 Each instance independently represents a hydrogen atom or a linear C atom. 1-6 It is an alkyl group, preferably a hydrogen atom or a linear C 1-3 The alkyl group is preferably a hydrogen atom or a methyl group.

[0116] In the above formula, t is an integer greater than or equal to 2, independently in each occurrence.

[0117] In a preferred embodiment, t is an integer between 2 and 10, preferably between 2 and 6, independently in each occurrence.

[0118] In the above formula, R 14 Each instance independently represents 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, and more preferably a fluorine atom. In a preferred embodiment, R 14 This is a hydrogen atom.

[0119] In the above formula, R 15 Each instance independently consists of a single bond, an oxygen atom, a C1-C6 alkylene group, or a C1-C6 alkylene oxy group.

[0120] In one embodiment, R15 In each instance, these are independently an oxygen atom, a C1-C6 alkylene group, or a C1-C6 alkylene oxy group.

[0121] In a preferred embodiment, R 15 It is a single bond.

[0122] In one embodiment, equation (S1) is given by the following equation (S1-a). [ka] [In the formula, R 11 , R 12 , R 13 , X 11 , and n1 are equivalent to the description in the above formula (S1); t1 and t2 are, independently in each occurrence, integers greater than or equal to 1, preferably integers between 1 and 10, more preferably integers between 2 and 10, for example, integers between 1 and 5 or integers between 2 and 5; The order in which each repeating unit, denoted by t1 and t2 and enclosed in parentheses, exists is arbitrary within the expression.

[0123] In a preferred embodiment, formula (S1) is the following formula (S1-b). [ka] [In the formula, R 11 , R 12 , R 13 , X 11 n1 and t have the same meaning as described in the above formula (S1).

[0124] In the above formula, R a1 In each occurrence, -Z is independent. 1 -SiR 21 p1 R 22 q1 R 23 r1 That is the case.

[0125] The above Z 1Each instance is independently either an oxygen atom or a divalent organic group. (Note: Z follows) 1 The structure described as follows is (SiR 21 p1 R 22 q1 R 23 r1 ) is joined to it.

[0126] In a preferred embodiment, Z 1 It is a divalent organic group.

[0127] In a preferred embodiment, Z 1 is, Z 1 It does not contain any element that forms a siloxane bond with the Si atom to which it is bonded. Preferably, in formula (S3), (Si-Z 1 -Si) does not contain a siloxane bond.

[0128] The above Z 1 Preferably, C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2 is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3 -Phenylene-(CH2) z4 -(wherein z3 is an integer from 0 to 6, for example, an integer from 1 to 6, and z4 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0129] In a preferred embodiment, Z 1 C 1-6 Alkylene group or -(CH2) z3 -Phenylene-(CH2) z4-, preferably -phenylene-(CH2) z4 - is Z 1 If the group is such that it can have higher light resistance, especially UV resistance.

[0130] In another preferred embodiment, the above Z 1 C 1-3 It is an alkylene group. In one embodiment, Z 1 This could be -CH2CH2CH2-. In another embodiment, Z 1 It can be -CH2CH2-.

[0131] The above R 21 In each occurrence, -Z is independent. 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ That is the case.

[0132] The above Z 1’ Each instance is independently either an oxygen atom or a divalent organic group. (Note: Z follows) 1’ The structure described as follows is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) is joined to it.

[0133] In a preferred embodiment, Z 1’ It is a divalent organic group.

[0134] In a preferred embodiment, Z 1’ is, Z 1’ It does not contain any element that forms a siloxane bond with the Si atom to which it is bonded. Preferably, in formula (S3), (Si-Z 1’ -Si) does not contain a siloxane bond.

[0135] The above Z 1’ Preferably, C 1-6 Alkylene group, -(CH2) z1’ -O-(CH2)z2’ -(wherein z1' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3’ -Phenylene-(CH2) z4’ -(wherein z3' is an integer between 0 and 6, for example between 1 and 6, and z4' is an integer between 0 and 6, for example between 1 and 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0136] In a preferred embodiment, Z 1’ C 1-6 Alkylene group or -(CH2) z3’ -Phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ - is Z 1’ If the group is such that it can have higher light resistance, especially UV resistance.

[0137] In another preferred embodiment, the above Z 1’ C 1-3 It is an alkylene group. In one embodiment, Z 1’ This could be -CH2CH2CH2-. In another embodiment, Z 1’ It can be -CH2CH2-.

[0138] The above R 21’ In each occurrence, -Z is independent. 1” -SiR 22” q1” R 23” r1” That is the case.

[0139] The above Z 1” Each instance is independently either an oxygen atom or a divalent organic group. (Note: Z follows) 1”The structure described as follows is (SiR 22” q1” R 23” r1” ) is joined to it.

[0140] In a preferred embodiment, Z 1” It is a divalent organic group.

[0141] In a preferred embodiment, Z 1” is, Z 1” It does not contain any element that forms a siloxane bond with the Si atom to which it is bonded. Preferably, in formula (S3), (Si-Z 1” -Si) does not contain a siloxane bond.

[0142] The above Z 1” Preferably, C 1-6 Alkylene group, -(CH2) z1” -O-(CH2) z2” -(wherein z1'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3” -Phenylene-(CH2) z4” -(wherein z3'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z4'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0143] In a preferred embodiment, Z 1” C 1-6 Alkylene group or -(CH2) z3” -Phenylene-(CH2) z4” -, preferably -phenylene-(CH2) z4” - is Z 1” If the group is such that it can have higher light resistance, especially UV resistance.

[0144] In another preferred embodiment, the above Z 1” C 1-3 It is an alkylene group. In one embodiment, Z 1” This could be -CH2CH2CH2-. In another embodiment, Z 1” It can be -CH2CH2-.

[0145] The above R 22” Each of these groups is independently either a hydroxyl group or a hydrolyzable group in its respective appearance.

[0146] The above R 22” Preferably, each occurrence is independently a hydrolyzable group.

[0147] The above R 22” Preferably, in each occurrence, independently, -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0148] The above R 23” Each instance independently represents either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0149] The above R23” In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0150] The above q1'' is an integer between 0 and 3, independently of each occurrence, and the above r1'' is an integer between 0 and 3, independently of each occurrence. Note that the sum of q1'' and r1'' is (SiR 22” q1” R 23” r1” In units of 3, it is 3.

[0151] The above q1'' is (SiR 22” q1” R 23” r1” Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0152] The above R 22’ Each of these groups is independently either a hydroxyl group or a hydrolyzable group in its respective appearance.

[0153] R 22’ Preferably, each occurrence is independently a hydrolyzable group.

[0154] R 22’ Preferably, in each occurrence, independently, -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). jExamples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0155] The above R 23’ Each instance independently represents either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0156] R 23’ In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0157] The above p1' is an integer between 0 and 3, independently of each occurrence; q1' is an integer between 0 and 3, independently of each occurrence; and r1' is an integer between 0 and 3, independently of each occurrence. Note that the sum of p', q1', and r1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ In units of 3, it is 3.

[0158] In one embodiment, p1' is 0.

[0159] In one embodiment, p1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1' is 3.

[0160] In one embodiment, q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0161] In one embodiment, p1' is 0 and q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0162] The above R 22 Each of these groups is independently either a hydroxyl group or a hydrolyzable group in its respective appearance.

[0163] R 22 Preferably, each occurrence is independently a hydrolyzable group.

[0164] R 22 Preferably, in each occurrence, independently, -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0165] The above R 23 Each instance independently represents either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0166] R 23 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0167] The above p1 is an integer between 0 and 3, independently of each occurrence; q1 is an integer between 0 and 3, independently of each occurrence; and r1 is an integer between 0 and 3, independently of each occurrence. Note that the sum of p1, q1, and r1 is (SiR 21 p1 R 22 q1 R 23 r1 In units of 3, it is 3.

[0168] In one embodiment, p1 is 0.

[0169] In one embodiment, p1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1 is 3.

[0170] In one mode, q1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0171] In one embodiment, p1 is 0 and q1 is (SiR21 p1 R 22 q1 R 23 r1 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0172] In the above formula, R b1 Each of these groups is independently either a hydroxyl group or a hydrolyzable group in its respective appearance.

[0173] The above R b1 Preferably, each occurrence is independently a hydrolyzable group.

[0174] The above R b1 Preferably, in each occurrence, independently, -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0175] In the above formula, R c1 Each instance independently represents either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0176] The above R c1 In this, the monovalent organic group is preferably C1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0177] The above k1 is an integer between 0 and 3, independently in each occurrence; l1 is an integer between 0 and 3, independently in each occurrence; and m1 is an integer between 0 and 3, independently in each occurrence. Note that the sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 In units of 3, it is 3.

[0178] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1 Each unit is an integer between 1 and 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0179] In the above equations (1) and (2), R Si When is a group represented by formula (S3), preferably, at least two, preferably three, Si atoms to which a hydroxyl group or hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0180] In a preferred embodiment, the group represented by formula (S3) is -Z 1 -SiR 22 q1 R 23 r1 (In the formula, q1 is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1 is an integer between 0 and 2.) -Z 1’ -SiR 22’ q1’ R 23’ r1’ (In the formula, q1' is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1' is an integer between 0 and 2.) or -Z 1”-SiR 22” q1” R 23” r1” (wherein the formula, q1'' is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1'' is an integer between 0 and 2.) Z 1 , Z 1’ , Z 1” , R 22 , R 23 , R 22’ , R 23’ , R 22” , and R 23” This is synonymous with the above.

[0181] In a preferred embodiment, in formula (S3), R 21’ If present, at least one, preferably all R 21’ In this, q1'' is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0182] In a preferred embodiment, in formula (S3), R 21 If present, at least one, preferably all R 21 In this case, p1' is 0, and q1' is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0183] In a preferred embodiment, in formula (S3), R a1 If present, at least one, preferably all R a1 In this case, p1 is 0, and q1 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0184] In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

[0185] R d1 In each occurrence, -Z is independent. 2 -CR 31 p2 R 32 q2R 33 r2 That is the case.

[0186] Z 2 Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 2 The structure described as follows is (CR) on the right side. 31 p2 R 32 q2 R 33 r2 ) is joined to it.

[0187] In a preferred embodiment, Z 2 It is a divalent organic group.

[0188] The above Z 2 Preferably, C 1-6 Alkylene group, -(CH2) z5 -O-(CH2) z6 -(wherein z5 is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6 is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7 -Phenylene-(CH2) z8 -(wherein z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0189] In a preferred embodiment, Z 2 C 1-6 Alkylene group or -(CH2) z7 -Phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 - is Z 2 If the group is such that it can have higher light resistance, especially UV resistance.

[0190] In another preferred embodiment, the above Z 2 C 1-3 It is an alkylene group. In one embodiment, Z 2 This could be -CH2CH2CH2-. In another embodiment, Z 2 It can be -CH2CH2-.

[0191] R 31 In each occurrence, -Z is independent. 2’ -CR 32’ q2’ R 33’ r2’ That is the case.

[0192] Z 2’ Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 2’ The structure described as follows is (CR) on the right side. 32’ q2’ R 33’ r2’ ) is joined to it.

[0193] The above Z 2’ Preferably, C 1-6 Alkylene group, -(CH2) z5’ -O-(CH2) z6’ -(wherein z5' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7’ -Phenylene-(CH2) z8’ -(wherein z7' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0194] In a preferred embodiment, Z 2’ C 1-6 Alkylene group or -(CH2) z7’ -Phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ - is Z 2’ If the group is such that it can have higher light resistance, especially UV resistance.

[0195] In another preferred embodiment, the above Z 2’ C 1-3 It is an alkylene group. In one embodiment, Z 2’ This could be -CH2CH2CH2-. In another embodiment, Z 2’ It can be -CH2CH2-.

[0196] The above R 32’ In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 That is the case.

[0197] The above Z 3 Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 3 The structure described as follows is (SiR 34 n2 R 35 3-n2 ) is joined to it.

[0198] In one embodiment, Z 3 It is an oxygen atom.

[0199] In one embodiment, Z 3 It is a divalent organic group.

[0200] The above Z 3 Preferably, C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6”-(wherein z5'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7” -Phenylene-(CH2) z8” -(wherein z7'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0201] In a preferred embodiment, Z 3 C 1-6 Alkylene group or -(CH2) z7” -Phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” - is Z 3 If the group is such that it can have higher light resistance, especially UV resistance.

[0202] In another preferred embodiment, the above Z 3 C 1-3 It is an alkylene group. In one embodiment, Z 3 This could be -CH2CH2CH2-. In another embodiment, Z 3 It can be -CH2CH2-.

[0203] The above R 34 Each of these groups is independently either a hydroxyl group or a hydrolyzable group in its respective appearance.

[0204] R 34 Preferably, each occurrence is independently a hydrolyzable group.

[0205] R 34 Preferably, in each occurrence, independently, -OR j, -OCOR j , -O-N=CR j 2, -NR j 2, -NHR j , -NCO, or a halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), more preferably -OR j (i.e., an alkoxy group). As R j , there are unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one aspect, R j is a methyl group, and in another aspect, R j is an ethyl group.

[0206] The above R 35 is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0207] In the above R 35 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and still more preferably a methyl group.

[0208] In the above formula, n2 is, for each (SiR 34 n2 R 35 3-n2 ) unit, independently an integer of 0 to 3. However, when R Si is a group represented by the formula (S4), at the terminal portions of the formulas (1) and (2), n2 is 1 to 3 (SiR 34 n2 R 35 3-n2) There is at least one unit. That is, in such a terminal portion, all n2 do not become 0 simultaneously. In other words, in the terminal portions of formula (1) and formula (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0209] n2 is, for each (SiR 34 n2 R 35 3-n2 ) unit, independently preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0210] The above R 33’ is, in each occurrence, independently a hydrogen atom, a hydroxyl group or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0211] In the above R 33’ , the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (where s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6). And more preferably a C 1-20 alkyl group, even more preferably a C 1-6 alkyl group, particularly preferably a methyl group.

[0212] In one aspect, R 33’ is a hydroxyl group.

[0213] In another aspect, R 33’ is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0214] The above q2' is an integer between 0 and 3, independently of each occurrence, and the above r2' is an integer between 0 and 3, independently of each occurrence. Note that the sum of q2' and r2' is (CR 32’ q2’ R 33’ r2’ In units of 3, it is 3.

[0215] q2' is (CR 32’ q2’ R 33’ r2’ Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0216] R 32 In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 This is the case. 3 -SiR 34 n2 R 35 3-n2 The above R 32’ This is equivalent to the description in [the relevant section].

[0217] The above R 33 Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0218] The above R 33 In this, the monovalent organic group is preferably C 1-20 Alkyl or -(C s H 2s ) t1 -(OC s H 2s ) t2 (wherein s is an integer from 1 to 6, preferably from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably from 2 to 10, more preferably from 2 to 6.) and more preferably C 1-20 Alkyl alkyl groups, more preferably C1-6 is an alkyl group, particularly preferably a methyl group.

[0219] In one embodiment, R 33 is a hydroxyl group.

[0220] In another embodiment, R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0221] Each p2 is, in each occurrence, independently an integer from 0 to 3, each q2 is, in each occurrence, independently an integer from 0 to 3, and each r2 is, in each occurrence, independently an integer from 0 to 3. Incidentally, the sum of p2, q2, and r2 is 3 in the (CR 31 p2 R 32 q2 R 33 r2 ) unit.

[0222] In one embodiment, p2 is 0.

[0223] In one embodiment, p2 may be, independently for each (CR 31 p2 R 32 q2 R 33 r2 ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p2 is 3.

[0224] In one embodiment, q2 is, independently for each (CR 31 p2 R 32 q2 R 33 r2 ) unit, an integer from 1 to 3, preferably an integer from 2 to 3, more preferably 3.

[0225] In one embodiment, p2 is 0 and q2 is (CR 31 p2 R32 q2 R 33 r2 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0226] The above R e1 In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 This is the case. 3 -SiR 34 n2 R 35 3-n2 The above R 32’ This is equivalent to the description in [the relevant section].

[0227] The above R f1 Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0228] The above R f1 In this, the monovalent organic group is preferably C 1-20 Alkyl or -(C s H 2s ) t1 -(OC s H 2s ) t2 (wherein s is an integer from 1 to 6, preferably from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably from 2 to 10, more preferably from 2 to 6.) and more preferably C 1-20 Alkyl alkyl groups, more preferably C 1-6 Alkyl groups, particularly preferably methyl groups.

[0229] In one embodiment, R f1 This is a hydroxyl group.

[0230] In another embodiment, R f1 This is a monovalent organic group, preferably C 1-20It is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0231] The above k2 is an integer between 0 and 3, independently in each occurrence; l2 is an integer between 0 and 3, independently in each occurrence; and m2 is an integer between 0 and 3, independently in each occurrence. Note that the sum of k2, l2, and m2 is (CR d1 k2 R e1 l2 R f1 m2 In units of 3, it is 3.

[0232] In the above equations (1) and (2), R Si When is a group represented by formula (S4), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0233] In one embodiment, R Si When is a group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 The units are present in two or more units at each terminal portion of formula (1) and formula (2), for example, 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.

[0234] In a preferred embodiment, in formula (S4), R 32’ If present, at least one, preferably all R 32’ In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0235] In a preferred embodiment, in formula (S4), R 32 If present, at least one, preferably all R 32 In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0236] In a preferred embodiment, in formula (S4), R e1 If present, at least one, preferably all R a1 In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0237] In a preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0238] In the above equations (1) and (2), R Si When is a group represented by formula (S4), preferably, at least two, preferably three, Si atoms to which a hydroxyl group or hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0239] The above R g1 and R h1 In each occurrence, -Z is independent. 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 Here, R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 n1, k1, l1, m1, k2, l2, and m2 have the same meaning as above.

[0240] In a preferred embodiment, R g1 and R h1These are, independently, -Z 4 -SiR 11 n1 R 12 3-n1 That is the case.

[0241] The above Z 4 Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 4 The structure described as follows is (SiR 11 n1 R 12 3-n1 ) joins.

[0242] In one embodiment, Z 4 It is an oxygen atom.

[0243] In one embodiment, Z 4 It is a divalent organic group.

[0244] The above Z 4 Preferably, C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein z5'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7” -Phenylene-(CH2) z8” -(wherein z7'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0245] In a preferred embodiment, Z 4 C 1-6 Alkylene group or -(CH2) z7”-Phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” - is Z 3 If the group is such that it can have higher light resistance, especially UV resistance.

[0246] In another preferred embodiment, the above Z 4 C 1-3 It is an alkylene group. In one embodiment, Z 4 This could be -CH2CH2CH2-. In another embodiment, Z 4 It can be -CH2CH2-.

[0247] In the above equations (1) and (2), R Si When is a group represented by formula (S5), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0248] In one embodiment, R Si These are groups represented by formulas (S2), (S3), (S4), or (S5). These compounds can form surface treatment layers with high surface slipperiness.

[0249] In one embodiment, R Si These are groups represented by formulas (S3), (S4), or (S5). Because these compounds have multiple hydrolyzable groups at one end, they can form a surface treatment layer that adheres strongly to the substrate and has high abrasion resistance.

[0250] In one embodiment, R Si This is a group represented by formula (S3) or (S4). Since these compounds may have multiple hydrolyzable groups branched from a single Si or C atom at one end, they can form a surface treatment layer with even higher wear resistance.

[0251] In one embodiment, R Si This is a base represented by equation (S1).

[0252] In one embodiment, R Si This is a base represented by equation (S2).

[0253] In one embodiment, R Si This is a base represented by formula (S3).

[0254] In one embodiment, R Si This is a base represented by formula (S4).

[0255] In one embodiment, R Si This is a base represented by equation (S5).

[0256] In the above equations (1) and (2), X A The fluoropolyether portion (R) primarily provides water repellency and surface slipperiness. F1 and R F2 ) and the part that provides bonding ability to the substrate (R Si It is understood to be a linker that connects ) and . Therefore, the X A The group may be a single bond or any other group, as long as the compounds represented by formulas (1) and (2) can exist stably.

[0257] 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 are X A It can change depending on the valence of α. The sum of α and β is X A It is the same as the valence of X. For example, X A If is a 10-valent organic group, the sum of α and β is 10, and for example, α can be 9 and β 1, α can be 5 and β 5, or α can be 1 and β 9. Also, X A If it is a divalent organic group, then α and β are 1.

[0258] In equation (2) above, γ is an integer from 1 to 9. γ is X A It can change depending on the valence of X. That is, γ is X A This is the value obtained by subtracting 1 from the valence of [the element].

[0259] X AEach of these is independently a single bond or a 2-10 valent organic group;

[0260] The above X A The 2-10 valent organic group in is preferably a 2-8 valent organic group. In one embodiment, such a 2-10 valent organic group is preferably a 2-4 valent organic group, and more preferably a 2 valent organic group. In another embodiment, such a 2-10 valent organic group is preferably a 3-8 valent organic group, and more preferably a 3-6 valent organic group.

[0261] In one embodiment, X A It is a single-bonded or divalent organic group, where α is 1 and β is 1.

[0262] In one embodiment, X A It is a single-bonded or divalent organic group, and γ is 1.

[0263] In one embodiment, X A is a 3- to 6-valent organic group, with α being 1 and β being 2- to 5.

[0264] In one embodiment, X A γ is a 3- to 6-valent organic group, and γ is 2- to 5.

[0265] In one embodiment, X A It is a trivalent organic group, with α being 1 and β being 2.

[0266] In one embodiment, X A It is a trivalent organic group, and γ is 2.

[0267] X A However, 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'). [ka]

[0268] In one embodiment, X A It is a single bond.

[0269] In another embodiment, X A It is a divalent organic group.

[0270] In one embodiment, X A For example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In formula: R 51 This is a single bond, -(CH2) s5 - or o-, m- or p-phenylene group, preferably -(CH2) s5 -and, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2. X 51 is, -(X 52 ) l5 - represents, X 52 In each instance, these independently include -O-, -S-, o-, m- or p-phenylene groups, -C(O)O-, and -Si(R 53 )2-,-(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -, -O-CONR 54 -, -NR 54 -and-(CH2) n5 - Represents a group selected from the group consisting of, R 53 In each appearance, independently, a phenyl group and C are present. 1-6 Alkyl alkyl group or C 1-6 Represents an alkoxy group, preferably a phenyl group or C 1-6 It is an alkyl group, more preferably a methyl group, R 54 Each instance independently comprises a hydrogen atom, a phenyl group, or C. 1-6 Represents an alkyl group (preferably a methyl group), In each occurrence, m5 is an integer between 1 and 100, preferably between 1 and 20, independently. n5 is, in each occurrence, independently an integer between 1 and 20, preferably an integer between 1 and 6, more preferably an integer between 1 and 3. l5 is an integer between 1 and 10, preferably between 1 and 5, more preferably between 1 and 3. p5 is either 0 or 1. q5 is either 0 or 1. Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary. A divalent organic group represented by X is an example. Here, X A (typically X A The hydrogen atom of the fluorine atom, C 1-3 Alkyl and C 1-3 It may be substituted with one or more substituents selected from fluoroalkyl groups. In a preferred embodiment, X A These groups are not substituted by these groups.

[0271] In a preferred embodiment, the above X A These are, independently, -(R 51 ) p5 -(X 51 ) q5 -R 52 - is R 52 This is a single bond, -(CH2) t5 - or o-, m- or p-phenylene group, preferably -(CH2) t5 - is the case. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Here, R 52 (typically R 52 The hydrogen atom of the fluorine atom, C 1-3 Alkyl and C 1-3 It may be substituted with one or more substituents selected from fluoroalkyl groups. In a preferred embodiment, R 56 These groups are not substituted by these groups.

[0272] Preferably, the above X A Each of them operates independently. single bond, C 1-20 Alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 5 - [In the formula, R 51 and R 52 This is synonymous with the above, X 53 teeth, -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -Si(R 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-, -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54 -(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54-(o-, m- or p-phenylene)-Si(R 53 )2- (In the formula, R 53 , R 54 And m5 has the same meaning as above, u5 represents an integer between 1 and 20, preferably between 2 and 6, more preferably between 2 and 3. X 54 teeth, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (In the formula, each symbol has the same meaning as above.) [This represents...] It is possible.

[0273] More preferably, the above X A Each of them operates independently. single bond, C 1-20 Alkylene group, -(CH2) s5 -X 53 -, -(CH2) s5 -X 53 -(CH2) t5 - -X 54 -, or -X 54 -(CH2) t5 - [In the formula, X 53 , X 54 s5 and t5 have the same meaning as above. That is the case.

[0274] More preferably, the above X A Each of them operates independently. single bond, C 1-20 Alkylene group, -(CH2) s5 -X 53 -(CH2) t5 -, or -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as above.] It is possible.

[0275] In a preferred embodiment, the above X A Each of them operates independently. single bond C 1-20 Alkylene group, -(CH2) s5 -X 53 -, or -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 -O-, -CONR 54 -, or -O-CONR 54 -and, R 54 Each instance independently comprises a hydrogen atom, a phenyl group, or C. 1-6 Represents an alkyl group, s5 is an integer between 1 and 20. t5 is an integer between 1 and 20. It is possible.

[0276] In a preferred embodiment, the above X A Each of them operates independently. -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [In the formula, R 54 Each instance independently comprises a hydrogen atom, a phenyl group, or C. 1-6 Represents an alkyl group, s5 is an integer between 1 and 20. t5 is an integer between 1 and 20. It is possible.

[0277] In one embodiment, the above X A Each of them operates independently. single bond, C 1-20 Alkylene group, -(CH2) s5 -O-(CH2) t5 -, -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, or -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [In the formula, R 53 m5, s5, t5, and u5 have the same meaning as above, and v5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. That is the case.

[0278] In the above formula, -(C v H 2v )- may be a linear or branched chain, and may be, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0279] The above X A These are, independently, a fluorine atom and a carbon atom. 1-3 Alkyl and C 1-3 Fluoroalkyl groups (preferably C 1-3 It may be substituted with one or more substituents selected from perfluoroalkyl groups. In one embodiment, X A This is a non-substitution.

[0280] Furthermore, the above X A In each equation, the left side is R F1 or R F2 Combined, the right side is R Si Combine.

[0281] In one embodiment, X A These are, independently, -OC 1-6 It may be a group other than an alkylene group.

[0282] In another embodiment, X A Examples include the following bases: [ka] [ka] [In the formula, R 41 Each of these independently consists of a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 An alkoxy group, preferably a methyl group; D is -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), and [ka] (In the formula, R 42 These are, independently, hydrogen atoms and C 1-6 alkyl group or C 1-6 (This represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.) It is a base selected from, E is -(CH2) n -(n is an integer from 2 to 6), D is the R of the molecular backbone. F1 or R F2 E is bonded to R Si [Combine with...]

[0283] The above X A Specific examples include: single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -CH2OCF2CHFOCF2-, -CH2OCF2CHFOCF2CF2-, -CH2OCF2CHFOCF2CF2CF2-、 -CH2OCH2CF2CF2OCF2-、 -CH2OCH2CF2CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-, -(CH2)5-, -(CH2)6-, -CO-, -CONH-, -CONH-CH2-, -CONH-(CH2)2-, -CONH-(CH2)3-, -CONH-(CH2)4-, -CONH-(CH2)5-, -CONH-(CH2)6-, -CON(CH3)-CH2-, -CON(CH3)-(CH2)2-, -CON(CH3)-(CH2)3-, -CON(CH3)-(CH2)4-, -CON(CH3)-(CH2)5-, -CON(CH3)-(CH2)6-, -CON(Ph)-CH2- (where Ph represents phenyl), -CON(Ph)-(CH2)2- (wherein Ph means phenyl), -CON(Ph)-(CH2)3-(wherein Ph represents phenyl), -CON(Ph)-(CH2)4-(wherein Ph represents phenyl), -CON(Ph)-(CH2)5-(wherein Ph represents phenyl), -CON(Ph)-(CH2)6-(wherein Ph represents phenyl), -CONH-(CH2)2NH(CH2)3-, -CONH-(CH2)6NH(CH2)3-, -CH2O-CONH-(CH2)3-, -CH2O-CONH-(CH2)6-, -S-(CH2)3-, -(CH2)2S(CH2)3-, -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -C(O)O-(CH2)3-、 -C(O)O-(CH2)6-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、 -OCH2-、 -O(CH2)3-、 -OCFHCF2-、

Chem.

[0284] In yet another aspect, X A is, independently of each other, of the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1This is a base represented by -. In the formula, x1, y1, and z1 are each independent integers between 0 and 10, the sum of x1, y1, and z1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

[0285] In the above formula, R 16 In each appearance, the oxygen atom, phenylene, carbasoliene, and -NR appear independently. 18 -(In the formula, R 18 R represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, 18 This is an oxygen atom or a divalent polar group.

[0286] The above-mentioned "divalent polar group" is not particularly limited, but includes -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 -(In these formulas, R 19 Examples include (where represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.

[0287] In the above formula, R 17 Each instance is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0288] In yet another embodiment, X A Examples include the following bases: [ka] [In the formula, R 41Each of these independently consists of a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 The alkoxy group is preferably a methyl group; each X A In the base, any some of T are R of the molecular backbone. F1 or R F2 The following groups that bind to them: -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), or [ka] [In the formula, R 42 These are, independently, hydrogen atoms and C 1-6 alkyl group or C 1-6 This represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. And some of the other T's are R's of the molecular backbone. Si If bonded, the remaining T, if present, independently consists of a methyl group, a phenyl group, and C. 1-6 It is an alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.

[0289] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, but examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.

[0290] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, but examples include residues of benzotriazoles, hydroxybenzophenones, substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0291] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups are: [ka] These are some examples.

[0292] In this embodiment, X A Each of these can independently be a 3- to 10-valent organic group.

[0293] In yet another embodiment, X A Examples include the following bases: [ka] [In the formula, R 25 , R 26 and R 27 These are each independently 2-6 valent organic groups, R 25 is at least one R F1 Combined with R 26 and R 27 Each of these has at least one R Si [Combine with...]

[0294] In one embodiment, the above R 25 C is a single bond. 1-20 Alkylene group, C 3-20 Cycloalkylene group, C 5-20 Arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 - is the case. Above, R57 and R 59 Each of them is independently a single bond, C 1-20 Alkylene group, C 3-20 Cycloalkylene group, or C 5-20 It is an arylene group. 58 These are -O-, -S-, -CO-, -O-CO-, or -COO-.

[0295] In one embodiment, the above R 26 and R 27 Each is independently a hydrocarbon, or a group having at least one atom selected from N, O, and S in the end or main chain of a hydrocarbon, preferably C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2- are examples. Here, R 36 Each of these 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. 37 R is N, O, or S, preferably N or O. 38 is, -R 45 -R 46 -R 45 -, -R 46 -R 45 -or-R 45 -R 46 - is the case. Here, R 45 Each of these is an alkyl group having 1 to 6 carbon atoms. 46 is N, O, or S, and preferably O.

[0296] In this embodiment, X A Each of these can independently be a 3- to 10-valent organic group.

[0297] In yet another embodiment, X A For example, see below: [ka] [In the formula, X aThis refers to a single-bonded or divalent organic group. Examples of groups represented by

[0298] The above X a X is a single bond or a divalent linking group that is directly bonded to an isocyanuric ring. a Preferably, the group is a divalent group containing a single bond, an alkylene group, or at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond. More preferably, the group is a divalent hydrocarbon group having 1 to 10 carbon atoms containing a single bond, an alkylene group having 1 to 10 carbon atoms, or at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.

[0299] X a The formula is as follows: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (In the formula, X 121 ~X 124 These are H, F, OH, or -OSi(OR) respectively, independently. 121 )3(In the formula, three R 121 These are, independently, alkyl groups having 1 to 4 carbon atoms. The above X a1 These are -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (where the left side of each bond is CX). 121 X 122 It joins to ( ). x1 is an integer between 0 and 10, y1 is either 0 or 1, and z1 is an integer between 1 and 10. A group represented by is even more preferable.

[0300] The above X a1 -O- or -C(=O)O- are preferred.

[0301] The above X a The formula is as follows: -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - (In the formula, m11 is an integer between 1 and 3, m12 is an integer between 1 and 3, and m13 is an integer between 1 and 3.) A base represented by -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - (In the formula, m14 is an integer between 1 and 3, m15 is an integer between 1 and 3, and m16 is an integer between 1 and 3.) A base represented by -(CF2) m17 -(CH2) m18 - (In the formula, m17 is an integer between 1 and 3, and m18 is an integer between 1 and 3.) A base represented by -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - (In the formula, m19 is an integer between 1 and 3, m20 is an integer between 1 and 3, and m21 is an integer between 1 and 3.) A base represented by, -(CH2) m22 - (In the formula, m22 is an integer between 1 and 3.) A group represented by is particularly preferred.

[0302] The above X a While not particularly limited, specifically, -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, -(CF2) n5 -(n5 is an integer between 0 and 4.), -(CF2) n5 -(CH2) m5-(n5 and m5 are integers between 0 and 4, respectively), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- These are some examples.

[0303] In this embodiment, X A Each of these can independently be a divalent or trivalent organic group.

[0304] The fluorine-containing silane compound represented by formula (1) or formula (2) above is not particularly limited, but is 5 × 10 2 ~1 × 10 5 It may have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, from the viewpoint of wear resistance. Note that this "average molecular weight" refers to the number average molecular weight, and "average molecular weight" refers to the number average molecular weight. 19 The value shall be measured by 1F-NMR.

[0305] In one embodiment, the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (1).

[0306] In another embodiment, the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (2).

[0307] In another embodiment, the fluorine-containing silane compound in the surface treatment agent of the present disclosure is the compound represented by formula (1) and the compound represented by formula (2).

[0308] In the surface treatment agent of this disclosure, the compound represented by formula (2) is preferably 0.1 mol% or more and 35 mol% or less relative to the total amount of the compound represented by formula (1) and the compound represented by formula (2). The lower limit of the content of the compound represented by formula (2) relative to the total amount of the compound represented by formula (1) and the compound represented by 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%, and especially possibly 5 mol%. The upper limit of the content of the compound represented by formula (2) relative to the total amount of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol%, even more preferably 20 mol%, even more preferably 15 mol%, or 10 mol%. The amount of the compound represented by formula (2) relative to the sum of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, even more preferably 0.2 mol% to 10 mol%, even more preferably 0.5 mol% to 10 mol%, and particularly preferably 1 mol% to 10 mol%, for example, 2 mol% to 10 mol% or 5 mol% to 10 mol%. By setting the amount of the compound represented by formula (2) within this range, wear resistance can be further improved.

[0309] In one embodiment, the surface treatment agent of the present disclosure comprises two or more fluorine-containing silane compounds represented by formula (1) or (2). By including multiple fluorine-containing silane compounds, friction durability can be further improved.

[0310] In one embodiment, the surface treatment agent of the present disclosure is R Si However, it includes two or more fluorine-containing silane compounds represented by formula (1) or (2), each being a distinct group selected from formulas (S1), (S2), (S3), (S4), and (S5). Si The inclusion of a fluorine-containing silane compound can further improve friction resistance.

[0311] In one embodiment, the surface treatment agent of the present disclosure is R SiA fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S1), and R Si The compound comprises a fluorine-containing silane compound represented by formula (1) or (2), wherein is a group selected from formulas (S3), (S4), and (S5). Si A fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S1), and R Si The friction durability can be further improved by using in combination a fluorine-containing silane compound represented by formula (1) or (2), wherein the group is selected from formulas (S3), (S4), and (S5).

[0312] In one embodiment, the surface treatment agent of the present disclosure is R Si A fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S1), and R Si The compound comprises a fluorine-containing silane compound represented by formula (1) or (2), wherein the group is selected from formulas (S3) and (S4). Si A fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S1), and R Si The friction durability can be further improved by using in combination a fluorine-containing silane compound represented by formula (1) or (2), wherein the group is selected from formulas (S3) and (S4).

[0313] In one embodiment, the surface treatment agent of the present disclosure is R Si A fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S1), and R Si The compound contains a fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S3). Si A fluorine-containing silane compound represented by formula (1) or (2), in which is a group represented by formula (S1), and R Si By using a fluorine-containing silane compound represented by formula (1) or (2), in which is a group represented by formula (S3), friction durability can be further improved.

[0314] In one embodiment, the surface treatment agent of the present disclosure is R SiA fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S1), and R Si The compound contains a fluorine-containing silane compound represented by formula (1) or (2), wherein the group is represented by formula (S4). Si A fluorine-containing silane compound represented by formula (1) or (2), in which is a group represented by formula (S1), and R Si By using a fluorine-containing silane compound represented by formula (1) or (2), in which is a group represented by formula (S4), friction durability can be further improved.

[0315] The compounds represented by formula (1) or (2) above can be obtained, for example, by methods known to the present day, such as those described in International Publication No. 97 / 07155, Japanese Patent Publication No. 2008-534696, Japanese Patent Application Publication No. 2014-218639, Japanese Patent Application Publication No. 2017-82194, etc.

[0316] The content of the compound represented by formula (1) or (2) above may be preferably 0.01 to 50.0% by mass, 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, relative to the total surface treatment agent. By setting the content of the fluorine-containing silane compound within the above range, higher water-repellent and oil-repellent properties can be obtained.

[0317] The surface treatment agents used in this disclosure may include a solvent, a non-reactive fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"), a non-reactive silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like.

[0318] Examples of the above solvents include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl-2-hydroxybutyrate. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene Glycol ethers such as propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols 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; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Examples include fluorine-containing 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), Zeolora H, HFE7100, HFE7200, HFE7300, etc. Alternatively, mixed solvents of two or more of these are also possible.

[0319] Examples of fluorinated oils are not limited to those represented by the following general formula (3) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ...(3) In the formula, Rf 5 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1―16 Rf represents a perfluoroalkyl group. 6 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1-16 Rf represents a perfluoroalkyl group, a fluorine atom, or a hydrogen atom. 5 and Rf 6 More preferably, each independently, C 1-3 It is a perfluoroalkyl group. a', b', c', and d' represent the number of repeating units of the four types of perfluoro(poly)ether that constitute the main backbone of the polymer, and are independent integers between 0 and 300, with the sum of a', b', c', and d' being at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscripts a', b', c', or d' is arbitrary in the formula. Of these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0320] Examples of perfluoro(poly)ether compounds represented by the above general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one or a mixture of two or more). Rf 5 -(OCF2CF2CF2) b” -Rf 6 ...(3a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 ...(3b) In these equations, Rf 5 and Rf 6As stated above, in equation (3a), b'' is an integer between 1 and 100; in equation (3b), a'' and b'' are independently integers between 0 and 30, and c'' and d'' are independently integers between 1 and 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a'', b'', c'', and d'' is arbitrary within the equation.

[0321] From another perspective, fluorine-containing oils have the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented as a perfluoroalkyl group. It may also be a chlorotrifluoroethylene oligomer.

[0322] The above-mentioned fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0323] The fluorine-containing oil may be present in the surface treatment agent in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass. In one embodiment, the surface treatment agent is substantially free of fluorine-containing oil. Substantially free of fluorine-containing oil means that it is either completely free of fluorine-containing oil or may contain trace amounts of fluorine-containing oil.

[0324] In one embodiment, the average molecular weight of the fluorine-containing oil may be greater than the average molecular weight of the fluorine-containing silane compound. By using such an average molecular weight, better frictional durability and surface lubricity can be obtained, especially when forming a surface treatment layer by vacuum deposition.

[0325] In one embodiment, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluorine-containing silane compound. By using such an average molecular weight, it is possible to form a cured product with high frictional durability and high surface slipperiness while suppressing a decrease in the transparency of the surface treatment layer obtained from such a compound.

[0326] Fluorine-containing oils contribute to improving the surface slipperiness of layers formed by surface treatment agents.

[0327] As the silicone oil mentioned above, for example, a linear or cyclic silicone oil with 2,000 or fewer siloxane bonds may be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0328] In the above surface treatment agent, the silicone oil may be included in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the above fluorine-containing silane compounds (the sum of these in the case of two or more types, and the same applies hereinafter).

[0329] Silicone oil contributes to improving the surface lubricity of the surface-treated layer.

[0330] Examples of catalysts include acids (e.g., acetic acid, trifluoroacetic acid, etc.), bases (e.g., ammonia, triethylamine, diethylamine, etc.), and transition metals (e.g., Ti, Ni, Sn, etc.).

[0331] The catalyst promotes the hydrolysis and dehydration condensation of the above-mentioned fluorine-containing silane compound, thereby facilitating the formation of the layer formed by the above-mentioned surface treatment agent.

[0332] Other components besides those listed above include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0333] The surface treatment agent used in this disclosure can be formed into pellets by impregnating porous materials, such as porous ceramic materials, or metal fibers, such as steel wool compressed into a cotton-like form. These pellets can be used, for example, in vacuum deposition.

[0334] The thickness of the surface treatment layer is not particularly limited. In the case of optical components, the thickness of the layer is preferably in the range of 1 to 50 nm, preferably 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability, and antifouling properties.

[0335] The above-mentioned surface treatment layer can be formed, for example, by forming a layer of the surface treatment agent on the above-mentioned intermediate layer and then post-treating this layer as needed.

[0336] The formation of the above-mentioned surface treatment agent layer can be carried out by applying the above-mentioned surface treatment agent to the surface of the intermediate layer so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating methods can be used.

[0337] Examples of wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

[0338] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0339] Furthermore, coating using the atmospheric pressure plasma method is also possible.

[0340] When using the wet coating method, the above surface treatment agent may be diluted with a solvent before being applied to the intermediate layer. From the viewpoint of the stability of the above surface treatment agent and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 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 13 CH2CH3 (e.g., AsahiClean® AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeolora® H manufactured by Nippon Zeon Co., Ltd.); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Limited), Alkyl perfluoroalkyl ethers such as perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or as a mixture of two or more. Among these, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0341] When using the dry coating method, the above surface treatment agent may be applied to the dry coating method as is, or it may be diluted with the above solvent before being applied to the dry coating method.

[0342] The layer formation of the above surface treatment agent is preferably carried out so that the surface treatment agent exists in the layer together with a catalyst for hydrolysis and dehydration condensation. For convenience, in the case of the wet coating method, the catalyst may be added to the diluted solution of the surface treatment agent immediately before applying it to the surface of the intermediate layer after diluting the surface treatment agent with a solvent. In the case of the dry coating method, the catalyst-added surface treatment agent may be directly vapor-deposited (usually by vacuum deposition), or a pellet-like material impregnated with the catalyst-added surface treatment agent may be used for vapor deposition (usually by vacuum deposition).

[0343] Any suitable acid or base can be used as a catalyst. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0344] As described above, a layer derived from the surface treatment agent is formed on the surface of the intermediate layer, and the article of this disclosure is manufactured. The surface treatment layer obtained thereby has high friction resistance. In addition to high friction resistance, the layer may also have water repellency, oil repellency, stain resistance (for example, preventing the adhesion of dirt such as fingerprints), waterproofness (preventing water from entering electronic components, etc.), surface slipperiness (or lubricity, for example, ease of wiping off dirt such as fingerprints, and excellent tactile feel to the fingers), depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0345] The articles of this disclosure may further be optical materials having the above-mentioned surface treatment layer as the outermost layer.

[0346] The articles of this disclosure may be optical components, but are not limited to these. Examples of optical components include: lenses such as those in eyeglasses; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces for optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces for watches.

[0347] Furthermore, the articles of this disclosure may be medical devices or medical materials.

[0348] The articles of this disclosure have been described in detail above. However, the articles of this disclosure and the methods for manufacturing them are not limited to those exemplified above. [Examples]

[0349] The articles of this disclosure will be described below in the examples, but this disclosure is not limited to the following examples. In these examples, all chemical formulas shown below represent the average composition, and the order of the repeating units constituting the fluoropolyether ((CF2CF2CF2O), (CF(CF3)CF2O), (CF2CF2O), (CF2O), etc.) is arbitrary.

[0350] Preparation example A surface treatment agent was prepared by dissolving a fluorine-containing silane compound, represented by the following formula (average composition), in hydrofluoroether (Novec HFE7200, 3M) to a concentration of 20 wt%. CF3O(CF2CF2O) 20 (CF2O) 16 CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 (Note that the average composition consists of 0.17 repeating units of (CF2CF2CF2CF2O) and (CF2CF2 The sample contained 0.18 repeating units of CF2O, but these were omitted due to their trace amount.

[0351] Examples 1-4 An aluminum oxide and silicon oxide layer was deposited to a thickness of 6 nm on a ceramic glass substrate by electron beam deposition to form intermediate layer 1. Next, a silicon oxide layer was deposited to a thickness of 10 nm on intermediate layer 1 by electron beam deposition to form intermediate layer 2. Then, a predetermined amount of the surface treatment agent prepared above was deposited to form a layer of the surface treatment agent. After that, the substrate with the layer of surface treatment agent was left to stand for 24 hours in an atmosphere of 20°C and 65% RH to cure the layer of surface treatment agent and obtain a surface treatment layer.

[0352] Comparative Example 1 A silicon oxide layer was deposited onto a ceramic substrate to a thickness of 16 nm by electron beam deposition to form an intermediate layer 2. Next, a predetermined amount of the surface treatment agent prepared above was deposited onto the intermediate layer 2 to form a layer of the surface treatment agent. Subsequently, the substrate with the surface treatment agent layer was left to stand for 24 hours in an atmosphere of 20°C and 65% RH to cure the surface treatment agent layer and obtain a surface treatment layer.

[0353] <Rating> For the functional film-coated articles obtained above, the Al content (at%) at 11-17 nm was determined using the method described above, starting from the surface layer of the intermediate layer. Furthermore, steel wool abrasion tests were performed on the functional film-coated articles obtained in each of the above examples.

[0354] Steel wool abrasion test The functional film-coated articles from Examples 1-4 and Comparative Example 1 were placed horizontally, and steel wool (grit #0000, dimensions 10mm x 10mm) was brought into contact with the exposed upper surface of the surface treatment layer. A load of 1000gf was applied, and then the steel wool was moved back and forth while the load was applied (distance: 60mm, speed: 40rpm). The water contact angle was measured after a certain number of reciprocations. The evaluation was stopped when the measured contact angle fell below 100°. The number of reciprocations at which the measured value fell below 100° was defined as the steel wool wear durability.

[0355] [Table 1] [Industrial applicability]

[0356] The articles of this disclosure can be suitably used in a variety of applications, for example, as optical components.

Claims

1. Substrate and An intermediate layer located on the aforementioned substrate, A surface treatment layer located on the aforementioned intermediate layer, formed from a surface treatment agent containing a fluorine-containing silane compound, An article having, The substrate is a ceramic glass containing a petalite crystalline phase and a lithium silicate crystalline phase. The aforementioned intermediate layer includes a first layer of aluminum oxide and silicon oxide, and a second layer of silicon oxide located above it. Goods.

2. The article according to claim 1, wherein in the substrate, the total mass of the petalite crystalline phase and the lithium silicate crystalline phase is greater than the total mass of other crystalline phases present in the ceramic glass.

3. The aforementioned ceramic glass consists of the following components: SiO ２ 55-80% by mass Al ２ O ３ 2-20% by mass Li ２ O: 5-20% by mass B ２ O ３ 0-10% by mass Na ２ O: 0-5% by mass ZnO: 0 to 10% by mass, P ２ O ５ : 0.5 to 6% by mass, and ZrO ２ 0.2-15% by mass An article according to claim 1 or 2, comprising:

4. The aforementioned ceramic glass further comprises the following components: K ２ O: 0~4%, MgO: 0-8%, TO ２ :0~5%, CEO ２ : 0-0.4%, and SnO ２ :0.05~0.5% The article according to claim 3, which contains the following:

5. The aforementioned aluminum oxide is Al ２ O ３ The silicon dioxide is SiO ２ The article according to claim 1 or 2.

6. The article according to claim 1 or 2, wherein in the preceding layer, the content of aluminum is 0.5 to 60.0 at% with respect to the total amount of aluminum and silicon.

7. The article according to claim 1 or 2, wherein in the preceding layer, the content of aluminum is 0.7 to 50.5 at% with respect to the total amount of aluminum and silicon.

8. The article according to claim 1 or 2, wherein the thickness of the intermediate layer is 5 nm to 35 nm.

9. The article according to claim 1 or 2, wherein the thickness of the intermediate layer is 10 nm to 30 nm.

10. The article according to claim 1 or 2, wherein the ratio of the thickness of the first layer to the thickness of the second layer is 0.1 to 10.

11. The fluorine-containing silane compound is defined by the following formula (1) or (2): 【Chemistry 1】 [In the formula: R Ｆ１ Each occurrence is independent of Rf １ -R Ｆ -O ｑ - and; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ C may be independently substituted with one or more fluorine atoms in each occurrence. １－１６ It is an alkyl group; Rf ２ C may be substituted with one or more fluorine atoms. １－６ It is an alkylene group; R Ｆ In each occurrence, it is independently a divalent fluoropolyether group; p is either 0 or 1; q is either 0 or 1 in each occurrence, independently; R Ｓｉ In each occurrence, it is independently a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a Si atom to which a monovalent organic group is bonded; at least one R Ｓｉ This is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ Each of these is independently a single bond or a 2- to 10-valent organic group, and the valency of X A is equal to the sum of α and β in formula (1) and γ + 1 in formula (2); α is an integer between 1 and 9; β is an integer between 1 and 9; Each of the γ values ​​is an independent integer between 1 and 9. The article according to claim 1 or 2, which is at least one fluoropolyether group-containing compound represented by .

12. Rf １ In each occurrence, C is independent. １－１６ It is a perfluoroalkyl group, Rf ２ In each occurrence, C is independent. １－６ It is a perfluoroalkylene group, The article according to claim 11.

13. R Ｆ Each occurrence is independent of the formula: -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ R Ｆａ ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [In the formula, R Ｆａ In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers between 0 and 200, the sum of a, b, c, d, e, and f is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary within the expression. The article according to claim 11, which is a base represented by

14. R Ｆａ The article according to claim 13, wherein is a fluorine atom.

15. R Ｆ Each occurrence independently satisfies the following equations (f1), (f2), (f3), (f4), (f5), or (f6): -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ - (f1) [In the formula, d is an integer between 1 and 200, and e is 0 or 1.] -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f2) [In the formula, c and d are each independent integers between 0 and 30; e and f are each independent integers between 1 and 200; The sum of c, d, e, and f is an integer between 10 and 200; The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. -(R ６ -R ７ ) ｇ - (f3) [In the formula, R ６ OCF ２ or OC ２ F ４ And; R ７ is a group selected from OC ２ F ４ OC ３ F ６ OC ４ F ８ OC ５ F １０ and OC ６ F １２ or a combination of two or three groups selected from these groups; g is an integer between 2 and 100. -(R ６ -R ７ ) ｇ -R ｒ -(R ７’ -R ６’ ) ｇ’ - (f4) [In the formula, R ６ OCF ２ or OC ２ F ４ And, R ７ OC ２ F ４ , OC ３ F ６ , OC ４ F ８ , OC ５ F １０ and OC ６ F １２ It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. R ６’ OCF ２ or OC ２ F ４ And, R ７’ OC ２ F ４ , OC ３ F ６ , OC ４ F ８ , OC ５ F １０ and OC ６ F １２ It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. g' is an integer between 2 and 100. R ｒ teeth, 【Chemistry 2】 (In the formula, * indicates the bonding position.) That is. -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f5) [In the formula, e is an integer between 1 and 200, a, b, c, d, and f are each independent integers between 0 and 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f5) [In the formula, f is an integer between 1 and 200, a, b, c, d, and e are each independent integers between 0 and 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The article according to claim 11, which is a base represented by

16. R Ｓｉ This is expressed by the following formulas (S1), (S2), (S3), (S4), or (S5): 【Transformation 3】 [In the formula: R １１ Each instance is independently either a hydroxyl group or a hydrolyzable group; R １２ Each instance is independently either a hydrogen atom or a monovalent organic group; n1 is (SiR １１ ｎ１ R １２ ３－ｎ１ Each unit is an independent integer between 0 and 3; X １１ Each instance is independently either a single bond or a divalent organic group; R １３ Each instance is independently either a hydrogen atom or a monovalent organic group; t is an integer greater than or equal to 2, independently in each occurrence; R １４ Each instance independently represents a hydrogen atom, a halogen atom, or -X. １１ -SiR １１ ｎ１ R １２ ３－ｎ１ And; R １５ Each instance independently consists of a single bond, an oxygen atom, a C1-C6 alkylene group, or a C1-C6 alkylene oxy group; R ａ１ In each occurrence, independently, -Z １ -SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ And; Z １ Each instance is independently either an oxygen atom or a divalent organic group; R ２１ In each occurrence, independently, -Z １’ -SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ And; R ２２ Each instance is independently either a hydroxyl group or a hydrolyzable group; R ２３ Each instance is independently either a hydrogen atom or a monovalent organic group; p1 is an integer between 0 and 3, independently in each occurrence; q1 is an integer between 0 and 3, independently in each occurrence; r1 is an integer between 0 and 3, independently in each occurrence; The sum of p1, q1, and r1 is SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ In terms of units, it is 3; Z １’ Each instance is independently either an oxygen atom or a divalent organic group; R ２１’ In each occurrence, independently, -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” And; R ２２’ Each instance is independently either a hydroxyl group or a hydrolyzable group; R ２３’ Each instance is independently either a hydrogen atom or a monovalent organic group; p1' is an integer between 0 and 3, independently in each occurrence; q1' is an integer between 0 and 3, independently in each occurrence; r1' is an integer between 0 and 3, independently in each occurrence; The sum of p1', q1', and r1' is SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ In terms of units, it is 3; Z １” Each instance is independently either an oxygen atom or a divalent organic group; R ２２” Each instance is independently either a hydroxyl group or a hydrolyzable group; R ２３” Each instance is independently either a hydrogen atom or a monovalent organic group; q1'' is an integer between 0 and 3, independently in each occurrence; r1'' is an integer between 0 and 3, independently in each occurrence; The sum of q1" and r1" is SiR ２２” ｑ１” R ２３” ｒ１” In terms of units, it is 3; R ｂ１ Each instance is independently either a hydroxyl group or a hydrolyzable group; R ｃ１ Each instance is independently either a hydrogen atom or a monovalent organic group; k1 is an integer between 0 and 3, independently in each occurrence; l1 is an integer between 0 and 3, independently in each occurrence; m1 is an integer between 0 and 3, independently in each occurrence; The sum of k1, l1, and m1 is SiR ａ１ ｋ１ R ｂ１ ｌ１ R ｃ１ ｍ１ In terms of units, it is 3; R ｄ１ In each occurrence, independently, -Z ２ -CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ And; Z ２ Each instance is independently a single bond, an oxygen atom, or a divalent organic group; R ３１ In each occurrence, independently, -Z ２’ -CR ３２’ ｑ２’ R ３３’ ｒ２’ And; R ３２ In each occurrence, independently, -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ And; R ３３ Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is an integer between 0 and 3, independently in each occurrence; q2 is an integer between 0 and 3, independently in each occurrence; r² is an integer between 0 and 3, independently in each occurrence; The sum of p2, q2, and r2 is SiR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ In terms of units, it is 3; Z ２’ Each instance is independently a single bond, an oxygen atom, or a divalent organic group; R ３２’ In each occurrence, independently, -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ And; R ３３’ Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is an integer between 0 and 3, independently in each occurrence; r²' is an integer between 0 and 3, independently in each occurrence; The sum of q2' and r2' is SiR ３２’ ｑ２’ R ３３’ ｒ２’ In terms of units, it is 3; Z ３ Each instance is independently a single bond, an oxygen atom, or a divalent organic group; R ３４ Each instance is independently either a hydroxyl group or a hydrolyzable group; R ３５ Each instance is independently either a hydrogen atom or a monovalent organic group; n² is an integer between 0 and 3, independently in each occurrence; R ｅ１ In each occurrence, independently, -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ And; R ｆ１ Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 is an integer between 0 and 3, independently in each occurrence; l2 is an integer between 0 and 3, independently in each occurrence; m² is an integer between 0 and 3, independently in each occurrence; The sum of k2, l2, and m2 is CR ｄ１ ｋ２ R ｅ１ ｌ２ R ｆ１ ｍ２ In terms of units, it is 3; R ｇ１ and R ｈ１ In each occurrence, independently, -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 And; Z ４ Each instance is independently a single bond, an oxygen atom, or a divalent organic group; However, in formulas (S1), (S2), (S3), (S4), and (S5), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded. The article according to claim 11, which is a base represented by

17. R Ｓｉ The article according to claim 11, wherein is formula (S3), (S4), or (S5).

18. R Ｓｉ The article according to claim 11, wherein is formula (S3) or (S4).

19. The article according to claim 11, wherein α, β, and γ are 1.

20. X Ａ These are, independently, trivalent organic groups. Either α is 1 and β is 2, or α is 2 and β is 1. γ is 2. The article according to claim 11.

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