Article and method for manufacturing article

Abstract

An article includes a substrate and a surface treatment layer which is disposed on the substrate and is surface-treated with a surface treatment agent, the surface treatment layer having a surface roughness Sdr of 30% or more in an arbitrary measurement area range of 5-50 [mu] m square, and the surface treatment agent including a compound having a chain group and a reactive silyl group.

Description

Technical Field

[0001] This disclosure relates to articles and methods of manufacturing articles. Background Technology

[0002] In recent years, in order to improve appearance, visibility, and other properties, there has been a search for technologies that make fingerprints less likely to adhere to the surface of objects and technologies that facilitate the removal of dirt. As a specific method, methods for surface-treating objects using surface treatment agents are known.

[0003] For example, Patent Document 1 describes an article comprising: a substrate; and a layer formed on the substrate by a composition comprising a silane compound containing a siloxane group.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2023 / 017830 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] In surface-treated layers formed by surface treatment agents, improved liquid repellency is required.

[0009] This disclosure was made in view of the following circumstances, and one embodiment of the present invention aims to solve the problem of providing an article having a surface treatment layer with excellent liquid repellency and a method for manufacturing the article.

[0010] Solution for solving the problem

[0011] This disclosure includes the following methods.

[0012] <1>

[0013] An article comprising a substrate and a surface treatment layer, the surface treatment layer being disposed on the substrate and surface-treated with a surface treatment agent.

[0014] The surface roughness Sdr of the surface treatment layer is above 30% within any measurement area of ​​5~50μm square.

[0015] Surface treatment agents contain compounds with chain-like groups and reactive silyl groups.

[0016] <2>

[0017] according to <1> The article wherein the compound having a chain group and a reactive silyl group is a compound having a chain organo(poly)siloxane residue and a reactive silyl group.

[0018] <3>

[0019] according to <1> or <2> The article wherein the reactive silane is represented by the following formula (S1) or formula (S3).

[0020] -Si(R) 2 ) n L 3-n …(S1)

[0021] -[Si(L) 2 )2-P] r1 -Si(L 2 )3…(S3)

[0022] In formula (S1),

[0023] R 2 Each is an independent hydrocarbon group.

[0024] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0025] n is an integer between 0 and 2.

[0026] In formula (S3),

[0027] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0028] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0029] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0030] r1 is an integer from 1 to 3.

[0031] <4>

[0032] according to <2> The article wherein the chain-like organo(poly)siloxane residues are represented by the following formula (B1).

[0033]

[0034] In formula (B1),

[0035] R 3 Each is an independent hydrocarbon group.

[0036] k1 is a number greater than or equal to 1.

[0037] This refers to the bonding site with adjacent atoms.

[0038] <5>

[0039] according to <1> ~ <4> The article in any one of the following statements, wherein the compound having a chain group and a reactive silyl group is represented by the following formula (C), (C2) or (D), (D2), (E) or (E2).

[0040]

[0041]

[0042] In formula (C),

[0043] T 11 It is a monovalent group that does not contain reactive silyl groups.

[0044] B can be independently -O- or -C (=O)-.

[0045] r can be 0 or 1 independently.

[0046] R 3 Each is an independent hydrocarbon group.

[0047] k1 are each an independent number greater than or equal to 1.

[0048] p1 is an integer greater than or equal to 1.

[0049] A 11 It is a (p1+q1) valence linker.

[0050] q1 is an integer greater than or equal to 1.

[0051] R 2 Each is an independent hydrocarbon group.

[0052] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0053] n is an independent integer from 0 to 2.

[0054] In formula (C2),

[0055] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0056] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0057] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0058] r1 is an integer from 1 to 3.

[0059] T 11 B, r, R 3 k1, p1, A 11 The definitions of q1 and q1 are the same as those in equation (C).

[0060]

[0061]

[0062] In equation (D),

[0063] R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -,

[0064] T 11 Each is an independent monovalent group.

[0065] B can be independently -O- or -C (=O)-.

[0066] r can be 0 or 1 independently.

[0067] R 3 Each is an independent hydrocarbon group.

[0068] k1 are each an independent number greater than or equal to 1.

[0069] A 12 Each is an independent (q1+1) valence linker.

[0070] Each q1 is an independent integer greater than or equal to 1.

[0071] R 2 Each is an independent hydrocarbon group.

[0072] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0073] n is an independent integer from 0 to 2.

[0074] In equation (D2),

[0075] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0076] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0077] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0078] r1 is an independent integer from 1 to 3.

[0079] R 4 k1, A 12 The definitions of q1 and q1 are the same as those in equation (D).

[0080]

[0081]

[0082] In formula (E),

[0083] B 11 It is a monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups; or it is a monovalent group comprising a branched alkyl group.

[0084] u1 is an integer greater than or equal to 1.

[0085] A 13 It is a (q1+u1) valence linker.

[0086] q1 is an integer greater than or equal to 1.

[0087] R 2 Each is an independent hydrocarbon group.

[0088] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0089] n is an independent integer from 0 to 2.

[0090] In formula (E2),

[0091] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0092] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0093] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0094] r1 is an independent integer from 1 to 3.

[0095] B 11 u1, A 13 The definitions of q1 and q1 are the same as those in equation (E).

[0096] <6>

[0097] according to <5> The items mentioned above, wherein,

[0098] In equations (C) and (C2), k1 is a number between 3 and 500.

[0099] In equations (D) and (D2), k1 is a number between 3 and 500.

[0100] <7>

[0101] according to <5> or <6> The items mentioned above, wherein,

[0102] In equations (C), (C2), (E), and (E2), q1 is an integer from 1 to 4.

[0103] In equations (D) and (D2), q1 is an integer from 1 to 4, each independently.

[0104] <8>

[0105] according to <1> ~ <7> The article described in any one of the following statements, wherein the substrate is glass.

[0106] <9>

[0107] according to <1> ~ <8> The article described in any one of the following is an optical component.

[0108] <10>

[0109] according to <1> ~ <9> The article mentioned in any one of these examples is a display or a touch panel.

[0110] <11>

[0111] A method for manufacturing an article, wherein a surface treatment agent is used to treat a substrate to produce an article having a surface treatment layer formed on the substrate.

[0112] The surface roughness Sdr of the surface treatment layer is above 30% within any measurement area of ​​5~50μm square.

[0113] Surface treatment agents contain compounds with chain-like groups and reactive silyl groups.

[0114] <12>

[0115] according to <11> The method for manufacturing the article, wherein the compound having chain-like groups and reactive silyl groups is a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

[0116] <13>

[0117] according to <11> or <12> The method for manufacturing the article, wherein the substrate is a substrate with a surface roughness Sdr of 30% or more in any measured area ranging from 5 to 50 μm square.

[0118] <14>

[0119] according to <11> ~ <13> The method of manufacturing the article according to any one of the following methods, wherein the reactive silane is represented by the following formula (S1) or formula (S3).

[0120] -Si(R) 2 ) n L 3-n …(S1)

[0121] -[Si(L) 2 )2-P] r1 -Si(L 2 )3…(S3)

[0122] In formula (S1),

[0123] R 2 Each is an independent hydrocarbon group.

[0124] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0125] n is an integer between 0 and 2.

[0126] In formula (S3),

[0127] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0128] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0129] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0130] r1 is an integer from 1 to 3.

[0131] <15>

[0132] according to <12> The method of manufacturing the article, wherein the chain-like organo(poly)siloxane residues are represented by the following formula (B1).

[0133]

[0134] In formula (B1),

[0135] R 3Each is an independent hydrocarbon group.

[0136] k1 is a number greater than or equal to 1.

[0137] This refers to the bonding site with adjacent atoms.

[0138] <16>

[0139] according to <11> ~ <15> The method of manufacturing the article according to any one of the following methods, wherein the compound having a chain group and a reactive silyl group is represented by the following formula (C), (C2), (D), (D2), (E) or (E2).

[0140]

[0141]

[0142] In formula (C),

[0143] T 11 It is a monovalent group that does not contain reactive silyl groups.

[0144] B can be independently -O- or -C (=O)-.

[0145] r can be 0 or 1 independently.

[0146] R 3 Each is an independent hydrocarbon group.

[0147] k1 are each an independent number greater than or equal to 1.

[0148] p1 is an integer greater than or equal to 1.

[0149] A 11 It is a (p1+q1) valence linker.

[0150] q1 is an integer greater than or equal to 1.

[0151] R 2 Each is an independent hydrocarbon group.

[0152] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0153] n is an independent integer from 0 to 2.

[0154] In formula (C2),

[0155] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0156] L 2 At least 4 L in 2It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0157] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0158] r1 is an integer from 1 to 3.

[0159] T 11 B, r, R 3 k1, p1, A 11 The definitions of q1 and q1 are the same as those in equation (C).

[0160]

[0161]

[0162] In equation (D),

[0163] In equation (D),

[0164] R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -,

[0165] T 11 Each is an independent monovalent group.

[0166] B can be independently -O- or -C (=O)-.

[0167] r can be 0 or 1 independently.

[0168] R 3 Each is an independent hydrocarbon group.

[0169] k1 are each an independent number greater than or equal to 1.

[0170] A 12 Each is an independent (q1+1) valence linker.

[0171] Each q1 is an independent integer greater than or equal to 1.

[0172] R 2 Each is an independent hydrocarbon group.

[0173] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0174] n is an independent integer from 0 to 2.

[0175] In equation (D2),

[0176] L2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0177] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0178] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0179] r1 is an independent integer from 1 to 3.

[0180] R 4 k1, A 12 The definitions of q1 and q1 are the same as those in equation (D).

[0181]

[0182]

[0183] In formula (E),

[0184] B 11 It is a monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups; or it is a monovalent group comprising a branched alkyl group.

[0185] u1 is an integer greater than or equal to 1.

[0186] A 13 It is a (q1+u1) valence linker.

[0187] q1 is an integer greater than or equal to 1.

[0188] R 2 Each is an independent hydrocarbon group.

[0189] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0190] n is an independent integer from 0 to 2.

[0191] In formula (E2),

[0192] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0193] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0194] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0195] r1 is an independent integer from 1 to 3.

[0196] B 11 u1, A 13 The definitions of q1 and q1 are the same as those in equation (E).

[0197] The effects of the invention

[0198] According to one embodiment of the present invention, an article having a surface treatment layer with excellent liquid repellency and a method for manufacturing the article are provided. Detailed Implementation

[0199] In this disclosure, within the numerical range represented by "~", the values ​​recorded before and after "~" are respectively taken as the minimum and maximum values.

[0200] In the numerical ranges described in this disclosure, the upper or lower limit of a numerical range can be replaced by the upper or lower limit of other numerical ranges described in different stages. Furthermore, the upper or lower limit of the numerical ranges described in this specification can also be replaced by the values ​​shown in the embodiments.

[0201] In this disclosure, "surface treatment layer" refers to a layer formed on the surface of a substrate through surface treatment.

[0202] In this disclosure, when a compound or group is represented by a specific formula (X), the compound or group represented by the formula (X) is sometimes referred to as compound (X) or compound X, and group (X) or group X, respectively.

[0203] In this disclosure, organosiloxane residues refer to organosiloxane residues or organopolysiloxane residues.

[0204] In this disclosure, “Me” sometimes refers to methyl.

[0205] [thing]

[0206] The disclosed article comprises a substrate and a surface treatment layer disposed on the aforementioned substrate and surface-treated with a surface treatment agent, wherein the surface roughness Sdr of the surface treatment layer is 30% or more in any measured area of ​​5 to 50 μm square, and the surface treatment agent comprises a compound having chain groups and reactive silyl groups.

[0207] In one embodiment, the article of this disclosure preferably comprises a substrate and a surface treatment layer disposed on the aforementioned substrate and surface-treated with a surface treatment agent, wherein the surface roughness Sdr of the surface treatment layer is 30% or more in any measured area of ​​5 to 50 μm square, and the surface treatment agent comprises a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

[0208] Hereinafter, compounds having chain-like groups and reactive silyl groups will also be referred to as "specific silane compounds," wherein compounds having chain-like organo(poly)siloxane residues and reactive silyl groups will also be referred to as "specific silane compound A" (it should be noted that "compound 1" and "compound 2" described later are one embodiment of this designation). In this disclosure, the description of specific silane compounds shall also apply to cases where "specific silane compound" is replaced with "specific silane compound A," provided there is no contradiction.

[0209] The article according to this disclosure has a surface treatment layer with excellent liquid repellency.

[0210] The reason for this effect is still uncertain, but the following is a speculation.

[0211] Typically, it is difficult to improve liquid repellency in silicone-based materials. However, it is believed that in surface-treated layers treated with a surface-treatment agent containing a compound having chain-like organo(poly)siloxane residues and reactive silyl groups, liquid repellency is improved due to the uneven shape of the surface-treated layer by making the surface roughness Sdr of any measured area in the range of 5 to 50 μm square more than 30%.

[0212] On the other hand, Patent Document 1 does not contain any description of the surface roughness of the surface treatment layer.

[0213] The following is a detailed description of the components of the items disclosed herein.

[0214] The articles disclosed herein include a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent of the present disclosure.

[0215] <Substrate>

[0216] There is no particular limitation on the type of substrate. For example, a substrate that is required to be water-repellent can be mentioned. Examples of substrates include: substrates that are sometimes used when they come into contact with other articles (such as styluses) or human fingers; substrates that are sometimes held by human fingers during operation; and substrates that are sometimes placed on other articles (such as a platform).

[0217] Materials that can be used as substrates include metals, resins, glass, sapphire, ceramics, semiconductors, stone, fibers, nonwoven fabrics, paper, wood, fur, natural leather, artificial leather, ceramics, and their composites. Glass can also be chemically strengthened.

[0218] Examples of substrates include building materials, decorative building materials, interior decoration products, transportation equipment (e.g., automobiles), billboards, notice boards, drinking vessels, tableware, sinks, ornamental items (e.g., plaques, boxes), laboratory equipment, furniture, fiber products, and packaging containers; glass or resin used in art, sports, and games; and glass or resin used in the exterior parts (excluding the display) of devices such as mobile phones (e.g., smartphones), portable information terminals, game consoles, and remote controls. The substrate can be in the form of a sheet or a film.

[0219] In applications involving optical components, glass is the preferred substrate.

[0220] As a substrate, it is suitable for touch panel substrates, display substrates, and eyeglass lenses, and is particularly suitable for touch panel substrates. Glass or transparent resin is preferred as the material for touch panel substrates.

[0221] The substrate can also be a substrate with surface treatments such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment applied to one or both sides. Surface-treated substrates exhibit better adhesion to the surface-treated layer, and the wear resistance of the surface-treated layer is further improved. Therefore, it is preferable to perform surface treatment on the surface of the substrate that contacts the surface-treated layer. Furthermore, when a base layer (described later) is provided, the surface-treated substrate exhibits better adhesion to the base layer, and the wear resistance of the surface-treated layer is further improved. Therefore, when a base layer is provided, it is preferable to perform surface treatment on the surface of the substrate that contacts the base layer.

[0222] <Surface Treatment Layer>

[0223] The surface treatment layer can be formed on a portion of the surface of the substrate or on the entire surface of the substrate. The surface treatment layer can be spread into a film on the surface of the substrate or distributed in a dotted pattern.

[0224] In the surface treatment layer, compounds having chain groups and reactive silyl groups (in one form, compounds having chain organo(poly)siloxane residues and reactive silyl groups) are contained in a state in which some or all of the reactive silyl groups have been hydrolyzed and the silanol groups have undergone dehydration condensation reaction.

[0225] The thickness of the surface treatment layer is preferably 1~100 nm, more preferably 1~50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effects brought about by the surface treatment can be fully obtained. If the thickness of the surface treatment layer is less than 100 nm, the utilization efficiency is high. The thickness of the surface treatment layer can be calculated as follows: using a thin film analysis X-ray diffractometer (product name "ATX-G", manufactured by Rigaku Corporation), the interference pattern of reflected X-rays is obtained by the X-ray reflectivity method, and the thickness is calculated from the vibration period of the interference pattern.

[0226] The surface treatment layer can be directly applied to the surface of the substrate, or a base layer can be disposed between the substrate and the surface treatment layer. From the viewpoint of further improving the liquid repellency of the surface treatment layer, the articles of this disclosure preferably include a substrate, a base layer disposed on the substrate, and a surface treatment layer disposed on the base layer that has been surface-treated with the surface treatment agent of this disclosure.

[0227] The substrate layer is preferably a layer containing an oxide of silicon and at least one specific element selected from the group consisting of elements from group 1, group 2, group 4, group 5, group 13 and group 15 of the periodic table.

[0228] The elements in Group 1 of the periodic table (hereinafter also referred to as "Group 1 elements") are lithium, sodium, potassium, rubidium, and cesium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing fluctuations in the composition of the substrate layer between samples, lithium, sodium, and potassium are preferred as Group 1 elements, and sodium and potassium are more preferred. The substrate layer may also contain two or more Group 1 elements.

[0229] The elements in Group 2 of the periodic table (hereinafter also referred to as "Group 2 elements") refer to beryllium, magnesium, calcium, strontium, and barium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing fluctuations in the composition of the substrate layer between samples, magnesium, calcium, and barium are preferred as Group 2 elements, and magnesium and calcium are more preferred. The substrate layer may also contain two or more Group 2 elements.

[0230] The elements in Group 4 of the periodic table (hereinafter also referred to as "Group 4 elements") refer to titanium, zirconium, and hafnium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing fluctuations in the composition of the substrate layer between samples, titanium and zirconium are preferred as Group 4 elements, with titanium being more preferred. The substrate layer may also contain two or more Group 4 elements.

[0231] The elements in Group 5 of the periodic table (hereinafter also referred to as "Group 5 elements") are vanadium, niobium, and tantalum. Vanadium is particularly preferred as a Group 5 element from the viewpoint of superior wear resistance in surface treatment layers. The base layer may also contain two or more Group 5 elements.

[0232] The elements in Group 13 of the periodic table (hereinafter also referred to as "Group 13 elements") refer to boron, aluminum, gallium, and indium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing fluctuations in the composition of the substrate layer between samples, boron, aluminum, and gallium are preferred as Group 13 elements, and boron and aluminum are more preferred. The substrate layer may also contain two or more Group 13 elements.

[0233] The elements in Group 15 of the periodic table (hereinafter also referred to as "Group 15 elements") refer to nitrogen, phosphorus, arsenic, antimony, and bismuth. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing fluctuations in the composition of the substrate layer between samples, phosphorus, antimony, and bismuth are preferred as Group 15 elements, and phosphorus and bismuth are more preferred. The substrate layer may also contain two or more Group 15 elements.

[0234] As specific elements contained in the base layer, elements from Group 1, Group 2, and Group 13 are preferred because the surface treatment layer has better wear resistance. Elements from Group 1 and Group 2 are more preferred, and elements from Group 1 are even more preferred.

[0235] As a specific element, it can contain only one element or two or more elements.

[0236] The oxide contained in the substrate layer can be a mixture of individual oxides of the above-mentioned elements (silicon and specific elements) (e.g., a mixture of silicon oxide and oxides of specific elements), a composite oxide containing two or more of the above-mentioned elements, or a mixture of individual oxides of the above-mentioned elements and composite oxides.

[0237] From the viewpoint of having better wear resistance of the surface treatment layer, the ratio of the total molar concentration of the specific element in the substrate layer to the molar concentration of silicon in the substrate layer (specific element / silicon) is preferably 0.02 to 2.90, more preferably 0.10 to 2.00, and even more preferably 0.20 to 1.80.

[0238] The molar concentration (mol%) of each element in the substrate can be determined, for example, by depth-direction analysis based on X-ray photoelectron spectroscopy (XPS) using ion sputtering.

[0239] The base layer can be a single layer or multiple layers. The base layer can also have uneven surfaces.

[0240] The thickness of the substrate layer is preferably 1~100 nm, more preferably 1~50 nm, and even more preferably 2~20 nm. If the thickness of the substrate layer is above the lower limit mentioned above, the adhesion of the surface treatment layer based on the substrate layer is further improved, and the wear resistance of the surface treatment layer is more excellent. If the thickness of the substrate layer is below the upper limit mentioned above, the wear resistance of the substrate layer itself is excellent.

[0241] The thickness of the basal layer was determined by cross-sectional observation of the basal layer based on transmission electron microscopy (TEM).

[0242] The substrate layer can be formed, for example, by vapor deposition or wet coating using vapor deposition materials.

[0243] The vapor deposition material used in the vapor deposition method preferably contains oxides containing silicon and specific elements.

[0244] Specific examples of vapor deposition materials include powder, melt, sintered body, granulated body, and fragmented body. From an operational point of view, melt, sintered body, and granulated body are preferred.

[0245] Here, "molten body" refers to a solid obtained by melting the powder of vapor-deposited material at high temperature and then cooling and solidifying it. "Sintered body" refers to a solid obtained by sintering the powder of vapor-deposited material; if necessary, a molded body formed by pressing the powder can also be used instead of the powder of vapor-deposited material. "Granulated body" refers to a solid obtained by mixing the powder of vapor-deposited material with a liquid medium (such as water or organic solvent) to obtain granules, and then drying the granules.

[0246] Vaporized materials can be manufactured, for example, by the following methods.

[0247] • A method of mixing silicon oxide powder with powder of oxides of specific elements to obtain powder of vapor deposition material.

[0248] • A method for obtaining granules by mixing the powder of the above-mentioned vapor deposition material with water, and then drying the granules to obtain granulated vapor deposition material.

[0249] • A method for obtaining a sintered body by drying a mixture of silicon-containing powder (e.g., powder composed of silicon oxide, silica sand, silica gel), powder containing a specific element (e.g., powder of oxide of a specific element, carbonate, sulfate, nitrate, oxalate, hydroxide), and water, and then firing the dried mixture or a molded body formed by pressing it.

[0250] • A method of obtaining a melt by melting a powder containing silicon (e.g., powder composed of silicon oxide, silica sand, silica gel) and a powder containing a specific element (e.g., powder of oxide of a specific element, carbonate, sulfate, nitrate, oxalate, hydroxide) at a high temperature and then cooling and solidifying the melt.

[0251] As a specific example of a vapor deposition method that uses vapor deposition materials, vacuum vapor deposition can be cited. Vacuum vapor deposition is a method in which vapor deposition materials are evaporated and adhered to the surface of a substrate in a vacuum chamber.

[0252] The preferred temperature for vapor deposition (e.g., the temperature of the vessel in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is 100 to 3,000°C, more preferably 500 to 3,000°C.

[0253] The pressure during vapor deposition (for example, the pressure inside the tank where the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 1 Pa or less, and more preferably 0.1 Pa or less.

[0254] When using vapor deposition materials to form the base layer, one vapor deposition material can be used, or two or more vapor deposition materials containing different elements can be used.

[0255] Specific examples of evaporation methods for vapor-deposited materials include: a resistance heating method in which the vapor-deposited material is melted and evaporated on a boat made of a high-melting-point metal; and an electron gun method in which the vapor-deposited material is irradiated with an electron beam and directly heated to melt and evaporate its surface. From the viewpoint that high-melting-point substances can also evaporate due to localized heating, and from the viewpoint that areas not irradiated by the electron beam are at low temperatures and there is no concern about reaction with the container or contamination of impurities, the electron gun method is preferred as an evaporation method for vapor-deposited materials.

[0256] Evaporation methods for depositing materials can utilize multiple boats or a single boat containing all the depositing materials. Deposition methods can include co-deposition and alternating deposition. Specifically, examples include: using a mixture of silicon dioxide and a specific source in the same boat; co-deposition of silicon dioxide and a specific element source in different boats; and alternating deposition in different boats. The deposition conditions and sequence are appropriately selected based on the composition of the substrate.

[0257] In wet coating methods, it is preferable to form a base layer on a substrate by using a coating liquid containing a silicon-containing compound, a compound containing a specific element, and a liquid medium.

[0258] Specific examples of silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.

[0259] Specific examples of compounds containing a particular element include oxides of a particular element, alkoxides of a particular element, carbonates of a particular element, sulfates of a particular element, nitrates of a particular element, oxalates of a particular element, and hydroxides of a particular element.

[0260] As a liquid medium, examples may be the same liquid medium optionally included in the surface treatment agents described later.

[0261] The content of the liquid medium is preferably 80 to 99.99% by mass, more preferably 90 to 99.9% by mass, relative to the total amount of coating liquid used to form the base layer.

[0262] Specific examples of wet coating methods used to form a substrate layer include spin coating, wiping coating, spray coating, scraper coating, dip coating, mold coating, inkjet coating, flow coating, roller coating, casting, Langmuir-Blodgett method, and gravure coating.

[0263] Preferably, the coating film is dried after the wet coating liquid is applied. The drying temperature of the coating film is preferably 20~200°C, more preferably 80~160°C.

[0264] (Surface roughness Sdr)

[0265] The surface roughness Sdr of the surface treatment layer is above 30% within any measurement area of ​​5~50μm square.

[0266] Surface roughness Sdr is defined in ISO 25178-2:2012 and is an indicator of how much the unfolded area (surface area) of a defined region increases relative to the area of ​​the defined region. It should be noted that the Sdr of a flat surface is 0 (zero).

[0267] In this disclosure, the surface roughness Sdr is measured using atomic force microscopy. Measurements were taken at three locations within a square region of 5–50 μm on one side of the surface-treated layer, and the average value was used.

[0268] From the viewpoint of improving liquid repellency, the surface roughness Sdr is preferably 20% or more, more preferably 30% or more. On the other hand, from the viewpoint of transparency and designability, the surface roughness Sdr is preferably 100% or less, more preferably 50% or less.

[0269] As a method to make the surface roughness Sdr of the surface treatment layer 30% or more in any measurement area of ​​5 to 50 μm square, the following methods can be cited as examples.

[0270] Method 1: Use a substrate with a surface roughness Sdr of 30% or higher.

[0271] Method 2: Set a base layer on the substrate, and make the surface roughness of the base layer greater than 30%.

[0272] In method 1 above, by using a substrate with a surface roughness Sdr of 30% or more, it is possible to make the surface roughness Sdr of the surface treatment layer disposed on the substrate 30% or more.

[0273] In this case, it is preferable to directly provide the surface treatment layer on the substrate without providing a base layer, or if a base layer is provided on the substrate, the thickness of the base layer is less than 1 μm.

[0274] Furthermore, the thickness of the surface treatment layer is preferably 1 μm or less. If the thickness of the surface treatment layer is 1 μm or less, the unevenness of the substrate surface is easily reflected directly on the unevenness of the surface treatment layer surface.

[0275] It should be noted that substrates with a base layer that are usually available are considered as simple "substrates". Alternatively, substrates with a base layer and a surface roughness Sdr of 30% or higher can also be used.

[0276] Methods for achieving a surface roughness Sdr of 30% or more on a substrate include, for example, sandblasting and etching, with etching being preferred.

[0277] Etching can be either dry etching or wet etching.

[0278] In addition, etching can be chemical etching, physical etching, or a combination of chemical and physical etching.

[0279] To achieve a surface roughness Sdr of 30% or higher, it is preferable to pre-clean the substrate before etching.

[0280] The preferred cleaning process includes ultrasonic cleaning using an alkaline solution, ultrasonic cleaning using ultrapure water, and ozone cleaning.

[0281] Ultrasonic cleaning using an alkaline aqueous solution can remove inorganic substances adhering to the surface of a substrate. The ultrasonic cleaning time using an alkaline aqueous solution is, for example, 1 to 30 minutes.

[0282] By using ultrapure water for ultrasonic cleaning, alkaline solutions can be removed, improving the cleaning efficiency in subsequent processes. The ultrasonic cleaning time using ultrapure water is, for example, 1 to 30 minutes.

[0283] Ozone cleaning can remove organic matter adhering to the surface of the substrate.

[0284] Examples of gases used for etching (processing gases) include hydrogen fluoride and fluorine. The processing gas may contain a carrier gas and a diluent gas. Examples of carrier and diluent gases include nitrogen and argon. Water may also be included in the processing gas.

[0285] When the gas being processed contains hydrogen fluoride, the concentration of hydrogen fluoride is preferably 0.01 to 20% by volume, more preferably 0.1 to 5% by volume.

[0286] The flow rate of the processed gas is preferably 1~200 SLM (Standard Liters per Minute), more preferably 30~80 SLM.

[0287] The etching temperature is preferably 400~800℃, more preferably 500~700℃.

[0288] The etching time is preferably 1 to 600 seconds, more preferably 10 to 500 seconds, even more preferably 200 to 500 seconds, and particularly preferably 300 to 500 seconds.

[0289] When the processing gas contains hydrogen fluoride gas, after etching, in order to remove the fluoride formed on the surface of the substrate, it is preferable to use an acidic solution (e.g., an aqueous solution of hydrochloric acid) to clean the substrate.

[0290] In method 2 above, by providing a base layer on the substrate and making the surface roughness Sdr of the base layer 30% or more, the surface roughness Sdr of the surface treatment layer disposed on the base layer can be made to be 30% or more.

[0291] In this case, the thickness of the surface treatment layer is preferably less than 1 μm. If the thickness of the surface treatment layer is less than 1 μm, the unevenness of the substrate surface is easily reflected directly in the unevenness of the surface treatment layer.

[0292] Methods for achieving a surface roughness Sdr of 30% or more in the substrate layer include, for example, sandblasting and etching, with etching being preferred. The preferred method for etching is as described above.

[0293] (Surface treatment agent)

[0294] The surface treatment layer was treated with a surface treatment agent.

[0295] The surface treatment agent comprises a compound having a chain-like group (in one manner, a chain-like organo(poly)siloxane residue) and a reactive silyl group (specific silane compound A).

[0296] The following is a detailed description of each component contained in the surface treatment agent.

[0297] <Specific silane compounds>

[0298] The specific silane compound has a chain-like group and a reactive silyl group. Specific silane compound A has a chain-like organo(poly)siloxane residue and a reactive silyl group. The surface treatment agent disclosed herein may contain only one specific silane compound or may contain two or more specific silane compounds.

[0299] (Chain group)

[0300] Certain silane compounds contain chain-like groups. These chain-like groups can be straight chains without branches or branched chains. As long as a particular silane compound contains chain-like groups, it may have other structures, such as cyclic structures, or it may not have them.

[0301] There are no particular restrictions on chain-like groups as long as they have a chain structure formed by the connection of two or more atoms. Examples include chain-like hydrocarbon groups; chain-like organo(poly)siloxane residues; and chains with -O-, -S-, -C(=O)NH-, -NHC(=O)-, or -N(R) atoms at the end of the chain-like hydrocarbon group or between carbon atoms. d The group consisting of at least one of the following: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene; combinations thereof, etc. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0302] Examples of chain-like hydrocarbon groups include straight-chain or branched chain-like hydrocarbon groups with 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80. As chain-like hydrocarbon groups, alkylene groups are preferred, and alkylene groups with the aforementioned number of carbon atoms are more preferred. From the viewpoint of forming a surface-treated layer with excellent acid resistance, hot water resistance, and abrasion resistance, chain-like hydrocarbon groups with 13 or more carbon atoms are preferred.

[0303] The chain-like hydrocarbon group has a terminal or carbon-carbon atom spacing of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R)-. d The number of carbon atoms in at least one of the groups consisting of -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene is the same as that described above. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0304] In one embodiment, chain-like organo(poly)siloxane residues are preferred as chain-like groups. The chain-like organo(poly)siloxane residues are described in detail below.

[0305] (Chain-like organo(poly)siloxane residues)

[0306] A specific silane compound may contain one or more chain-like organo(poly)siloxane residues. In the case where a specific silane compound contains two or more chain-like organo(poly)siloxane residues, these residues may be the same or different.

[0307] Examples of chain organo(poly)siloxane residues include those represented by formulas (B1) or (B2) below.

[0308]

[0309]

[0310] In formula (B1),

[0311] R 3 Each is an independent hydrocarbon group.

[0312] k1 is a number greater than or equal to 1.

[0313] This refers to the bonding site with adjacent atoms.

[0314] In formula (B2),

[0315] R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -,

[0316] T 11 Each is an independent monovalent group.

[0317] B can be independently -O- or -C (=O)-.

[0318] r can be 0 or 1 independently.

[0319] R 3 Each is an independent hydrocarbon group.

[0320] k1 are each an independent number greater than or equal to 1.

[0321] * indicates the bonding site with an adjacent atom.

[0322] In equations (B1) and (B2), R is used as... 3Examples of hydrocarbon groups shown include aliphatic and aromatic hydrocarbon groups. The hydrocarbon group is preferably aliphatic, and more preferably alkyl. The alkyl group can be any of straight-chain alkyl, branched alkyl, and cyclic alkyl, preferably straight-chain alkyl, more preferably methyl, ethyl, n-propyl, or n-butyl, and even more preferably methyl. Additionally, phenyl is preferred as an aromatic hydrocarbon group.

[0323] In formulas (B1) and (B2), k1 is a number greater than or equal to 1, preferably a number from 1 to 600, more preferably a number from 1 to 500, even more preferably a number from 3 to 500, particularly preferably a number from 9 to 50, extremely preferably a number from 11 to 30, and most preferably a number from 11 to 25.

[0324] In equation (B2), R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 - Preferably, a hydrocarbon group. Details of the hydrocarbon group are related to R. 3 The same applies to the hydrocarbon groups shown.

[0325] T 11 Each is an independent monovalent group, specifically as described in formula (C) below, where T is the same. 11 same.

[0326] The specific manner of B and r is the same as that of B and r in equation (C) described later.

[0327] (Reactive silane)

[0328] The number of reactive silane alkyl groups contained in the specific silane compound is 1 or more. From the viewpoint of further improving the wear resistance of the surface treatment layer, 1 to 18 is preferred, 1 to 12 is more preferred, 1 to 8 is even more preferred, 1 to 6 is particularly preferred, and 1 to 4 is extremely preferred. In one embodiment, the number of reactive silane alkyl groups contained in the specific silane compound is preferably 2 to 18, more preferred, 2 to 12, even more preferred, 2 to 8, and particularly preferred, 2 to 6. The number of reactive silane alkyl groups may be 1.

[0329] Reactive silyl groups refer to groups with reactive groups bonded to Si atoms. Preferably, the reactive group is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0330] Hydrolyzable groups are groups that become hydroxyl groups through hydrolysis. That is, Si-L 1 (L) 1The hydrolyzable silane group (represented by a hydrolyzable group) undergoes a hydrolysis reaction to become a silanol group (represented by Si-OH). The silanol groups further react with each other to form Si-O-Si bonds. Alternatively, the silanol groups can undergo a dehydration condensation reaction with silanol groups from oxides present on the substrate surface to form Si-O-Si bonds.

[0331] Examples of hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, amino groups, and -ON=CR groups. r 2. An isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group with 1 to 4 carbon atoms. The aryloxy group is preferably an aryloxy group with 3 to 10 carbon atoms. The aryl group of the aryloxy group includes heteroaryl groups. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group with 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group with 1 to 6 carbon atoms. R r Each is an alkyl group having 1 to 10 carbon atoms.

[0332] Examples of groups having hydrolyzable groups include those having the hydrolyzable groups described above. Preferably, the group having a hydrolyzable group is -OL. A -L B L A It is an alkylene group, L B It is a hydrolyzable group. The alkylene group preferably has 1 to 10 carbon atoms. B The hydrolyzable groups indicated have the same meaning as the hydrolyzable groups mentioned above, and the preferred methods are also the same.

[0333] The reactive silyl group is preferably a group represented by the following formula (S1).

[0334] -Si(R) 2 ) n L 3-n …(S1)

[0335] In formula (S1),

[0336] R 2 Each is an independent monovalent hydrocarbon group.

[0337] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0338] n is an integer between 0 and 2.

[0339] When a molecule contains multiple reactive silane groups, these reactive silane groups may be the same or different from each other. From the viewpoint of ease of obtaining the raw materials and ease of manufacturing the compound, it is preferable that the multiple reactive silane groups are the same.

[0340] R 2Each is an independent monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. R 2 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0341] L can be a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Details of hydrolyzable groups and groups having hydrolyzable groups are as described above.

[0342] From the viewpoint of ease of compound manufacture, L is preferably an alkoxy or halogen atom with 1 to 4 carbon atoms. From the viewpoint of less venting during coating and better storage stability of the compound, L is preferably an alkoxy with 1 to 4 carbon atoms, and more preferably an ethoxy or methoxy atom.

[0343] n is an integer from 0 to 2, preferably 0 or 1, and more preferably 0. By having multiple Ls, the adhesion of the surface treatment layer to the substrate becomes stronger.

[0344] When n is 1 or less, the multiple L's present in one molecule can be the same or different from each other. From the viewpoint of ease of obtaining raw materials and ease of manufacturing the compound, it is preferable that the multiple L's are the same. When n is 2, the multiple R's present in one molecule... 2 They can be the same or different from each other. From the viewpoint of ease of obtaining raw materials and ease of manufacturing compounds, multiple Rs are preferred. 2 same.

[0345] From the viewpoint of excellent uniformity and durability of the surface-treated layer, the reactive silane is preferably alkoxysilane or trichlorosilane. From the viewpoint of ease of handling of byproducts generated during the reaction with the substrate, the reactive silane is more preferably alkoxysilane. As an alkoxysilane, dialkoxysilane or trialkoxysilane is preferred, and trialkoxysilane is more preferred.

[0346] In addition, the reactive silyl group can be a group represented by the following formula (S2).

[0347] >SiL2…(S2)

[0348] L is the same as L in equation (S1).

[0349] The reactive silyl group is also preferably represented by the group shown in the following formula (S3).

[0350] -[Si(L) 2 )2-P] r1 -Si(L 2 )3…(S3)

[0351] In formula (S3),

[0352] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0353] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0354] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0355] r1 is an integer from 1 to 3.

[0356] When there are multiple groups (S3) in a molecule, the multiple groups (S3) can be the same or different from each other. From the viewpoint of ease of obtaining raw materials and ease of manufacturing the compound, it is preferable that the multiple groups (S3) are the same.

[0357] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0358] Details of hydrolyzable groups and groups having hydrolyzable groups are as described above.

[0359] From the perspective of the ease of compound preparation, L 2 The hydrolyzable groups or groups containing hydrolyzable groups are preferably alkoxy groups with 1 to 4 carbon atoms, epoxy-modified alkoxy groups, or halogen atoms. From the viewpoint of less venting during coating and better storage stability of the compound, L... 2 Preferably, the alkoxy group has 1 to 4 carbon atoms, and more preferably, the ethoxy or methoxy group.

[0360] As L 2 Examples of hydrocarbon groups include alkyl, cycloalkyl, alkenyl, and allyl groups. From the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0361] r1 is an integer from 1 to 3. From the viewpoint of ease of synthesis, it is preferably 1 to 2, and more preferably 1.

[0362] A group (S3) possesses multiple L 2 At least four of the groups in the group (S3) are hydrolyzable groups, groups having hydrolyzable groups, or hydroxyl groups. Thus, the group (S3) bonds more firmly to the substrate, resulting in a surface treatment layer with excellent durability. From this perspective, the number of hydrolyzable groups, groups having hydrolyzable groups, and hydroxyl groups in the group (S3) is preferably 4 to 9, more preferably 4 to 7, and even more preferably 4 or 5.

[0363] It should be noted that multiple L molecules exist within one molecule. 2 They can be the same or different from each other. For example, multiple Ls 2 They can be the same hydrolyzable groups.

[0364] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. Here, "an organic group having one carbon atom bonded to the two adjacent Si atoms" means that the Si atoms are connected to each other via one carbon atom. Examples of P include hydrocarbon groups, such as -CH2-, -C(CH3)2-, etc. From the viewpoint of the durability of the surface treatment layer, oxygen atoms, -CH2-, or -C(CH3)2- are preferred as P, oxygen atoms or -CH2- are more preferred, and oxygen atoms are even more preferred.

[0365] From the viewpoint of excellent durability of the surface treatment layer, the group (S3) is preferably -[Si(OR)] 12 )2-O] r1 -Si(OR) 12 )3, wherein, particularly preferred is -Si(OR) with r1=1. 12 )2-O-Si(OR 12 3. Here, R 12 Each is an independent hydrocarbon group. Examples of hydrocarbon groups include alkyl, cycloalkyl, alkenyl, and allyl groups; from the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. R 12 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0366] Specific examples of the group (S3) include -Si(OCH3)2-O-Si(OCH3)3, -Si(OCH3)2-CH2-Si(OCH3)3, -Si(OCH3)2-C(CH3)2-Si(OCH3)3, -Si(OCH2CH3)2-O-Si(OCH3)3, -Si(OCH3)2-O-Si(OCH2CH) 3) 3. -Si(OCH2CH3)2-O-Si(OCH2CH3)3. -Si(OCH2CH3)2-CH2-Si(OCH3)3. -Si(OCH3)2-CH2-Si(OCH2CH3)3. -Si(OCH2CH3)2-CH2-Si(OCH2CH3)3. Si(OCH3)3, -Si(OCH3)2-C(CH3)2-Si(OCH2CH3)3, -Si(OCH2CH3)2-C(CH3)2-Si(OCH2CH3)3, -Si(OH)2-O-Si(OH)3, -Si(OH)2-O-Si(OCH3)3, -Si(OCH3)2-O-Si(OH)3, -Si( OH)2-CH2-Si(OH)3, -Si(OH)2-CH2-Si(OCH3)3, -Si(OCH3)2-CH2-Si(OH)3, -Si(OH)2-C(CH3)2-Si(OH)3, -Si(OH)2-C(CH3)2-Si(OCH3)3, -Si(OCH3)2-C(CH3)2-Si(OH)3.

[0367] The number-average molecular weight (Mn) of the specific silane compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000.

[0368] If Mn is above 500, the surface treatment layer exhibits superior wear resistance. If Mn is below 20,000, the viscosity is easily adjusted to an appropriate range, and the solubility is improved, resulting in excellent operability during film formation.

[0369] Surface treatment agents may contain impurities such as byproducts generated during the manufacturing process of specific silane compounds.

[0370] The content of the specific silane compound relative to the total amount of the surface treatment agent is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass. In the case of the surface treatment agent used in the wet coating method, the content of the specific silane compound relative to the total amount of the surface treatment agent can be 0.01 to 10% by mass, 0.02 to 5% by mass, 0.03 to 3% by mass, or 0.05 to 2% by mass.

[0371] Examples of specific silane compounds include compounds having chain-like organo(poly)siloxane residues and a reactive silyl group connected to only one end of the aforementioned chain-like organo(poly)siloxane residues (hereinafter also referred to as "Compound 1"), and compounds having chain-like organo(poly)siloxane residues and reactive silyl groups connected to both ends of the aforementioned chain-like organo(poly)siloxane residues (hereinafter also referred to as "Compound 2").

[0372] As a specific silane compound, compound 1 can be used alone, compound 2 can be used alone, or compound 1 and compound 2 can be used in combination. In any case, compound 1 can be used alone or in combination with two or more compounds, and compound 2 can be used alone or in combination with two or more compounds.

[0373] [Compound 1]

[0374] The first compound has a chain-like organo(poly)siloxane residue and a reactive silyl group attached only to one end of the aforementioned chain-like organo(poly)siloxane residue. In this disclosure, "a reactive silyl group attached only to one end of the chain-like organo(poly)siloxane residue" means a reactive silyl group attached directly or indirectly via other chemical structures to one end of the chain-like organo(poly)siloxane residue.

[0375] (Chain-like organo(poly)siloxane residues)

[0376] The first compound contains chain-like organo(poly)siloxane residues. The first compound may contain one or more chain-like organo(poly)siloxane residues. When the first compound contains two or more chain-like organo(poly)siloxane residues, these residues may be the same or different. When the first compound contains two or more chain-like organo(poly)siloxane residues, there may be no chain-like organo(poly)siloxane residues with reactive silyl groups attached to both ends, and at least one chain-like organo(poly)siloxane residue may have a reactive silyl group attached to one end.

[0377] Details of the chain organo(poly)siloxane residues are as described in the section on chain organo(poly)siloxane residues contained in a particular silane compound. In particular, the chain organo(poly)siloxane residues are preferably represented by formula (B1) or (B2), more preferably by formula (B1).

[0378] (Reactive silane)

[0379] Details of reactive silanes are described in the section on reactive silanes contained in a particular silane compound.

[0380] The number of reactive silyl groups contained in the first compound is 1 or more at each end of the chain organo(poly)siloxane residues. From the viewpoint of further improving the wear resistance of the surface treatment layer, it is preferably 1 to 18 at each end of the chain organo(poly)siloxane residues, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, the number of reactive silyl groups contained in the first compound is preferably 2 to 18 at each end of the chain organo(poly)siloxane residues, more preferably 2 to 12, even more preferably 2 to 8, and particularly preferably 2 to 6. The number of reactive silyl groups at each end of the chain organo(poly)siloxane residues may be 1.

[0381] (Compound (C))

[0382] In one embodiment, the first compound is preferably represented by the following formula (C).

[0383]

[0384] In formula (C),

[0385] T 11 It is a monovalent group that does not contain reactive silyl groups.

[0386] B can be independently -O- or -C (=O)-.

[0387] r can be 0 or 1 independently.

[0388] R 3 Each is an independent hydrocarbon group.

[0389] k1 are each an independent number greater than or equal to 1.

[0390] p1 is an integer greater than or equal to 1.

[0391] A 11 It is a (p1+q1) valence linker.

[0392] q1 is an integer greater than or equal to 1.

[0393] R2 Each is an independent hydrocarbon group.

[0394] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0395] n is an independent integer from 0 to 2.

[0396] In equation (C), R 3 and k1 and R in equation (B1) 3 The same applies to k1.

[0397] R 2 L and n and R in equation (S1) 2 The same applies to L and n.

[0398] In equation (C), T 11 It is a monovalent group.

[0399] As T 11 Examples include: alkyl groups, T 1 3M 1 - (Here, M) 1 For Si, Sn or Ge, T 1 Each is independently a hydrocarbon group or a trialkylsilyloxy group), T 1 3M 1 -R 1 - (Here, M) 1 For Si, Sn or Ge, T 1 Each is independently a hydrocarbon group or a trialkylsilyloxy group, R 1 It can be an alkylene group, a monovalent cyclic polysiloxane residue or a monovalent cage-like polysiloxane residue, or a combination of a monovalent cyclic polysiloxane residue or a monovalent cage-like polysiloxane residue and a divalent hydrocarbon group.

[0400] T 11 The alkyl group shown can be any of the following: straight-chain alkyl, branched alkyl, and cyclic alkyl, preferably straight-chain or branched alkyl. The alkyl group can have 1 or more carbon atoms. When the alkyl group has 2 or more carbon atoms, the number of carbon atoms is preferably 2 to 30, more preferably 3 to 28, and even more preferably 4 to 22.

[0401] As T 1 3M 1 -and T 1 3M 1 -R 1 M in - 1 Si is preferred.

[0402] As T 1 3M 1 -and T 1 3M1 -R 1 - in T 1 Preferably alkyl or trialkylsiloxy, more preferably methyl, butyldimethylsiloxy, trimethylsiloxy, or triethylsiloxy.

[0403] As R 1 Preferably, it is an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 5 carbon atoms, and particularly preferably an ethylene group.

[0404] In one approach, T 11 Preferably alkyl or trialkylsilyl, more preferably methyl or trimethylsilyl.

[0405] The monovalent cyclic polysiloxane residues are preferably groups represented by the following formula (T1).

[0406] In equation (T1),

[0407] R T Each is independently a hydrocarbon group or a hydrocarbon group with substituents.

[0408] s is an integer from 1 to 4.

[0409]

[0410] As R T The hydrocarbon group shown can be, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Preferably, the hydrocarbon group is an aliphatic hydrocarbon group, and more preferably an alkyl group.

[0411] R T In the hydrocarbon group represented, the alkyl group can be any type of straight-chain alkyl, branched alkyl, and cyclic alkyl, preferably a straight-chain alkyl. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4. Specifically, the alkyl group is preferably methyl, ethyl, n-propyl, or n-butyl, more preferably methyl.

[0412] As R T The hydrocarbon groups contained in the substituted hydrocarbon groups shown can be, for example, aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group can be any type of straight-chain alkyl, branched alkyl, and cyclic alkyl, and is preferably a straight-chain alkyl. The alkyl group contained in the substituted alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 2 to 4.

[0413] As R TSubstituents in the hydrocarbon groups shown can be, for example, halogen atoms, hydroxyl groups, alkoxy groups, trialkylsilyl ethers, trialkylsilyl groups, amino groups, nitro groups, cyano groups, sulfonyl groups, and trifluoromethyl groups.

[0414] Multiple R T They can be the same or different from each other; from the point of view of ease of manufacture, the same is preferred.

[0415] Examples of monovalent cyclic polysiloxane residues include the following groups.

[0416]

[0417] The monovalent cage-like polysiloxane residues are preferably groups represented by the following formula (T2).

[0418] In equation (T2),

[0419] R 5 Each is independently a hydrocarbon group or a trialkylsilyloxy group.

[0420]

[0421] As R 5 The hydrocarbon group shown can be, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group can be any of the following: straight-chain alkyl, branched alkyl, and cyclic alkyl, preferably a straight-chain alkyl or branched alkyl, more preferably methyl, ethyl, n-propyl, n-butyl, or isobutyl, and even more preferably isobutyl.

[0422] R 5 The alkyl group contained in the trialkylsilyloxy group can be any of the following: straight-chain alkyl, branched alkyl, and cyclic alkyl, preferably a straight-chain alkyl, more preferably methyl, ethyl, n-propyl, or n-butyl, and even more preferably methyl. R 5 In the case of trialkylsiloxy groups, the three alkylsiloxy groups may be the same or different from each other; from the viewpoint of ease of manufacture, it is preferred that they be the same.

[0423] Examples of monovalent cage-like polysiloxane residues include the following groups.

[0424]

[0425] Examples of divalent hydrocarbon groups in combinations of monovalent cyclic polysiloxane residues or monovalent cage-like polysiloxane residues and divalent hydrocarbon groups include alkylene groups. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

[0426] In formula (C), each B is independently -O- or -C (=O)-, preferably -O-.

[0427] In formula (C), p1 is an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0428] When p1 is 2 or higher, multiple T 11 -B r -[Si(R 3 )2-O] k1 -Si(R) 3 )2- can be the same or different from each other.

[0429] In formula (C), A 11 It is a (p1+q1) valence linker. As A 11 Examples include alkylene groups, organo(poly)siloxane residues, polyepoxyalkyl groups, and combinations thereof; as well as combinations thereof with (p1+1) valence groups and / or (q1+1) valence groups.

[0430] As an alkylene group, examples include those that may or may not have an ether-like oxygen atom, a sulfur atom, -C(=O)NH-, -NHC(=O)-, or -N(R). d An alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, consisting of at least one of the following groups: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene.

[0431] Examples of organo(poly)siloxane residues include the groups shown in the aforementioned formula (B1).

[0432] Examples of polyepoxyalkylene compounds include (XO). m The indicated groups. Here, each X is an alkylene group having 1 to 5 carbon atoms, and m is an integer of 1 or more. The number of carbon atoms in X is preferably 1 to 4, more preferably 2 or 3. m is preferably 1 to 200, more preferably 1 to 20, and even more preferably 1 to 10.

[0433] As A 11 The formula A(Si(R) can be cited as an example. 2 ) n L 3-n ) q1 A in the middle.

[0434] In formula (C), q1 is an integer greater than or equal to 1, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and extremely preferably 2 to 4. q1 may also be 1.

[0435] When q1 is an integer greater than 2, multiple [Si(R)] 2 ) n L 3-n They can be the same or different from each other.

[0436] In one approach, T in equation (C) 11 Preferably, it is trialkylsilyl or alkyl, more preferably trimethylsilyl or methyl.

[0437] B is preferably 0, and r is 0 or 1.

[0438] R 3 Methyl is preferred.

[0439] k1 is preferably 1~100.

[0440] p1 is preferably 1.

[0441] A 11 Preferably, it is an alkylene group having 1 to 30 carbon atoms, or Si(R) removed from the group (3-1A) described later. 2 ) n L 3-n The resulting group is more preferably an alkylene group having 1 to 30 carbon atoms, or a group (3-1A-4) having Si (R) removed from it. 2 ) n L 3-n The resulting functional group.

[0442] q1 is preferably an integer from 1 to 4.

[0443] (Compound (C2))

[0444] In another embodiment, the first compound is preferably represented by the following formula (C2).

[0445]

[0446] In formula (C2),

[0447] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0448] L 2 At least 4 L in 2It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0449] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0450] r1 is an integer from 1 to 3.

[0451] T 11 B, r, R 3 k1, p1, A 11 The definitions of q1 and q1 are the same as those in equation (C).

[0452] In equation (C2), T 11 B, r, R 3 k1, p1, A 11 The specific method of q1 is the same as that in equation (C).

[0453] In formula (C2), L 2 The specific methods of P and r1 are the same as those of L in equation (S3). 2 The specific methods for P and r1 are the same.

[0454] The number-average molecular weight (Mn) of the first compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000. In one embodiment, the Mn of the first compound may be 500 to 5,000 or 500 to 3,000.

[0455] If Mn is above 500, the surface treatment layer exhibits superior wear resistance. If Mn is below 20,000, the viscosity is easily adjusted to an appropriate range, and the solubility is improved, resulting in excellent operability during film formation.

[0456] The surface treatment agent may contain only one first compound or two or more first compounds.

[0457] Surface treatment agents may also include impurities such as byproducts generated during the manufacturing process of the first compound.

[0458] The content of the first compound relative to the total amount of the surface treatment agent is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass. In the case of a surface treatment agent used in a wet coating method, the content of the first compound relative to the total amount of the surface treatment agent can be 0.01 to 10% by mass, 0.02 to 5% by mass, 0.03 to 3% by mass, or 0.05 to 2% by mass.

[0459] The content of the first compound is preferably 5% by mass or more and less than 65% by mass relative to the total solid content of the surface treatment agent, more preferably 10 to 64% by mass, and can be 20 to 60% by mass or 30 to 50% by mass.

[0460] [Compound 2]

[0461] The second compound has chain-like organo(poly)siloxane residues and reactive silyl groups respectively attached to both ends of the aforementioned chain-like organo(poly)siloxane residues. In this disclosure, "reactive silyl groups respectively attached to both ends of the chain-like organo(poly)siloxane residues" refers to reactive silyl groups directly or indirectly attached to both ends of the chain-like organo(poly)siloxane residues via other chemical structures.

[0462] (Chain-like organo(poly)siloxane residues)

[0463] The second compound contains chain-like organo(poly)siloxane residues. The second compound may contain one or more chain-like organo(poly)siloxane residues. When the second compound contains two or more chain-like organo(poly)siloxane residues, these residues may be the same or different. When the second compound contains two or more chain-like organo(poly)siloxane residues, at least one chain-like organo(poly)siloxane residue may have a reactive silyl group attached to both ends.

[0464] Details of the chain organo(poly)siloxane residues are as described in the section on chain organo(poly)siloxane residues contained in a particular silane compound. In particular, the chain organo(poly)siloxane residues are preferably represented by formula (B1) or (B2), more preferably by formula (B1).

[0465] (Reactive silane)

[0466] Details of reactive silanes are described in the section on reactive silanes contained in a particular silane compound.

[0467] The second compound contains at least one reactive silyl group at each end of the chain organo(poly)siloxane residues. From the viewpoint of further improving the wear resistance of the surface treatment layer, it is preferably 1 to 18 at each end of the chain organo(poly)siloxane residues, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, the second compound contains at least 2 to 18 reactive silyl groups at each end of the chain organo(poly)siloxane residues, more preferably 2 to 12, even more preferably 2 to 8, and particularly preferably 2 to 6. The number of reactive silyl groups at each end of the chain organo(poly)siloxane residues may be 1.

[0468] (Compound (D))

[0469] In one embodiment, the second compound is preferably represented by the following formula (D).

[0470]

[0471] In equation (D),

[0472] R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -,

[0473] T 11 Each is an independent monovalent group.

[0474] B can be independently -O- or -C (=O)-.

[0475] r can be 0 or 1 independently.

[0476] R 3 Each is an independent hydrocarbon group.

[0477] k1 are each an independent number greater than or equal to 1.

[0478] A 12 Each is an independent (q1+1) valence linker.

[0479] Each q1 is an independent integer greater than or equal to 1.

[0480] R 2 Each is an independent hydrocarbon group.

[0481] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0482] n is an independent integer from 0 to 2.

[0483] In equation (D), R 4 and k1 and R in equation (B2) 4 The same applies to k1.

[0484] R 2 L and n and R in equation (S1) 2 The same applies to L and n.

[0485] As A 12 Examples include alkylene groups, organo(poly)siloxane residues, polyepoxyalkyl groups, and combinations thereof; as well as combinations thereof with (q1+1) valence groups.

[0486] As an alkylene group, examples include those that may or may not have an ether-like oxygen atom, a sulfur atom, -C(=O)NH-, -NHC(=O)-, or -N(R). d An alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, consisting of at least one of the following groups: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2- and phenylene.

[0487] Examples of organo(poly)siloxane residues include the groups shown in formula (B1) or (B2) above.

[0488] Examples of polyepoxyalkylene compounds include (XO). m The indicated groups. Here, each X is an alkylene group having 1 to 5 carbon atoms, and m is an integer of 1 or more. The number of carbon atoms in X is preferably 1 to 4, more preferably 2 or 3. m is preferably 1 to 100, more preferably 1 to 10, and even more preferably 1 to 5.

[0489] As A 12 The formula A(Si(R) can be cited as an example. 2 ) n L 3-n ) q1 The (q1+1) valence group in A.

[0490] Each q1 is an integer greater than or equal to 1, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and extremely preferably 2 to 4. q1 may also be 1.

[0491] When q1 is an integer greater than 2, multiple [Si(R)] 2) n L 3-n They can be the same or different from each other.

[0492] In one approach, R 4 Methyl is preferred.

[0493] k1 is preferably a number between 1 and 100.

[0494] A 12 Preferably, it is an alkylene group having 1 to 30 carbon atoms, or Si(R) removed from the group (3-1A) described later. 2 ) n L 3-n The resulting group is more preferably an alkylene group having 1 to 30 carbon atoms, or a group (3-1A-4) having Si (R) removed from it. 2 ) n L 3-n The resulting functional groups.

[0495] q1 is preferably an integer from 1 to 4.

[0496] (Compound (D2))

[0497] In another embodiment, the second compound is preferably represented by the following formula (D2).

[0498]

[0499] In equation (D2),

[0500] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0501] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0502] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0503] r1 is an independent integer from 1 to 3.

[0504] R 4 k1, A 12 The definitions of q1 and q1 are the same as those in equation (D).

[0505] In equation (D2), R 4 k1, A 12 The specific method of q1 is the same as that in equation (D).

[0506] In formula (D2), L2 The specific methods of P and r1 are the same as those of L in equation (S3). 2 The specific methods for P and r1 are the same.

[0507] The number-average molecular weight (Mn) of the second compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000. In one embodiment, the Mn of the second compound may be 500 to 5,000, or may be 500 to 3,000 or less.

[0508] If Mn is above 500, the surface treatment layer exhibits superior wear resistance. If Mn is below 20,000, the viscosity is easily adjusted to an appropriate range, and the solubility is improved, resulting in excellent operability during film formation.

[0509] The surface treatment agent may contain only one second compound or two or more second compounds.

[0510] The surface treatment agent may contain impurities such as byproducts generated during the manufacturing process of the second compound.

[0511] The content of the second compound relative to the total amount of the surface treatment agent is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass. In the case of a surface treatment agent used in a wet coating method, the content of the second compound relative to the total amount of the surface treatment agent can be 0.01 to 10% by mass, 0.02 to 5% by mass, 0.03 to 3% by mass, or 0.05 to 2% by mass.

[0512] The content of the second compound relative to the total solids content of the surface treatment agent is preferably more than 35% by mass and less than 95% by mass, more preferably 36 to 90% by mass, and can be 40 to 80% by mass or 50 to 70% by mass. The content of the second compound can be 35 to 95% by mass.

[0513] [Compound (E) or (E2)]

[0514] In one manner, a particular silane compound may be a compound represented by formula (E).

[0515]

[0516] In formula (E),

[0517] B 11 It is a monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups; or it is a monovalent group comprising a branched alkyl group.

[0518] u1 is an integer greater than or equal to 1.

[0519] A 13 It is a (q1+u1) valence linker.

[0520] q1 is an integer greater than or equal to 1.

[0521] R 2 Each is an independent hydrocarbon group.

[0522] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0523] n is an independent integer from 0 to 2.

[0524] In equation (E), R 2 L and n and R in equation (S1) 2 The same applies to L and n.

[0525] q1 is the same as q1 in equation (C).

[0526] B 11 It is a monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups; or it is a monovalent group comprising a branched alkyl group. The monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups, may or may not comprise Si, Ge, or Sn with directly bonded hydroxyl or hydrolyzable groups.

[0527] In one approach, B 11 It can be a group having a group (a) or a group (b).

[0528]

[0529]

[0530] In formula (a),

[0531] R 51 For - (R 61 -SiR 53 2) ma -R 53 The group shown, here R 61 Each is independently an oxygen atom or an alkylene group having 1 to 6 carbon atoms, R 53 Each is independently a hydrocarbon group or R 51' R 51' With R 51 The meanings are the same, where ma is an integer from 1 to 5, and R 51 In the middle, R 51' The number is less than 20.

[0532] R 52 It is a hydrocarbon group.

[0533] na is an integer from 1 to 3.

[0534] z is 0 or 1.

[0535] * indicates the bonding site with an adjacent atom.

[0536] In equation (b),

[0537] R 54 Each is an independent hydrocarbon group.

[0538] nb is an integer from 1 to 5.

[0539] z is 0 or 1.

[0540] * indicates the bonding site with an adjacent atom.

[0541] R 61 The alkylene groups having 1 to 6 carbon atoms can be straight-chain or branched. Preferably, the alkylene groups having 1 to 6 carbon atoms are alkylene groups having 1 to 4 carbon atoms, and more preferably, alkylene groups having 2 to 4 carbon atoms.

[0542] R 53 The hydrocarbon group represented is preferably alkyl or aryl. The alkyl group can be straight-chain or branched. As an alkyl group, it is preferred to be an alkyl group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and even more preferably methyl, ethyl, n-propyl, isopropyl or tert-butyl.

[0543] R 52 The hydrocarbon group represented is preferably alkyl or aryl. The alkyl group can be straight-chain or branched. As an alkyl group, it is preferred to be an alkyl group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and even more preferably methyl, ethyl, n-propyl, isopropyl or tert-butyl.

[0544] As a group having a group (a) or a group (b), examples can be given of a group (a) or a group (b) alone, and a group having a chain-like group attached to a group (a) or a group (b).

[0545] Examples of chain-like groups include chain-like hydrocarbon groups; chain-like organo(poly)siloxane residues; and groups with a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, or -N(R) at the end of the chain-like hydrocarbon group or between carbon-carbon atoms. dThe group consisting of at least one of the following: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene; combinations thereof, etc. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0546] Examples of chain-like hydrocarbon groups include straight-chain or branched chain-like hydrocarbon groups with 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80. As chain-like hydrocarbon groups, alkylene groups are preferred, and from the viewpoint of forming a surface treatment layer with excellent acid resistance, hot water resistance, and abrasion resistance, alkylene groups with 13 or more carbon atoms are preferred.

[0547] The chain-like hydrocarbon group has a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R)- at the end or between carbon-carbon atoms. d The number of carbon atoms in at least one of the groups consisting of -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene is the same as that described above. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0548] Examples of chain-like organo(poly)siloxane residues can be cited above as chain-like organo(poly)siloxane residues in specific silane compounds.

[0549] In one approach, B 11 It can be a group with a group (c).

[0550] -M 31 (R) 31 )2- …(c)

[0551] In equation (c),

[0552] M 31 For Sn or Ge,

[0553] R 31 Each is independently a hydrocarbon group or a trialkylsilyloxy group.

[0554] M 31 It can be Sn or Ge. Because Ge has a larger atomic size than Sn, it can further reduce the surface free energy and form a surface treatment layer with excellent fingerprint removal properties; therefore, M... 31 Ge is preferred.

[0555] R 31 It is a hydrocarbon group or a trialkylsilyloxy group.

[0556] Examples of hydrocarbon groups include alkyl, cycloalkyl, alkenyl, and allyl groups. From the perspective of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. 31 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, wherein -CH3 or -CH2CH3 is preferred.

[0557] Trialkylsilyloxy group preferably uses -O-SiR 40 3 represents the group. Wherein, R 40 Each is an independent hydrocarbon group. R 40 The hydrocarbon group in R is preferably alkyl or aryl, more preferably alkyl. 40 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. As R 40 Specific examples of hydrocarbon groups in this context include -CH3, -CH2CH3, and -C(CH3)3.

[0558] As a group having a group (c), examples can be given of group (c) alone, and in the M of group (c). 31 A group having an organic group attached to one or both sides. Examples of organic groups include monovalent organic groups, divalent organic groups, and combinations thereof. However, a group without monovalent organic groups attached to either side is also an organic group.

[0559] Examples of monovalent organic groups include hydrocarbon groups, trialkylsilyloxy groups, or organopolysiloxane groups. Group (c) can be M... 31 (R) 31 )3-.

[0560] Examples of divalent organic groups include chain-like hydrocarbon groups; chain-like organo(poly)siloxane residues; and groups with carbon-carbon atoms at the end of the chain-like hydrocarbon group or with a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, or -N(R)-. d The group consisting of at least one of the following: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene; combinations thereof, etc. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0561] Examples of chain-like hydrocarbon groups include straight-chain or branched chain-like hydrocarbon groups with 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80. Examples of chain-like hydrocarbon groups include alkyl or alkylene groups. From the viewpoint of forming a surface treatment layer with excellent acid resistance, hot water resistance, and abrasion resistance, chain-like hydrocarbon groups are preferably alkylene groups with 13 or more carbon atoms.

[0562] The chain-like hydrocarbon group has a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R)- at the end or between carbon-carbon atoms. d The number of carbon atoms in at least one of the groups consisting of -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene is the same as that described above. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0563] Examples of chain-like organo(poly)siloxane residues can be cited above as chain-like organo(poly)siloxane residues in specific silane compounds.

[0564] In one approach, B 11 The branched alkyl group can be a monovalent group containing a branched alkyl group. The branched alkyl group is preferably unsubstituted. The branched alkyl group is preferably tert-butyl or contains tert-butyl. The branched alkyl group can contain one branch or multiple branches. The number of branches in the branched alkyl group can be 1 to 30, 1 to 20, 1 to 10, or 1 to 5.

[0565] As branched alkyl groups, examples include the groups represented by the following formulas.

[0566] [(CH3)3C-R] 22 -] m22 C(CH3) 3-m22 -

[0567] In the formula,

[0568] R 22 Each is independently an alkylene group having 1 to 6 carbon atoms.

[0569] m22 is an integer between 0 and 3.

[0570] Examples of monovalent groups containing branched alkyl groups include groups in which a chain-like group is attached to a carbon atom at the branch point of the branched alkyl group.

[0571] Examples of chain-like groups include chain-like hydrocarbon groups; chain-like organo(poly)siloxane residues; groups having at least one of the following selected from the group consisting of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2O-, -OS(=O)2- and phenylene; and combinations thereof.

[0572] Examples of chain-like hydrocarbon groups include straight-chain or branched chain-like hydrocarbon groups with 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80. As chain-like hydrocarbon groups, alkylene groups are preferred, and from the viewpoint of forming a surface treatment layer with excellent acid resistance, hot water resistance, and abrasion resistance, alkylene groups with 13 or more carbon atoms are preferred.

[0573] The chain-like hydrocarbon group has a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R)- at the end or between carbon-carbon atoms. d The number of carbon atoms in at least one of the groups consisting of -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2-, and phenylene is the same as that described above. d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0574] Examples of chain-like organo(poly)siloxane residues can be cited above as chain-like organo(poly)siloxane residues in specific silane compounds.

[0575] In equation (E), u1 is an integer greater than or equal to 1. From the viewpoint of ease of manufacture, u1 is preferably 1 to 6, and more preferably 1 to 4.

[0576] In equation (E), A 13 It is a (q1+u1) valence linker. As A 13 Examples of A in equation (C) can be cited. 11 The same specific example.

[0577] As compound (E), it can be the following compound: B 11 For group (a) or M 31 (R) 31 )3-, u1 is 1, A 13 The carbon atom-carbon atom gap can have or not have a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R)-. dThe alkylene group consisting of at least one of the following: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2- and phenylene, having 1 to 30 carbon atoms, and q1 being 1.

[0578] As compound (E), it can be the following compound: B 11 For group (a) or M 31 (R) 31 )3-, u1 is 1, A 13 The carbon atom-carbon atom gap can have or not have a selection of -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R)-. d The group consisting of at least one of the following: -, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)2NH-, -NHS(=O)2-, -S(=O)2-, -S(=O)2O-, -OS(=O)2- and phenylene, wherein q1 is 2 or 3.

[0579] R d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0580] Specific examples of compound (E) include the following compounds. In the following formulas, sa is preferably 1 to 30, more preferably 4 to 20, and even more preferably 5 to 15.

[0581]

[0582] In one approach, a particular silane compound may be a compound represented by formula (E2).

[0583]

[0584] In formula (E2),

[0585] L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0586] L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0587] Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms.

[0588] r1 is an independent integer from 1 to 3.

[0589] B 11 u1, A 13 The definitions of q1 and q1 are the same as those in equation (E).

[0590] B 11 u1, A 13 The specific method of q1 is the same as that in equation (E).

[0591] L 2 The specific methods of P and r1 are the same as those in equation (S3).

[0592] [Partial structures of compound 1, compound 2, and compound (E)]

[0593] Below, we will discuss A in equation (C). 11 (Si(R) 2 ) n L 3-n ) q1 A in formula (D) 12 (Si(R) 2 ) n L 3-n ) q1 A in the sum (E) 13 (Si(R) 2 ) n L 3-n ) q1 The preferred method will be described in detail below. The following will explain A in equation (C). 11 (Si(R) 2 ) n L 3-n ) q1 A in formula (D) 12 (Si(R) 2 ) n L 3-n ) q1 A in the sum (D) 13 (Si(R) 2 ) n L 3-n ) q1 Unified representation as A(Si(R) 2 ) n L 3-n ) q1 .

[0594] In formula (C), A is a group with a valence of (p1+q1); in formula (D), A is a group with a valence of (q1+1); and in formula (E), A is a group with a valence of (q1+u1).

[0595] A(Si(R)2 ) n L 3-n ) q1 The indicated group is preferably group (3-1A) or group (3-1B), more preferably group (3-1A).

[0596] -Q a -X 31 (-Q) b -Si(R) 2 ) n L 3-n ) h (-R) 31 ) i …(3-1A)

[0597] -Q c -[CH2C(R) 32 (-Q) d -Si(R) 2 ) n L 3-n )] y -R 33 …(3-1B)

[0598] It should be noted that in equations (3-1A) and (3-1B), R 2 The definitions of L and n are as described above.

[0599] In formula (3-1A), Q a It is a single bond or a divalent linker.

[0600] Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO2-, and -N(R) groups. d -, -C(O)-, -Si(R) a )2- and groups formed by combining two or more of them.

[0601] The aforementioned divalent hydrocarbon group can be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenyl group, or an alkyne group. The divalent saturated hydrocarbon group can be linear, branched, or cyclic; for example, an alkylene group can be mentioned. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 4 to 20, and particularly preferably 5 to 15. Furthermore, as a divalent aromatic hydrocarbon group, an aromatic hydrocarbon group with 5 to 20 carbon atoms is preferred; for example, a phenylene group can be mentioned. In addition, an alkenyl group or an alkyne group with 2 to 20 carbon atoms can also be used.

[0602] The above R a It is an alkyl group (preferably with 1 to 10 carbon atoms) or a phenyl group. The above R... d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0603] It should be noted that, for example, the groups formed by combining two or more of them can be: -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R) d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, possessing -C(O)N(R) d )-alkylene groups, having -N(R d )C(O)- alkylene groups, having -OC(O)N(R d Alkylenes with - ether oxygen atoms, alkylenes with -S-, alkylenes with -OC(O)-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, having -N(R d C(O)N(R) d )-alkylene groups, having -SO2N(R d )-alkylene, and alkylene-Si(R a )2-Phenylidene-Si(R a 2.

[0604] In equation (3-1A), X 31 It can be a single bond, alkylene group, carbon atom, nitrogen atom, silicon atom, organo(poly)siloxane residue with 2 to 8 valences, or a cyclic group with (h+i+1) valences.

[0605] It should be noted that the aforementioned alkylene groups may have -O-, silylenoid skeleton groups, divalent organo(poly)siloxane residues, or dialkylmethylene silane groups. Alkylene groups may have multiple groups selected from the group consisting of -O-, silylenoid skeleton groups, divalent organo(poly)siloxane residues, and dialkylmethylene silane groups.

[0606] X 31 The number of carbon atoms in the alkylene group shown is preferably 1 to 20, more preferably 1 to 10.

[0607] Examples of organo(poly)siloxane residues with valences of 2 to 8 include divalent organo(poly)siloxane residues and (w2+1) valence organo(poly)siloxane residues, which will be discussed later.

[0608] In equation (3-1A), X31 In the case of a cyclic group with a valence of (h+i+1), Q a 、(-Q b -Si(R) 2 ) n L 3-n ) and R 31 It is directly bonded to the atoms that make up the ring. This ring is a ring other than the organopolysiloxane ring.

[0609] X 31 The ring can be any type of monocyclic, fused polycyclic, bridged, spirocyclic, or aggregated polycyclic ring. The atoms constituting the ring can be a carbon ring composed solely of carbon atoms, or a heterocycle composed of heteroatoms with two or more valences and carbon atoms. Furthermore, the bonds between the atoms constituting the ring can be single bonds or multiple bonds. Moreover, the ring can be aromatic or non-aromatic.

[0610] As a monocyclic ring, 4-membered to 8-membered rings are preferred, and 5-membered and 6-membered rings are more preferred. As a fused polycyclic ring, a fused polycyclic ring consisting of two or more fused 4-membered to 8-membered rings is preferred, a fused polycyclic ring consisting of two or three rings selected from 5-membered and 6-membered rings bonded together, and a fused polycyclic ring consisting of one or two rings selected from 5-membered and 6-membered rings bonded to a 4-membered ring is more preferred. As a bridging ring, a bridging ring with a 5-membered or 6-membered ring as the largest ring is preferred, and a spiro ring consisting of two 4-membered to 6-membered rings is preferred. As an aggregated polycyclic ring, an aggregated polycyclic ring consisting of two or three rings selected from 5-membered and 6-membered rings bonded together by a single bond, 1 to 3 carbon atoms, or a heteroatom with a valence of 2 or 3 is preferred. It should be noted that in aggregated polycyclic rings, it is preferred that each ring is bonded with a Q. a 、(-Q b -Si(R) 2 ) n L 3-n ) and R 31 Any one of (i=1 or higher).

[0611] Nitrogen, oxygen, and sulfur atoms are preferred as heteroatoms constituting the aforementioned ring, and nitrogen and oxygen atoms are more preferred. The number of heteroatoms constituting the ring is preferably three or less. Furthermore, if the number of heteroatoms constituting the ring is two or more, these heteroatoms can be different.

[0612] As X 31The ring in the compound is preferably selected from the group consisting of aliphatic rings with 3 to 8 members, benzene rings, heterocyclic rings with 3 to 8 members, fused rings formed by two or three of these rings, bridged rings with a 5- or 6-membered ring as the largest ring, and polycyclic rings consisting of two or more of these rings, with the connecting group being a single bond and having alkylene, oxygen, or sulfur atoms with 3 or fewer carbon atoms.

[0613] Preferred rings are benzene rings, 5- or 6-membered aliphatic rings, 5- or 6-membered heterocycles having nitrogen or oxygen atoms, and fused rings consisting of 5- or 6-membered carbon rings and 4- to 6-membered heterocycles.

[0614] Specific examples of rings include the following: 1,3-cyclohexadiene ring, 1,4-cyclohexadiene ring, anthracene ring, cyclopropane ring, decahydronaphthalene ring, norbornene ring, norbornadiene ring, furan ring, pyrrole ring, thiophene ring, pyrazine ring, morpholine ring, aziridine ring, isoquinoline ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyrazole ring, pyran ring, pyridazine ring, pyrimidine ring, and indene ring. It should be noted that rings with an oxygen group (=O) are also shown below.

[0615]

[0616] X 31 The non-ring-forming connecting bonds of the atoms forming the ring are with Q. a 、(-Q b -Si(R) 2 ) n L 3-n ) or R 31 Linking bonds. In the presence of remaining linking bonds, these bonds are bonded to hydrogen atoms or substituents. Examples of such substituents include halogen atoms, alkyl groups (which may contain ether-like oxygen atoms between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0617] In addition, one carbon atom forming the ring has two atoms with Q. a 、(-Q b -Si(R) 2 ) n L 3-n ) or R 31 In the case of a bonded linkage, Q can be bonded to a single carbon atom. a and (-Q b -Si(R) 2 ) n L 3-n It can also bond two (-Q) b -Si(R) 2 ) nL 3-n ). Preferred Q a With (-Q) b -Si(R) 2 ) n L 3-n ) or R 31 Bonded to different ring-forming atoms. h (-Q) b -Si(R) 2 ) n L 3-n () can bond to different cyclic atoms, and two of them can bond to a single cyclic carbon atom, thus resulting in two (-Q) bonds. b -Si(R) 2 ) n L 3-n The cyclic carbon atoms of a ring can exist in more than two forms. (i R) 31 They can bond to different cyclic atoms, and two of them can bond to a single cyclic carbon atom, thus creating two R atoms. 31 There can be more than two cyclic carbon atoms.

[0618] From the perspective of improving the wear resistance of the surface treatment layer, X 31 Preferably, it is a carbon atom, nitrogen atom, silicon atom, organo(poly)siloxane residue with a valence of 4 to 8, or a cyclic group with a valence of (h+i+1), and more preferably a carbon atom.

[0619] In formula (3-1A), Q b It is a single bond or a divalent linker.

[0620] The definition of a divalent linker is the same as the above Q. a The definitions described herein are the same.

[0621] Among them, Q b Preferably, the alkylene group can have an ether-like oxygen atom. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and can be 2 to 10, 2 to 6, or 2 to 5. Examples include 2, 3, 8, 9, and 11. In addition, the aforementioned number of carbon atoms can be 1 to 10.

[0622] In equation (3-1A), R 31 It can be a hydrogen atom, a hydroxyl group, or an alkyl group.

[0623] The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3, and even more preferably 1.

[0624] X 31 In the case of a single bond or an alkylene group, h is 1 and i is 0.

[0625] X 31In the case of nitrogen atoms, h is an integer from 1 to 2, and i is an integer from 0 to 1, satisfying h + i = 2.

[0626] X 31 In the case of carbon or silicon atoms, h is an integer from 1 to 3, and i is an integer from 0 to 2, satisfying h + i = 3.

[0627] X 31 In the case of organo(poly)siloxane residues with valences of 2 to 8, h is an integer from 1 to 7, and i is an integer from 0 to 6, satisfying h+i=1~7.

[0628] X 31 In the case of a cyclic group with a valence of (h+i+1), h is an integer from 1 to 7 and i is an integer from 0 to 6, satisfying h+i=1~7.

[0629] There are two or more (-Q) b -Si(R) n L 3-n In the case of two or more (-Q) b -Si(R) n L 3-n The R values ​​can be the same or different. There are two or more R values. 31 In the case of two or more (-R) 31 They can be the same or different.

[0630] From the perspective of improving the wear resistance of the surface treatment layer, i is preferably 0.

[0631] In equation (3-1B), Q c It is a single bond or a divalent linker.

[0632] The definition of a divalent linker and the above Q a The definitions described herein are the same.

[0633] In equation (3-1B), R 32 The atom is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; from the perspective of ease of compound production, a hydrogen atom is preferred.

[0634] As an alkyl group, methyl is preferred.

[0635] In equation (3-1B), Q d It is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6. From the perspective of ease of compound preparation, Q... d Preferably, it is a single bond or CH2-.

[0636] In equation (3-1B), R 33 The atom can be a hydrogen atom or a halogen atom; from the perspective of ease of compound production, a hydrogen atom is preferred.

[0637] y is an integer from 1 to 10, preferably an integer from 1 to 6.

[0638] Two or more [CH2C(R)] 32 (-Q) d -Si(R) 2 ) n L 3-n [The characters] can be the same or different.

[0639] As a group (3-1A), groups (3-1A-1) to (3-1A-7) are preferred.

[0640] -(X) 32 ) s1 -Q b1 -Si(R) 2 ) n L 3-n …(3-1A-1)

[0641] -(X) 33 ) s2 -Q a2 -N[-Q b2 -Si(R) 2 ) n L 3-n ]2…(3-1A-2)

[0642] -Q a3 -Si(R) g )[-Q b3 -Si(R) 2 ) n L 3-n ]2…(3-1A-3)

[0643] -[Q e ] s4 -Q a4 -(O) t4 -C[-(O) u4 -Q b4 -Si(R) 2 ) n L 3-n ] 3-w1 (-R) 31 ) w1 …(3-1A-4)

[0644] -Q a5 -Si[-Q b5 -Si(R) 2 ) n L 3-n ]3…(3-1A-5)

[0645] -[Q e ] v -Q a6 -Z a [-Q b6 -Si(R) 2 ) n L 3-n ] w2 …(3-1A-6)

[0646] -[Q e ] s4 -Q a4 -(O) t4 -Z c [-(OQ b4 ) u4 -Si(R) 2 ) n L 3-n ] w3 (-OH) w4 …(3-1A-7)

[0647] It should be noted that in equations (3-1A-1) to (3-1A-7), R 2 The definitions of L and n are as described above.

[0648] Wherein, the group (3-1A) is preferably the group (3-1A-4).

[0649] In group (3-1A-1), X 32 -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d )-; or combinations thereof with divalent linking groups (where N and Q in the formula are...) b1 (bonding).

[0650] R d The definition is as described above.

[0651] s1 is either 0 or 1.

[0652] X 32 It is a divalent linker with -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d)-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d In the case of a combination of )-, the divalent linking group and Si(R) of formula (C) or (D) 3 )2 or Si(R) 4 )2 bond, or with B of formula (E) 11 Bonding.

[0653] Examples of divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyepoxyalkyl groups, and combinations thereof.

[0654] Q b1 It can be a single bond or an alkylene group. It should be noted that the alkylene group can have -O-, a silylene skeleton group, or a dialkylsilyl group. The alkylene group can have multiple groups selected from the group consisting of -O-, silylene skeleton groups, divalent organo(poly)siloxane residues, and dialkylsilyl groups.

[0655] It should be noted that when the alkylene group has -O-, silylene skeleton group, divalent organo(poly)siloxane residue or dialkylmethylene silyl group, these groups are preferably present between carbon atoms.

[0656] Q b1 The alkylene group shown preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 2 to 20, and particularly preferably 2 to 6. Alternatively, the aforementioned number of carbon atoms can be 1 to 10.

[0657] In group (3-1A-2), X 33 -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d )-; or combinations thereof with divalent linking groups.

[0658] R d The definition is as described above.

[0659] s2 is either 0 or 1. From the perspective of ease of compound production, s2 is preferably 0.

[0660] X 33 It is a divalent linker with -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d In the case of a combination of )-, the divalent linking group and Si(R) of formula (C) or (D) 3 )2 or Si(R) 4 )2 bond, or with B of formula (E) 11 Bonding.

[0661] Examples of divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyepoxyalkyl groups, and combinations thereof.

[0662] Q a2 It is a single bond, alkylene, -C(O)-, or an etheric oxygen atom between carbon atoms of alkylene with more than 2 carbon atoms, -C(O)-, -C(O)O-, -OC(O)-, -C(O)N(R) d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, -C(O)N(R) d )- or -NH- groups.

[0663] Q a2 The number of carbon atoms in the alkylene group shown is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3.

[0664] Q a2 The alkylene groups shown have ether-type oxygen atoms, -C(O)-, -C(O)O-, -OC(O)-, or -C(O)N(R) between carbon atoms. d )-、-N(R dC(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, -C(O)N(R) d The number of carbon atoms in the - or -NH- group is preferably 2 to 10, more preferably 2 to 6.

[0665] From the perspective of ease of compound production, Q a2 Single bonds are preferred.

[0666] Q b2 It is an alkylene group, or an alkylene group having a divalent organo(poly)siloxane residue, an ether oxygen atom, or a -NH- group between carbon atoms of the carbon atom of the carbon-carbon group with more than 2 carbon atoms.

[0667] Q b2 The alkylene group shown preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. Alternatively, the aforementioned number of carbon atoms can be 1 to 10.

[0668] Q b2 The number of carbon atoms in the alkylene group with 2 or more carbon atoms having divalent organo(poly)siloxane residues, ether oxygen atoms or -NH- groups between carbon atoms is preferably 2 to 10, more preferably 2 to 6.

[0669] As Q b2 From the perspective of ease of compound production, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- (where the right side is bonded to Si) are preferred.

[0670] Two [-Q] b2 -Si(R) 2 ) n L 3-n They can be the same or different.

[0671] In group (3-1A-3), Q a3 It is a single bond, or optionally an alkylene group with an ether-like oxygen atom. From the perspective of ease of compound preparation, Q... a3 Single bonds are preferred.

[0672] The number of carbon atoms in the alkylene group having an ether-like oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

[0673] Rg It can be a hydrogen atom, a hydroxyl group, or an alkyl group.

[0674] As R g From the viewpoint of easy compound production, hydrogen atoms or alkyl groups are preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4, and even more preferably methyl.

[0675] Q b3 A group that is an alkylene group, or an alkylene group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms.

[0676] Q b3 The alkylene group shown preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. Alternatively, the aforementioned number of carbon atoms can be 1 to 10.

[0677] Q b3 The number of carbon atoms in the alkylene group with etheric oxygen atoms or divalent organo(poly)siloxane residues between carbon atoms is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0678] From the perspective of ease of compound production, Q b3 Preferably, it is -CH2CH2-, -CH2CH2CH2-, or -CH2CH2CH2CH2CH2CH2CH2CH2-.

[0679] Two [-Q] b3 -Si(R) 2 ) n L 3-n They can be the same or different.

[0680] In group (3-1A-4), Q e is -C(O)O-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)- or -C(O)N(R) d )-; or combinations thereof with divalent linking groups.

[0681] Q e It is a divalent linker with -C(O)O-, -SO2N(R) d )-、-N(R d SO2-, -N(R) d C(O)- or -C(O)N(R) dIn the case of a combination of )-, the divalent linking group and Si(R) of formula (C) or (D) 3 )2 or Si(R) 4 )2 bond, or with B of formula (E) 11 Bonding.

[0682] Examples of divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyepoxyalkyl groups, and combinations thereof.

[0683] R 31 The definition is as described above. When w1 is 1 or 2, R... 31 Hydrogen atoms are preferred.

[0684] s4 is 0 or 1.

[0685] Q a4 It is a single bond, or optionally an alkylene group having an ether-like oxygen atom.

[0686] The number of carbon atoms in the alkylene group having an ether-like oxygen atom is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3.

[0687] t4 is 0 or 1 (where Q is 0 or 1). a4 (0 when it is a single bond).

[0688] As -Q a4 -(O) t4 From the perspective of ease of compound production, when s4 is 0, single bonds, -CH2O-, -CH2OCH2-, -CH2OCH2CH2O-, -CH2OCH2CH2OCH2-, and -CH2OCH2CH2CH2CH2OCH2- are preferred; when s4 is 1, single bonds, -CH2-, and -CH2CH2- are preferred.

[0689] Q b4 It is an alkylene group, and the alkylene group may have -O-, -C(O)N(R) d )-(R d (as defined above), silymine skeleton group, divalent organo(poly)siloxane residue or dialkylmethylenesilyl group.

[0690] It should be noted that when the alkylene group has an -O- or silanine skeleton group, it is preferable that the -O- or silanine skeleton group is present between carbon atoms. Additionally, the alkylene group has a -C(O)N(R) skeleton. d In the case of )-, dialkylmethylenesilyl or divalent organo(poly)siloxane residues, it is preferred that they are between carbon atoms or with (O) u4 These groups are located at the end of the bonded side.

[0691] Qb4 The alkylene group shown preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. Alternatively, the aforementioned number of carbon atoms can be 1 to 10.

[0692] u4 is either 0 or 1.

[0693] As - (O) u4 -Q b4 - From the perspective of easy compound production, the preferred compounds are -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2-, -CH2OCH2CH2CH2CH2CH2-, -OCH2CH2CH2-, -OSi(CH3)2CH2CH2CH2-, -OSi(CH3)2OSi(CH3)2CH2CH2CH2-, and -CH2CH2CH2Si(CH3)2PhSi(CH3)2CH2CH2- (wherein the right side is bonded to Si).

[0694] w1 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0695] There are two or more [-(O)] u4 -Q b4 -Si(R) 2 ) n L 3-n In the case of two or more [-(O) u4 -Q b4 -Si(R) 2 ) n L 3-n They can be the same or different.

[0696] There are two or more R 31 In the case of two or more (-R) 31 They can be the same or different.

[0697] In group (3-1A-5), Q a5 It can be an alkylene group that optionally has an ether-like oxygen atom.

[0698] The number of carbon atoms in the alkylene group having an ether-like oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

[0699] As Q a5 From the perspective of ease of compound production, -OCH2CH2CH2-, -OCH2CH2OCH2CH2CH2-, -CH2CH2-, and -CH2CH2CH2- (where the right side is bonded to Si) are preferred.

[0700] Q b5 A group that is an alkylene group, or an alkylene group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms.

[0701] Q b5 The alkylene group shown preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. Alternatively, the aforementioned number of carbon atoms can be 1 to 10.

[0702] Q b5 The number of carbon atoms in the alkylene group with etheric oxygen atoms or divalent organo(poly)siloxane residues between carbon atoms is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0703] As Q b5 From the perspective of ease of compound preparation, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- are preferred (wherein, the right side is related to Si(R)). 2 ) n L 3-n Bonding.

[0704] 3 [-Q] b5 -Si(R) 2 ) n L 3-n They can be the same or different.

[0705] Q in group (3-1A-6) e The definition is as defined in the group (3-1A-4) above.

[0706] v is 0 or 1.

[0707] Q a6 It can be an alkylene group that optionally has an ether-like oxygen atom.

[0708] The number of carbon atoms in the alkylene group having an ether-like oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

[0709] As Q a6 From the perspective of ease of compound preparation, -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, and -CH2CH2CH2- are preferred (where the right side is the same as Z). a (bonding).

[0710] Z aOrganosiloxane residues with a (w2+1) valence, or groups with an alkylene group between organosiloxane residues with a (w2+1) valence.

[0711] w2 is an integer between 2 and 7.

[0712] Examples of organo(poly)siloxane residues with a (w2+1) valence and groups with an alkylene group between organo(poly)siloxane residues with a (w2+1) valence include the following groups. Wherein, R in the following formula... a As stated above. Indicates the bonding site.

[0713]

[0714] Q b6 A group that is an alkylene group, or an alkylene group having an ether oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms.

[0715] Q b6 The alkylene group shown preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. Alternatively, the aforementioned number of carbon atoms can be 1 to 10.

[0716] Q b6 The number of carbon atoms in the alkylene group with etheric oxygen atoms or divalent organo(poly)siloxane residues between carbon atoms is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0717] As Q b6 From the perspective of ease of compound production, -CH2CH2- and -CH2CH2CH2- are preferred.

[0718] w2 of [-Q] b6 -Si(R) 2 ) n L 3-n They can be the same or different.

[0719] In group (3-1A-7), Z c Hydrocarbon groups with a valence of (w3+w4+1).

[0720] w3 is an integer greater than or equal to 4.

[0721] w4 is an integer greater than or equal to 0.

[0722] Q e s4, Qa4 t4, Q b4 The definition and preferred range of u4 are the same as those of the symbols in group (3-1A-4).

[0723] Z c It can be composed of hydrocarbon chains, or it can have ether-like oxygen atoms between carbon atoms in the hydrocarbon chain, preferably composed of hydrocarbon chains.

[0724] Z c The valence is preferably 5 to 20, more preferably 5 to 10, even more preferably 5 to 8, and particularly preferably 5 to 6.

[0725] Z c The number of carbon atoms is preferably 3 to 50, more preferably 4 to 40, and even more preferably 5 to 30.

[0726] w3 is preferably 4~20, more preferably 4~16, even more preferably 4~8, and particularly preferably 4~5.

[0727] w4 is preferably 0~10, more preferably 0~8, further preferably 0~6, particularly preferably 0~3, and most preferably 0~1.

[0728] There are two or more [-(OQ)] b4 ) u4 -Si(R) 2 ) n L 3-n In the case of two or more [-(OQ], b4 ) u4 -Si(R) 2 ) n L 3-n They can be the same or different.

[0729] Formula A(Si(R) 2 ) n L 3-n ) q1 A in the text can be a group (g2-1)~(g2-7).

[0730]

[0731] (-A) 1 -Q 12 -) e1 C(R) e2 ) 4-e1-e2 (-Q) 22 -) e2 …(g2-2)

[0732] -A 1 -Q 13 -N(-Q23 -)2…(g2-3)

[0733] (-A) 1 -Q 14 -) h1 Z 4 (-Q) 24 -) h2 …(g2-4)

[0734] (-A) 1 -Q 15 -) i1 Si(R) e3 ) 4-i1-i2 (-Q) 25 -) i2 …(g2-5)

[0735] -A 1 -Q 26 - (g2-6)

[0736] -A 1 -Q 12 -CH (-Q) 22 -)-Si(R e3 ) 3-i3 (-Q) 25 -) i3 …(g2-7)

[0737] In equations (g2-1) to (g2-7), A 1 Side and Si(R) 3 )2 or Si(R) 4 )2 bond, Q 22 Q 23 Q 24 Q 25 Or Q 26 Side and [-Si(R)] 2 ) n L 3-n ] Bonding.

[0738] A 1 For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O- or SO2NR 6 -

[0739] Q 11 It is a single bond, -O-, alkylene, or has -C(O)NR between carbon atoms in alkylene with more than 2 carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups.

[0740] Q 12 It is a single bond, an alkylene group, or an alkylene group having a -C(O)NR bond between carbon atoms. 6 -、-C(O)-、-NR 6 A has a group of - or O-, and A has two or more Q groups. 12 In the case of two or more Qs 12 They can be the same or different.

[0741] Q 13 It is a single bond (where A is a single bond). 1 -C(O)-, alkylene groups, and alkylene groups with more than 2 carbon atoms having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 A group with - or O-, or a group having -C(O)- at the N-side end of an alkylene group.

[0742] Q 14 In Q 14 The bonded Z 4 Q is the case where the atom in the equation is a carbon atom. 12 In Q 14 The bonded Z 4 Q is the case where the atom in the middle is nitrogen atom. 13 In A, there are more than two Qs 14 In the case of two or more Qs 14 They can be the same or different.

[0743] Q 15 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 A has a group of - or O-, and A has two or more Q groups. 15 In the case of two or more Qs 15 They can be the same or different.

[0744] Q 22 Alkylenes, wherein the carbon-carbon atoms of alkylenes having two or more carbon atoms have a -C(O)NR bond. 6 -、-C(O)-、-NR 6 - or O- groups, with -C(O)NR at the end of the alkylene group on the side not connected to Si. 6 -、-C(O)-、-NR 6 A group with - or O-, or a -C(O)NR group between carbon atoms of an alkylene group having 2 or more carbon atoms. 6 -、-C(O)-、-NR 6-or O- and has -C(O)NR at the end on the side not connected to Si. 6 -、-C(O)-、-NR 6 A has a group of - or O-, and A has two or more Q groups. 22 In the case of two or more Qs 22 They can be the same or different.

[0745] Q 23 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups, two Q 23 They can be the same or different.

[0746] Q 24 In Q 24 The bonded Z 4 Q is the case where the atom in the equation is a carbon atom. 22 In Q 24 The bonded Z 4 Q is the case where the atom in the middle is nitrogen atom. 23 A has more than two Qs 24 In the case of two or more Qs 24 They can be the same or different.

[0747] Q 25 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 A has a group of - or O-, and A has two or more Q groups. 25 In the case of two or more Qs 25 They can be the same or different.

[0748] Q 26 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups.

[0749] Q 22 Q 23 Q 24 Q 25 Q 26 When the carbon atoms are alkylene groups, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0750] Z 4 A group having a cyclic structure with a valence of (h1+h2), the group having Q14 Directly bonded carbon or nitrogen atoms and having Q 24 Directly bonded carbon or nitrogen atoms.

[0751] R e1 A is a hydrogen atom or an alkyl group, and A has two or more R atoms. e1 In the case of two or more R e1 They can be the same or different.

[0752] R e2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group.

[0753] R e3 It is an alkyl group. R 6 It consists of hydrogen atoms and alkyl or phenyl groups having 1 to 6 carbon atoms.

[0754] d1 is an integer from 0 to 3, preferably 1 or 2.

[0755] d2 is an integer from 0 to 3, preferably 1 or 2.

[0756] d1+d2 are integers from 1 to 3.

[0757] d3 is an integer from 0 to 3, preferably 0 or 1.

[0758] d4 is an integer from 0 to 3, preferably 2 or 3.

[0759] d3+d4 is an integer from 1 to 3.

[0760] d1+d3 is an integer from 1 to 5, preferably 1 or 2.

[0761] d2+d4 is an integer from 1 to 5, preferably 4 or 5.

[0762] e1+e2 is 3 or 4.

[0763] e1 is an integer from 1 to 3, preferably 1 or 2.

[0764] e2 is an integer from 1 to 3, preferably 2 or 3.

[0765] h1 is an integer greater than or equal to 1, preferably 1 or 2.

[0766] h2 is an integer greater than or equal to 1, preferably 2 or 3.

[0767] i1+i2 is 3 or 4.

[0768] i1 is an integer from 1 to 3, preferably 1 or 2.

[0769] i2 is an integer from 1 to 3, preferably 2 or 3.

[0770] i3 is 2 or 3.

[0771] From the perspectives of ease of compound manufacturing and superior wear resistance of the surface treatment layer, Q 11 Q 12 Q 13 Q 14 Q 15 Q 22 Q 23 Q 24 Q 25 and Q 26 The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can also have 2 to 10 or 2 to 6 carbon atoms. Examples include 2, 3, 8, 9, and 11 carbon atoms. Furthermore, the aforementioned number of carbon atoms can be 1 to 10, 1 to 6, or 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0772] As Z 4 The ring structure in the text can be exemplified by the ring structure described above, and the preferred method is also the same. It should be noted that, due to Q... 14 Q 24 With Z 4 The ring structures in Q are directly bonded, therefore, for example, there are no alkylene groups connected to the ring structures, and Q 14 Q 24 The case of further connection with the alkylene group.

[0773] From the perspective of ease of compound production, R e1 R e2 Or R e3 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 to 2.

[0774] From the perspective of easily manufacturing compounds, R e2 The number of carbon atoms in the alkyl portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0775] From the perspective of ease of compound manufacturing and further improvement of the wear resistance of the surface treatment layer, h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0776] As for h2, from the perspective of ease of compound manufacturing and further improvement of the wear resistance of the surface treatment layer, 2 to 6 is preferred, more preferably 2 to 4, and particularly preferably 2 or 3.

[0777] As Equation A(Si(R) 2 ) n L 3-n )q1 Other ways of A in the group can be exemplified by groups (g2-8) to (g2-14).

[0778]

[0779] (-A) 1 -Q 12 -) e1 C(R) e2 ) 4-e1-e2 (-Q) 22 -G 1 ) e2 …(g2-9)

[0780] -A 1 -Q 13 -N(-Q 23 -G 1 )2…(g2-10)

[0781] (-A) 1 -Q 14 -) h1 Z 4 (-Q) 24 -G 1 ) h2 …(g2-11)

[0782] (-A) 1 -Q 15 -) i1 Si(R) e3 ) 4-i1-i2 (-Q) 25 -G 1 ) i2 …(g2-12)

[0783] -A 1 -Q 26 -G 1 …(g2-13)

[0784] -A 1 -Q 12 -CH (-Q) 22 -G 1 )-Si(R e3 ) 3-i3 (-Q) 25 -G 1 ) i3 …(g2-14)

[0785] In equations (g2-8) to (g2-14), A 1 Side and Si(R) 3 )2 or Si(R) 4 )2 bond, G 1Side and [-Si(R)] 2 ) n L 3-n ] Bonding.

[0786] G 1 For the following groups (g3), A has two or more Gs 1 They can be the same or different. G 1 The symbols other than those in equations (g2-1) to (g2-7) are the same.

[0787] -Si(R) 13 ) 3-k3 (-Q) 3 -) k3 …(g3)

[0788] In group (g3), the Si side is related to Q. 22 Q 23 Q 24 Q 25 and Q 26 Connection, Q 3 Side and [-Si(R)] 2 ) n L 3-n [Connection. R] 13 It is an alkyl group. Q 3 Alkylenes, wherein the carbon-carbon atoms of alkylenes having two or more carbon atoms have a -C(O)NR bond. 6 -、-C(O)-、-NR 6 - or -O- groups, or (OSi(R) 9 )2) p -O-, two or more Qs 3 They can be the same or different. k3 is 2 or 3. R 6 It is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms. R 9 It is an alkyl, phenyl, or alkoxy group, with two Rs. 9 They can be the same or different. p is an integer from 0 to 5. When p is 2 or higher, two or more (OSi(R)) can be used. 9 2) They can be the same or different.

[0789] Starting from the aspects of easy compound manufacturing and further improvement of the wear resistance of the surface treatment layer, Q 3 The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can also have 2 to 10 or 2 to 6 carbon atoms. Examples include 2, 3, 8, 9, and 11 carbon atoms. Alternatively, the aforementioned number of carbon atoms can be 1 to 10, 1 to 6, or 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0790] From the perspective of ease of compound production, R 13 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0791] From the perspective of ease of compound production, R 9 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0792] From the perspective of the excellent storage stability of the compound, R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0793] p is preferably 0 or 1.

[0794] [Examples of Compound 1 and Compound 2]

[0795] The specific examples of the first and second compounds are described in detail below.

[0796] Specific examples of the first compound include the following compounds (1) to (3), (4A) and (5).

[0797] As a specific example of the second compound, the following compound (4B) can be cited.

[0798] Compound (1)

[0799] A compound comprising the following group 1a, a chain-like organo(poly)siloxane residue, a partial structure as an alkylene chain or polyepoxide chain having 3 or more carbon atoms, and the following group 1b.

[0800] Group 1a: -M 1 T 1 3

[0801] Group 1b: -Si(R) 2 ) n L 3-n

[0802] M 1 It is Si, Sn or Ge,

[0803] T 1 Each is independently a hydrocarbon group or a trialkylsilyloxy group.

[0804] R 2 Each is an independent monovalent hydrocarbon group.

[0805] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0806] n is an independent integer from 0 to 2.

[0807] R 2 L and n are related to R in the above formula (S1) 2 The same applies to L and n.

[0808] Details of group 1a are consistent with T in formula (C). 11 The T in the description 1 3M 1 The details are the same.

[0809] Compound (2)

[0810] A compound comprising an alkyl group having two or more carbon atoms, a chain-like organo(poly)siloxane residue, and a reactive silyl group.

[0811] Compound (3)

[0812] A compound comprising group 3a, a partial structure containing divalent chain organo(poly)siloxane residues, and group 3b, wherein the partial structure is a divalent chain organo(poly)siloxane residue, or a combination of a divalent chain organo(poly)siloxane residue with at least one of an alkylene chain and a polyepoxide chain.

[0813] Group 3a: a monovalent cyclic polysiloxane residue or a monovalent cage-like polysiloxane residue

[0814] Group 3b:-Si(R) 2 ) n L 3-n

[0815] R 2 Each is an independent monovalent hydrocarbon group.

[0816] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0817] n is an independent integer from 0 to 2.

[0818] R 2 L and n are related to R in the above formula (S1) 2 The same applies to L and n.

[0819] Compounds (4A) and (4B)

[0820] The compounds shown in formula (4A) or (4B) below

[0821] (R) T1 -R S -(-SiR T2 2-) q4 ) α-X A -R H β …(4A)

[0822] R H γ -X A -O p4 -R S -(-SiR T2 2-) q4 -X A -R H γ …(4B)

[0823] In equations (4A) and (4B),

[0824] R S Each is independently a divalent, straight-chain organosiloxane alkyl group.

[0825] R T1 Each is an independent hydrocarbon group.

[0826] R T2 Each is an independent hydrocarbon group.

[0827] p4 is either 0 or 1.

[0828] Each q4 is independently either 0 or 1.

[0829] R H The group is represented by any of the following formulas (W1) to (W4).

[0830] The above R H It contains two or more Si atoms bonded with hydroxyl or hydrolyzable groups.

[0831] X A Each is independently a single bond or a group represented by the following formula (W5).

[0832] α is an integer from 1 to 9.

[0833] β is an integer from 1 to 9.

[0834] Each γ is an independent integer from 1 to 9.

[0835] -(CH2CR 10 (R) 15 )X 11 -Si(R) 2 ) n81 L 3-n81 ) t -R 14 …(W1)

[0836] -SiR a1k81 L l81 R c1 m81 …(W2)

[0837] -CR d1 k82 R e1 l82 R f1 m82 …(W3)

[0838] -NR g1 R h1 …(W4)

[0839] In equations (W1) to (W4),

[0840] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0841] R 2 Each is an independent monovalent hydrocarbon group.

[0842] n 81 In each (SiR) 2 n81 L 3-n81 Each element in the unit contains an independent integer from 0 to 3.

[0843] X 11 Each is an independent single bond or a divalent organic group;

[0844] R 10 Each can be independently a hydrogen atom or a monovalent organic group;

[0845] Each t is an integer greater than 2;

[0846] R 14 Each can be independently a hydrogen atom, a halogen atom, or -X. 11 -Si(R) 2 ) n81 L 3-n81 ;

[0847] R 15 Each is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkene group having 1 to 6 carbon atoms;

[0848] R a1 Each independently is -Z 81 -SiR 21 p81 L q81 R 23 r81 ;

[0849] Z 81Each is an independent divalent organic group;

[0850] R 21 Each independently is -Z 1' -SiR 21' p1' L q1' R 23' r1' ;

[0851] R 23 Each is an independent monovalent organic group;

[0852] p81 are each an independent integer from 0 to 3;

[0853] q81 are each an independent integer from 0 to 3;

[0854] r81 are each an independent integer from 0 to 3;

[0855] p81+q81+r81 equals 3;

[0856] Z 1' Each is an independent divalent organic group;

[0857] R 21' Each independently is -Z 1” -SiL q1” R 23” r1” ;

[0858] R 23' Each is an independent monovalent organic group;

[0859] p1' is an independent integer from 0 to 3;

[0860] Each q1' is an independent integer from 0 to 3;

[0861] r1' is an independent integer from 0 to 3;

[0862] p1'+q1'+r1' is 3;

[0863] Z 1” Each is an independent divalent organic group;

[0864] R 23” Each is an independent monovalent organic group;

[0865] Each q1 is an independent integer from 0 to 3;

[0866] r1” is an integer from 0 to 3, which can be independently represented by each of the following:

[0867] q1”+r1” equals 3;

[0868] Rc1 Each is an independent monovalent organic group;

[0869] k81 are each an independent integer from 0 to 3;

[0870] l81 are each an independent integer from 0 to 3;

[0871] m81 are each an independent integer from 0 to 3;

[0872] k81+l81+m81 is 3;

[0873] R d1 Each independently is -Z 82 -CR 71 p82 R 72 q82 R 73 r82 ;

[0874] Z 82 Each can be independently a single bond, an oxygen atom, or a divalent organic group;

[0875] R 71 Each independently is -Z 2' -CR 32' q2' R 33' r2' ;

[0876] R 72 Each independently is -Z 83 -SiL n82 R 35 3-n82 ;

[0877] R 73 Each can be independently a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0878] p82 are each an independent integer from 0 to 3;

[0879] Each q82 is an independent integer from 0 to 3;

[0880] r82 represents an integer from 0 to 3 independently;

[0881] p82 + q82 + r82 equals 3;

[0882] Z 2' Each can be independently a single bond, an oxygen atom, or a divalent organic group;

[0883] R 32' Each independently is -Z 83 -SiL n82 R 353-n82 ;

[0884] R 33' Each can be independently a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0885] Each q2' is an independent integer from 0 to 3;

[0886] r2' are each an independent integer from 0 to 3;

[0887] q2'+r2' equals 3;

[0888] Z 83 Each can be independently a single bond, an oxygen atom, or a divalent organic group;

[0889] R 35 Each is an independent monovalent organic group;

[0890] n82 is an integer from 0 to 3, each of which is independent.

[0891] R e1 Each independently is -Z 83 -SiL n82 R 35 3-n82 ;

[0892] R f1 Each can be independently a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0893] k82 are each an independent integer from 0 to 3;

[0894] l82 is an integer from 0 to 3, each of which is independent.

[0895] m82 represents an integer from 0 to 3 independently.

[0896] k82+l82+m82 is 3;

[0897] R g1 and R h1 Each independently is -Z 84 -SiL n81 R 2 3-n81 -Z 84 -SiR a1 k81 L l81 R c1 m81 or -Z 84 -CR d1 k82 R e1 l82 R f1 m82 ;

[0898] Z 84 Each can be independently a single bond, an oxygen atom, or a divalent organic group;

[0899] In formulas (W1), (W2), (W3), and (W4), there are at least two Si atoms bonded with hydrolyzable groups, groups having hydrolyzable groups, or hydroxyl groups.

[0900] R 2 and L and R in the above formula (S1) 2 And L is the same.

[0901] -(R) 50 ) p5 -(X) 51 ) q5 - … (W5)

[0902] In formula (W5),

[0903] R 50 It is a single bond, -(CH2) s5 -or o-phenylene, m-phenylene, or p-phenylene

[0904] s5 is an integer from 1 to 20.

[0905] X 51 For - (X) 52 ) l5 -,

[0906] X 52 Each time it appears, it is independently selected from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -CO-, -C(O)O-, -CONR. 54 -、-O-CONR 54 -、-NR 54 - and - (CH2) n5 -The groups in the composition

[0907] R 54 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group.

[0908] Each occurrence of n5 is an independent integer from 1 to 20.

[0909] l5 is an integer from 1 to 10.

[0910] p5 is either 0 or 1.

[0911] q5 is either 0 or 1.

[0912] At least one of p5 and q5 is 1, (R 50 ) p5 and (X) 51 )q5 The order in which they exist is arbitrary.

[0913] X A Each is preferably a single bond, an alkylene group with 1 to 20 carbon atoms, or -(CH2). s5 -X 53 -、-X 53 -(CH2) t5 -or- (CH2) s5 -X 53 -(CH2) t5 -

[0914] X 53 For single bonds, -O-, -CO-, -CONR 54 -、-O-CONR 54 -、-O-(CH2) u5 -CONR 54 -or -O-(CH2) u5 -CO-,

[0915] R 54 Each time it appears, it is independently a hydrogen atom, a phenyl group, an alkyl group with 1 to 6 carbon atoms, or an oxyalkylene group with 1 to 10 carbon atoms.

[0916] s5 is an integer from 1 to 20.

[0917] t5 is an integer from 1 to 20.

[0918] u5 is preferably an integer from 1 to 20.

[0919] Compound (5)

[0920] The compound shown in formula (5) below.

[0921]

[0922] In equation (5),

[0923] Y represents a single bond or *-Si(R) s2 )2-L s1 -。 * indicates a bond with an oxygen atom.

[0924] Z represents a divalent hydrocarbon group with 1 to 10 oxygen or carbon atoms.

[0925] R a9 Each can independently represent a hydrocarbon group or a trialkylsilyloxy group. Wherein, R... a9 When all groups are hydrocarbons, R a9 The hydrocarbon group shown is an alkyl group.

[0926] R s1 Rs2 Each can be used independently to represent an alkyl group having 1 to 10 carbon atoms.

[0927] L s1 It represents a divalent hydrocarbon group with 1 to 10 carbon atoms.

[0928] X represents a group represented by any one of the following formulas (X-1) to (X-3).

[0929] n9 represents a number from 1 to 150.

[0930]

[0931] In equations (X-1) to (X-3),

[0932] L x1 and L x2 Each of these groups independently represents a divalent hydrocarbon group with 1 to 20 carbon atoms, and the methylene group (-CH2-) contained in this divalent hydrocarbon group can be replaced with -O- or -O-Si(R x7 )2-.

[0933] R x1 ~R x7 Each can independently represent a hydrocarbon group with 1 to 10 hydrogen or carbon atoms.

[0934] X a1 Each can be independently represented as a hydrolyzable group, a group having a hydrolyzable group, or a trialkoxysilyloxy group.

[0935] X a2 Each of these can independently represent a trialkylsilyl group, a hydrocarbon chain group, a siloxane skeleton group, a hydrolyzable group, a group with a hydrolyzable group, or a trialkoxysilyloxy group, X a2 In the case of a hydrolyzable group, X a2 With X a1 They can be the same or different.

[0936] n2 represents an integer from 1 to 50.

[0937] n3 represents a number from 2 to 5.

[0938] n4 represents a number from 0 to 5.

[0939] In equation (X-3), (Si(R) x4 (-L) x2 -Si(X) a2 (X) a1 )2)-O-) and (Si(R x5 (R) x6 The order of the units shown in )-O-) is arbitrary.

[0940] The following describes compounds (1) to (5).

[0941] (Compound (1))

[0942] Compound (1) is preferably a compound represented by the following formula (1A).

[0943] [T 1 3M 1 -(O) r -Z 1 ] p1 A(Si(R) 2 ) n L 3-n ) q1 … (1A)

[0944] In equation (1A),

[0945] M 1 It is Si, Sn or Ge,

[0946] T 1 Each is independently a hydrocarbon group or a trialkylsilyloxy group.

[0947] r is 0 or 1.

[0948] Z 1 Each is independently an alkylene chain or a polyepoxide chain, or a combination of an alkylene chain and a divalent chain-like organo(poly)siloxane residue, where A is a single bond or a (p1+q1) valence linking group.

[0949] R 2 Each is an independent monovalent hydrocarbon group.

[0950] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[0951] n are independent integers from 0 to 2.

[0952] p1 and q1 are each an independent integer greater than or equal to 1.

[0953] Among them, Z 1 When each is an alkylene chain or a polyepoxide chain independently, A is a (p1+q1) valence linking group containing chain-like organo(poly)siloxane residues.

[0954] T 1 and M 1 With the T in the above group 1a 1 and M 1 Similarly, the explanation is omitted.

[0955] M 1 Si is preferred.

[0956] T 1 Trialkylsiloxy is preferred, and butyldimethylsiloxy, trimethylsiloxy, or triethylsiloxy are more preferred.

[0957] R 2 L and n are related to R in the above formula (S1) 2 The same applies to L and n.

[0958] Z 1 The combination of the alkylene chain and the divalent chain organo(poly)siloxane residues shown is preferably represented by the following formulas (D3), (D4) or (D5).

[0959]

[0960] In formula (D3), Ak 1 and Ak 2 Each represents an alkylene chain independently. R 3 R in equation (B1) 3 Same. k11 is a number greater than or equal to 1. k12 is 0 or 1.

[0961] In equation (D4), Ak 3 It refers to an alkylene chain. R 3 R in equation (B1) 3 They are the same. k21 and k22 are each independently numbers greater than or equal to 1.

[0962] In equation (D5), Ak 4 It refers to an alkylene chain. R 3 R in equation (B1) 3 Same. k31 is a number greater than or equal to 1.

[0963] In formulas (D3), (D4), or (D5), *1 is connected to the group 1a side, and *2 is connected to the group 1b side.

[0964] As A, any group that does not impair the effects of this disclosure may be used. Examples include alkylene groups, carbon atoms, nitrogen atoms, silicon atoms, 2- to 8-valent organosiloxane residues, and groups from (3-1A), (3-1B), and (3-1A-1) to (3-1A-7) to remove Si (R) from the above groups. 2 ) n L 3-n The resulting functional groups.

[0965] A can also contain triterpenoid structures. Triterpenoid structures refer to partial structures formed by removing two or more hydrogens from triterpenoids.

[0966] Alternatively, A can be any of the above groups (g2-1) to (g2-14).

[0967] p1 is an integer greater than or equal to 1. From the perspective of superior water repellency of the surface treatment layer, p1 is preferably 1 to 6, and more preferably 2 to 4. p1 can also be 1.

[0968] When p1 is 2 or higher, multiple [T] 1 3M 1 -(O) r -Z 1 They can be the same or different from each other.

[0969] q1 is an integer greater than or equal to 1. From the perspective of superior wear resistance of the surface treatment layer, q1 is preferably 1 to 15, more preferably 1 to 6, further preferably 2 to 6, particularly preferably 2 to 4, and extremely preferably 2 or 3. q1 may also be 1.

[0970] When q1 is 2 or higher, multiple [Si(R)] 2 ) n L 3-n They can be the same or different from each other.

[0971] The group A(Si(R) in formula (1A) 2 ) n L 3-n ) q1 The preferred method is the same as the group A(Si(R) in the aforementioned "partial structure of compound 1, compound 2 and compound (E)" section. 2 ) n L 3-n ) q1 The preferred method is the same. Wherein, group A (Si (R) 2 ) n L 3-n ) q1 A in the equation (1A) and [T] 1 3M 1 -(O) r -Z 1 ] p1 Connection. Z 1 When the terminal end of the side of A that is bonded to Z is an alkylene chain, the relationship between A and Z... 1 The end of the bonded side is not an alkylene chain. Z 1 When the end of the side of A that is bonded to Z is a polyepoxide chain, the relationship between A and Z... 1 The end of the bonded side is not a polyepoxide chain.

[0972] Compound (1) is preferably a compound represented by the following formula (1B).

[0973]

[0974] In equation (1B), T 1 With T in group 1a 1 same.

[0975] R 3 R in equation (B1) 3 Same. k31 is the same as k31 in equation (D5).

[0976] A(Si(R) 2 ) n L 3-n ) q1 The groups shown are similar to A(Si(R) in formula (1A). 2 ) n L 3-n ) q1 The groups shown are the same.

[0977] Ak 4 With Ak in equation (D5) 4 same.

[0978] Compound (1) is preferably a compound represented by formula (1C), formula (1D) or formula (1E).

[0979]

[0980]

[0981]

[0982] In equations (1C), (1D), and (1E), R 3 R in equation (B1) 3 Same. k31 is the same as k31 in equation (D5).

[0983] A(Si(R) 2 ) n L 3-n ) q1 The groups shown are similar to A(Si(R) in formula (1A). 2 ) n L 3-n ) q1 The groups shown are the same.

[0984] Ak 4 With Ak in equation (D5) 4 same.

[0985] As a specific example of compound (1), the following compounds can be cited.

[0986] In the following formula, n10 is a number greater than or equal to 1. Preferably, n10 is a number between 1 and 60, but it can be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0987]

[0988] In the following formulas, k is preferably 1 to 80, more preferably 3 to 50, and even more preferably 3 to 30. m is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10. t is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10.

[0989] In the following formula, n10 is a number greater than or equal to 1. Preferably, n10 is a number between 1 and 60, but it can be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0990]

[0991] In the following formula, n10 is a number greater than or equal to 1. Preferably, n10 is a number between 1 and 60, but it can be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0992]

[0993] (Compound (2))

[0994] In compound (2), alkyl refers to an unsubstituted alkyl group. The alkyl group can be any of the following: straight-chain alkyl, branched alkyl, and cyclic alkyl, preferably straight-chain or branched alkyl. The alkyl group preferably has 2 to 30 carbon atoms, more preferably 3 to 28, and even more preferably 4 to 22.

[0995] In a compound, there may be only one alkyl group or there may be more than two alkyl groups.

[0996] Alkyl groups are monovalent and therefore located at the end of the compound.

[0997] Compound (2) is preferably a compound represented by the following formula (2A).

[0998] (T) 2 -Z 2 ) p1 A(Si(R) 2 ) n L 3-n ) q1 … (2A)

[0999] In equation (2A),

[1000] T 2 Alkyl groups having 2 or more carbon atoms

[1001] Z 2 It consists of divalent chain organo(poly)siloxane residues.

[1002] A is a single bond or a (p1+q1) valence linker.

[1003] R 2 Each is an independent monovalent hydrocarbon group.

[1004] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1005] n is an integer between 0 and 2.

[1006] p1 and q1 are each an independent integer greater than or equal to 1.

[1007] T 2 The preferred configuration of alkyl groups having 2 or more carbon atoms is as described above.

[1008] Z 2 The divalent chain organo(poly)siloxane residues shown are preferably groups represented by the above formula (B1).

[1009] R 2 L and n are related to R in the above formula (S1) 2 The same applies to L and n.

[1010] A(Si(R) 2 ) n L 3-n ) q1 In addition to the contents shown below, the groups shown are similar to A(Si(R) in the above formula (1A). 2 ) n L 3-n ) q1 The same applies to the groups shown.

[1011] p1 and q1 are the same as p1 and q1 in the above equation (1A).

[1012] A(Si(R) 2 ) n L 3-n ) q1 The indicated group is preferably group (3-1A) or group (3-1B), more preferably group (3-1A).

[1013] In formula (3-1A), Q a It is a single bond or a divalent linker.

[1014] Among them, Q a and Z 2 The end of the bonded side is not an oxysilyl group.

[1015] In equation (3-1A), X 31 It can be a single bond, alkylene group, carbon atom, nitrogen atom, silicon atom, organo(poly)siloxane residue with 2 to 8 valences, or a cyclic group with (h+i+1) valences.

[1016] Among them, Q a In the case of a single key, X 31 and Z 2 The terminal of the bonded side is not an oxysilyl group. In other cases, X 31 The terminal end can be oxysilyl.

[1017] In formula (3-1A), Q b It is a single bond or a divalent linker.

[1018] Among them, Q a and X 31 In the case of a single key, Q b and Z 2 The terminal of the bonded side is not an oxysilyl group. In other cases, Q b The terminal end can be oxysilyl.

[1019] Additionally, h is 1 and Q is 1. b In the case of alkylene, Q a -X 31 Q b The side end is not an alkylene group.

[1020] In equation (3-1B), Q c It is a single bond or a divalent linker.

[1021] Among them, Q c and Z 2 The end of the bonded side is not an oxysilyl group.

[1022] As a group (3-1A), groups (3-1A-1) to (3-1A-7) are preferred.

[1023] Among them, the groups (3-1A-1)~(3-1A-7) and Z 2 The end of the bonded side is not an oxysilyl group.

[1024] In group (3-1A-1), X 32 Preferably -O-, -S-, -N(R) d )-, -C(O)O-, -C(O)S-, -N(R d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d-, more preferably -C(O)O- or -C(O)N(R) d )-.

[1025] s1 is preferably 0, Q b1 Alkylenes with 2 to 6 carbon atoms are preferred.

[1026] In group (3-1A-2), X 33 Preferably -O-, -C(O)O-, or -C(O)N(R) d )-.

[1027] In formula (2A), A can be a group (g2-1)~(g2-7).

[1028] In equations (g2-1) to (g2-7), A 1 Side and Z 2 Bonding, Q 22 Q 23 Q 24 Q 25 Or Q 26 Side and [-Si(R)] 2 ) n L 3-n ] Bonding.

[1029] Other forms of A include groups (g2-8) to (g2-14).

[1030] In equations (g2-8) to (g2-14), A 1 Side and Z 2 Bonding, G 1 Side and [-Si(R)] 2 ) n L 3-n ] Bonding.

[1031] Compound (2) is preferably a compound represented by the following formula (2B).

[1032]

[1033] In equation (2B), R 51 It is an alkyl group with 2 or more carbon atoms.

[1034] R 52 and R 54 Each is an alkylene group independently.

[1035] R 53 is -C(O)O-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)- or -C(O)N(R)d )-.

[1036] R 3 R in equation (B1) 3 Same. k1 is the same as k1 in equation (B1).

[1037] X 31 (-Q) b -Si(R) 2 ) n L 3-n ) h (-R) 31 ) i The groups shown are X in group (3-1A) 31 (-Q) b -Si(R) 3 ) n L 3-n ) h (-R) 31 ) i The groups shown are the same.

[1038] t1 is either 0 or 1.

[1039] R 51 The preferred configuration of the alkyl group is as described in the alkyl group section above.

[1040] R 52 The alkylene group shown can be linear, branched, or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 4 to 20, and particularly preferably 5 to 15.

[1041] R 54 The alkylene group shown can be linear, branched, or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3.

[1042] As a compound (2), for example, the following compounds can be cited. In the following formula, n10 is a number of 1 or more, preferably a number of 1 to 60, but can be a number of 3 to 50, a number of 5 to 30, or a number of 7 to 25.

[1043]

[1044]

[1045]

[1046]

[1047]

[1048] (Compound (3))

[1049] Compound (3) is preferably a compound represented by the following formula (3A).

[1050] [T 3 -(O) r -Z 3 ] p1 A(Si(R) 2 ) n L 3-n ) q1 …(3A)

[1051] In equation (3A),

[1052] T 3 It consists of monovalent cyclic polysiloxane residues or monovalent cage-like polysiloxane residues.

[1053] r is 0 or 1.

[1054] Z 3 It is a divalent chain organo(poly)siloxane residue, or a combination of a divalent chain organo(poly)siloxane residue with at least one of an alkylene chain and a polyepoxide chain.

[1055] A is a single bond or a (p1+q1) valence linker.

[1056] R 2 Each is an independent monovalent hydrocarbon group.

[1057] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1058] n is an integer between 0 and 2.

[1059] p1 and q1 are each an independent integer greater than or equal to 1.

[1060] R 2 L and n are related to R in the above formula (S1) 2 The same applies to L and n.

[1061] A(Si(R) 2 ) n L 3-n ) q1 In addition to the contents shown below, the groups shown are similar to A(Si(R) in the above formula (1A). 2 ) n L 3-n ) q1 The same applies to the groups shown.

[1062] p1 and q1 are the same as p1 and q1 in the above equation (1A).

[1063] Details of monovalent cyclic polysiloxane residues or monovalent cage-like polysiloxane residues are as shown in T of formula (C). 11 As stated in the description.

[1064] A(Si(R) 2 ) n L 3-n ) q1 The indicated group is preferably group (3-1A) or group (3-1B), more preferably group (3-1A).

[1065] In formula (3-1A), Q a It is a single bond or a divalent linker.

[1066] Among them, Q a and Z 3 The end of the bonded side is not any of the following: alkylene, polyepoxide chain, or divalent organo(poly)siloxane residues.

[1067] Z 3 When the A-side terminal is an alkylene chain, Q a Preferably, divalent hydrocarbon groups other than alkylene groups, divalent heterocyclic groups, -O-, -S-, -SO2-, -N(R) d -, -C(O)-, -Si(R) a )2-, -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, possessing -C(O)N(R) d )-alkylene groups, having -N(R d )C(O)- alkylene groups, having -OC(O)N(R d Alkylenes with - ether oxygen atoms, alkylenes with -S-, alkylenes with -OC(O)-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, having -N(R d C(O)N(R) d )-alkylene groups, or those having -SO2N(R d)- alkylene groups, more preferably -OC(O)-, having -C(O)N(R d )-alkylene groups, having -OC(O)N(R d Alkylenes with -S-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, or those having -N(R d C(O)N(R) d Alkylenes having -C(O)O-, or alkylenes having -C(O)N(R)- d )-alkylene.

[1068] Z 3 When the A-side end is a polyoxyalkylene chain, Q a Preferably, it is a divalent hydrocarbon group other than an alkylene group, a divalent heterocyclic group, -SO2-, -C(O)-, or -Si(R)-. a )2-, -C(O)O-, -C(O)S-, -C(O)N(R d -, -SO2N(R) d -、Having -C(O)N(R) d alkylene groups having -C(O)O-, or alkylene groups having -SO2N(R)- d )- alkylene groups, more preferably -C(O)-.

[1069] Z 3 When the A-side terminal is a divalent chain organo(poly)siloxane residue, Q a Preferably, divalent hydrocarbon groups other than alkylene groups, divalent heterocyclic groups, -O-, -S-, -SO2-, -N(R) d -, -C(O)-, -Si(R) a )2-, -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, possessing -C(O)N(R) d )-alkylene groups, having -N(R d )C(O)- alkylene groups, having -OC(O)N(R dAlkylenes with - ether oxygen atoms, alkylenes with -S-, alkylenes with -OC(O)-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, having -N(R d C(O)N(R) d )-alkylene groups, or those having -SO2N(R d )-alkylene.

[1070] In equation (3-1A), X 31 It can be a single bond, alkylene group, carbon atom, nitrogen atom, silicon atom, organo(poly)siloxane residue with 2 to 8 valences, or a cyclic group with (h+i+1) valences.

[1071] Among them, in Q a In the case of a single key, X 31 and Z 3 The terminal of the bonded side is not any of the following: alkylene, polyepoxide chain, or divalent organo(poly)siloxane residue. In cases other than those described above, X 31 The terminal can be any of the following: alkylene, polyepoxide chain, and divalent organo(poly)siloxane residues.

[1072] In formula (3-1A), Q b It is a single bond or a divalent linker.

[1073] Among them, Q a and X 31 In the case of a single key, Q b and Z 3 The terminal of the bonded side is not any of the following: alkylene, polyepoxide chain, or divalent organo(poly)siloxane residue. In other cases, Q b The terminal can be any of the following: alkylene, polyepoxide chain, and divalent organo(poly)siloxane residues.

[1074] In formula (3-1A), Q a X 31 and Q b In the case of a single bond, [Si(R) 2 ) n L 3-n ] and Z 3 Direct bonding, Z 3 It is an alkylene chain.

[1075] In equation (3-1B), Q c It is a single bond or a divalent linker.

[1076] Among them, Q c and Z 3The end of the bonded side is not any of the following: alkylene, polyepoxide chain, or divalent organo(poly)siloxane residues.

[1077] As a group (3-1A), groups (3-1A-1) to (3-1A-7) are preferred.

[1078] Among them, the groups (3-1A-1)~(3-1A-7) and Z 3 The end of the bonded side is not any of the following: alkylene, polyepoxide chain, or divalent organo(poly)siloxane residues.

[1079] In group (3-1A-1), Z 3 When the A-side terminal is an alkylene chain, X 32 Preferably -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d -, more preferably -O-, -S-, -N(R) d )-, -C(O)O-, -C(O)S-, -N(R d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d -, more preferably -C(O)O- or -N(R) d )C(O)-.

[1080] Z 3 When the A-side end is a polyoxyalkylene chain, X 32 Preferably -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R) d - or -C(O)N(R) d -, more preferably -C(O)-.

[1081] Z 3 When the A-side terminal is a divalent chain organo(poly)siloxane residue, X 32 Preferably -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d)-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d )-, more preferably -O-.

[1082] Z 3 When the A-side terminal is an alkylene chain, it is preferable that s1 is 0 and Q is 0. b1 It is a single bond, or s1 is 1, and Q b1 It is an alkylene group having 2 to 6 carbon atoms.

[1083] Z 3 When the A-side end is a polyepoxide chain, it is preferable that s1 is 1 and Q is 1. b1 It is an alkylene group having 2 to 6 carbon atoms.

[1084] Z 3 When the A-side terminal is a divalent chain organo(poly)siloxane residue, it is preferable that s1 is 1 and Q is 1. b1 It is a single key.

[1085] In group (3-1A-2), Z 3 When the A-side terminal is an alkylene chain or a divalent chain organo(poly)siloxane residue, X 33 Preferably -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d )-.

[1086] Z 3 When the A-side end is a polyoxyalkylene chain, X 33 Preferably -C(O)O-, -C(O)S-, -SO2N(R) d - or -C(O)N(R) d )-.

[1087] In formula (3A), A can be a group (g2-1)~(g2-7).

[1088] In equations (g2-1) to (g2-7), A1 Side and Z 3 Bonding, Q 22 Q 23 Q 24 Q 25 Or Q 26 Side and [-Si(R)] 2 ) n L 3-n ] Bonding.

[1089] Other forms of A include groups (g2-8) to (g2-14).

[1090] In equations (g2-8) to (g2-14), A 1 Side and Z 3 Bonding, G 1 Side and [-Si(R)] 2 ) n L 3-n ] Bonding.

[1091] As a specific example of compound (3), the following compounds can be cited. In the following formula, n10 is a number of 1 or more, preferably a number of 1 to 60, but can be a number of 3 to 50, a number of 5 to 30, or a number of 7 to 25.

[1092]

[1093] (Compounds (4A), (4B))

[1094] In compounds (4A) and (4B),

[1095] X A Each independently is better as

[1096] -(CH2) s7 -O-(CH2) t7 -、

[1097] -(CH2) s7 -CONR 54 -(CH2) t7 -、

[1098] -(CH2) s7 -O-(CH2) u7 -CO-, or

[1099] -(CH2) s7 -O-(CH2) u7 -CONR 54 -(CH2) t7 -

[1100] R54 Each group is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an oxyalkylene group having 1 to 10 carbon atoms.

[1101] s7 is an integer from 1 to 20.

[1102] t7 is an integer from 1 to 20.

[1103] u7 is an integer from 1 to 20.

[1104] X A Each group is preferably represented by the following formula (W6).

[1105] In equation (W6), X a Each is an independent single bond or a divalent organic group.

[1106]

[1107] As specific examples of compound (4A), the following compounds can be cited.

[1108] ·(CH3)3Si-(OSi(CH3)2) 19 -(CH2) 10 -CONH-CH2C{CH2CH2CH2Si(OCH3)3}3

[1109] (Compound (5))

[1110] When the surface treatment agent of this disclosure contains compound (5), the surface treatment agent of this disclosure preferably also contains a metal compound.

[1111] The metal compound is preferably a compound represented by the following formula (M6a) or (M6b).

[1112]

[1113] In formula (M6a),

[1114] R k1 This refers to groups containing a siloxane skeleton, groups containing a hydrocarbon chain, or hydrolyzable groups.

[1115] Multiple X k1 Each of them independently represents a hydrolyzable group.

[1116] X k2 This indicates a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrolyzable group.

[1117] R k1 and X k1 The number of elements in the siloxane skeleton group is less than that in compound (5) (R a9)3Si-Z-(Si(R) s1 )2-O-) n9 -Y- indicates the number of elements in a molecular chain containing trialkylsilyl groups, R k1 and X k1 The longest straight chain of the hydrocarbon chain in the hydrocarbon-containing group contains fewer carbon atoms than that in compound (5) (R). a9 )3Si-Z-(Si(R) s1 )2-O-) n9 -Y- indicates the number of elements in a molecular chain containing trialkylsilyl groups.

[1118] R k1 and X k2 In the case of a group containing a siloxane skeleton or a group containing a hydrocarbon chain, R k1 With X k2 They can be the same or different.

[1119] X k2 In the case of a hydrolyzable group, X k2 With X k1 They can be the same or different. Also, R... k1 and X k2 They can be the same or different. M 4 This represents trivalent or tetravalent metal atoms capable of forming metal alkoxides. m14 is based on M. 4 Integers that represent 0 or 1.

[1120]

[1121] In formula (M6b),

[1122] R k3 Indicates hydrolyzable silane oligomer residues.

[1123] X k3 It indicates a hydrolyzable group, a fluorinated alkyl group with 1 to 4 carbon atoms, or an alkyl group with 1 to 4 carbon atoms.

[1124] As a specific example of compound (5), the following compounds can be cited. In the following formula, n10 is a number of 1 or more, preferably a number of 1 to 60, but can be a number of 3 to 50, a number of 5 to 30, or a number of 7 to 25.

[1125]

[1126] <Liquid Medium>

[1127] Surface treatment agents may contain liquid media.

[1128] The liquid medium can be only one type or two or more types.

[1129] Organic solvents are preferred for liquid media.

[1130] As organic solvents, examples include compounds composed only of hydrogen and carbon atoms, as well as compounds composed only of hydrogen, carbon, and oxygen atoms. Specifically, examples include hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, glycol-based organic solvents, and alcohol-based organic solvents.

[1131] Specific examples of hydrocarbon-based organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexane, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.

[1132] Specific examples of ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, and isophorone.

[1133] Specific examples of ether-based organic solvents include diethyl ether, cyclopentylmethyl ether, tetrahydrofuran, and 1,4-dioxane.

[1134] Specific examples of ester-based organic solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl acetate, ethylene glycol monoethyl ether acetate, etc. Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, γ-butyrolactone, triacetin, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

[1135] Specific examples of diol-based organic solvents include ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and so on. Propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butanediol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, pentane, triethylene glycol dimethyl ether, polyethylene glycol dimethyl ether.

[1136] Specific examples of alcohol-based organic solvents include methanol, ethanol, 1-propanol, isopropanol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isothietrol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, and methylcyclohexanol.

[1137] In addition, examples of organic solvents include halogenated organic solvents, nitrogen-containing compounds, sulfur-containing compounds, siloxane compounds, and fluorinated organic solvents.

[1138] Specific examples of halogenated organic solvents include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.

[1139] Examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolium ketone.

[1140] Examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

[1141] Examples of siloxane compounds include hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octaethyltrisiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, and decamethyltetrasiloxane.

[1142] Examples of fluorinated organic solvents include polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F...). 13 CH2CH3 (e.g., Asahiklin AC-6000 manufactured by AGC Corporation, a registered trademark); 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., ZEORORA H manufactured by ZEON CORPORATION, a registered trademark); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Corporation, a registered trademark); perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec 7100 manufactured by Sumitomo 3M Corporation, a registered trademark); perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec 7200 manufactured by Sumitomo 3M Corporation, a registered trademark); perfluorohexyl methyl ether (C2F5CF(OC)). Alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl can be straight-chain or branched) such as H3)C3F7) (e.g. Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.), CF3CH2OCF2CHF2 (e.g. Asahiklin (registered trademark) AE-3000 manufactured by AGC Co., Ltd.); and hydrofluoroolefins (HFO) such as 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (e.g. AMOLEA (registered trademark) AS-300 manufactured by AGC Co., Ltd.), Opteon (registered trademark) SF01, SF05, SF10, SF30, SF33, SF70, SF79, SF80 manufactured by The Chemours Company.

[1143] The content of the liquid medium relative to the total amount of the surface treatment agent is preferably 50 to 99.999% by mass, more preferably 80 to 99.99% by mass, and even more preferably 90 to 99.9% by mass. In the case of a surface treatment agent used in a wet coating method, the content of the liquid medium relative to the total amount of the surface treatment agent can be 90 to 99.99% by mass, 95 to 99.98% by mass, 97 to 99.97% by mass, or 98 to 99.95% by mass.

[1144] <Other Ingredients>

[1145] In addition to liquid media, surface treatment agents may contain other components without impairing the effects of this disclosure.

[1146] Other components include, for example, well-known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reactions of reactive silyl groups.

[1147] As catalysts, any suitable acid or base, transition metal (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds with non-shared electron pairs in their molecular structure, nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoramide compounds, amide compounds, urea compounds, etc.) can be used.

[1148] Examples of acid catalysts include acetic acid, formic acid, trifluoroacetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.

[1149] In addition, examples of alkaline catalysts include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine.

[1150] In addition, other components may include metal compounds with hydrolyzable groups (hereinafter, metal compounds with hydrolyzable groups will also be referred to as "specific metal compounds"). If the surface treatment agent contains a specific metal compound, the slip properties and antifouling properties of the surface treatment layer can be further improved. Examples of specific metal compounds include the following formulas (M1) to (M3).

[1151] M(X) b1 ) m11 (X) b2 ) m12 (X) b3 ) m13 …(M1)

[1152] Si(X) b4 (X) b5 3… (M2)

[1153] (X) b6 )3Si-(Y b1 )-Si(X b7 )3…(M3)

[1154] In formula (M1),

[1155] M represents a trivalent or tetravalent metal atom.

[1156] X b1 Each of them independently represents a hydrolyzable group.

[1157] X b2Each group independently represents a group containing a siloxane skeleton.

[1158] X b3 Each can be used independently to represent a group containing a hydrocarbon chain.

[1159] m11 is an integer between 2 and 4.

[1160] m12 and m13 are each independent integers from 0 to 2.

[1161] When M is a trivalent metal atom, m11+m12+m13 is 3; when M is a tetravalent metal atom, m11+m12+m13 is 4.

[1162] In formula (M2),

[1163] X b4 This indicates hydrolyzable silane oligomer residues.

[1164] X b5 Each can be independently represented as a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.

[1165] In formula (M3),

[1166] X b6 and X b7 Each can independently represent a hydrolyzable group or a hydroxyl group.

[1167] Y b1 It represents a divalent organic group.

[1168] In formula (M1), the metal represented by M also includes half-metals such as Si and Ge. As M, trivalent metals and tetravalent metals are preferred, Al, Fe, In, Hf, Si, Ti, Sn and Zr are more preferred, Al, Si, Ti and Zr are even more preferred, and Si is particularly preferred.

[1169] In equation (M1), X is... b1 The hydrolyzable groups shown can be exemplified by [-Si(R)] in the above-mentioned reactive silyl groups. 2 ) n L 3-n The L in the figure represents the same hydrolyzable group as the group in the figure.

[1170] X b2 The shown group containing a siloxane skeleton has a siloxane unit (-Si-O-), which can be linear or branched. As the siloxane unit, dialkylsiloxy is preferred, and examples include dimethylsiloxy and diethylsiloxy. The number of repetitions of the siloxane unit in the group containing the siloxane skeleton is 1 or more, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

[1171] The groups containing the siloxane skeleton may include a divalent hydrocarbon group in a portion of the siloxane skeleton. Specifically, a portion of the oxygen atoms in the siloxane skeleton may be replaced by a divalent hydrocarbon group. Examples of such divalent hydrocarbon groups include alkylene groups such as methylene, ethylene, propylene, and butylene.

[1172] Hydrolyzable groups, hydrocarbon groups (preferably alkyl groups), etc., can be bonded to the silicon atoms at the ends of groups containing siloxane skeletons.

[1173] The number of elements containing the siloxane skeleton is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. The aforementioned number of elements is preferably 10 or more.

[1174] As a group containing a siloxane backbone, preferably ＊ -(O-Si(CH3)2) n The group shown in CH3, where n is an integer from 1 to 5, and * indicates the bonding site with the adjacent atom.

[1175] X b3 The hydrocarbon-containing group shown can be a group consisting solely of a hydrocarbon chain, or a group having ether-like oxygen atoms between carbon atoms in the hydrocarbon chain. The hydrocarbon chain can be straight or branched, preferably straight. The hydrocarbon chain can be saturated or unsaturated, preferably saturated. The number of carbon atoms in the hydrocarbon-containing group is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. Alkyl groups are preferred as hydrocarbon-containing groups, more preferably methyl, ethyl, or propyl.

[1176] m1 is preferably 3 or 4.

[1177] As the compound represented by formula (M1), it is preferable to have compounds represented by formulas (M1-1) to (M1-5) where M is Si, and more preferably to have compounds represented by formula (M1-1). As the compound represented by formula (M1-1), tetraethoxysilane, tetramethoxysilane, and triethoxymethylsilane are preferred.

[1178] Si(X) b1 4…(M1-1)

[1179] CH3-Si(X) b1 3…(M1-2)

[1180] C2H5-Si(X) b1 3…(M1-3)

[1181] n-C3H7-Si(X) b1 3…(M1-4)

[1182] (CH3)2CH-Si(X) b1 3… (M1-5)

[1183] In formula (M2), X b4 The number of silicon atoms contained in the hydrolyzable silane oligomer residues shown is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The aforementioned number of silicon atoms is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.

[1184] The hydrolyzable silane oligomer residues may have alkoxy groups bonded to silicon atoms. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, and butoxy, with methoxy and ethoxy being preferred. The hydrolyzable silane oligomer residues may have one or more of these alkoxy groups, with one being preferred.

[1185] Examples of hydrolyzable silane oligomer residues include (C2H5O)3Si-(OSi(OC2H5)2)4O- ＊ Etc. Here, * indicates the bonding site with an adjacent atom.

[1186] In equation (M2), X is... b5 The hydrolyzable groups shown can be exemplified by [-Si(R)] in the above-mentioned reactive silyl groups. 2 ) n L 3-n The L in the figure represents the same hydrolyzable group, cyano group, hydrogen atom, allyl group, preferably alkoxy or isocyanate group. As an alkoxy group, an alkoxy group with 1 to 4 carbon atoms is preferred.

[1187] As X b5 Preferably, hydrolyzable groups are used.

[1188] Examples of compounds represented by formula (M2) include (H5C2O)3-Si-(OSi(OC2H5)2)4OC2H5.

[1189] The compound represented by formula (M3) is a compound with reactive silyl groups at both ends of a divalent organic group, namely a bissilane.

[1190] In formula (M3), X is used as b6 and X b7 Examples of hydrolyzable groups include alkoxy, acyloxy, ketoxime, alkenoxy, amino, aminooxy, amide, isocyanate, and halogen atoms, with alkoxy and isocyanate groups being preferred. As an alkoxy group, an alkoxy group with 1 to 4 carbon atoms is preferred, and methoxy and ethoxy groups are more preferred.

[1191] In formula (M3), X b6 and X b7 They can be the same group or different group. From the point of view of easy access, X b6 and Xb7 Preferably, the groups are the same as each other.

[1192] In formula (M3), Y b1 The Y-terminus is a divalent organic group consisting of reactive silyl groups at both ends. b1 The number of carbon atoms is preferably 1 to 8, more preferably 1 to 3.

[1193] As Y b1 Examples include alkylene, phenylene, and alkylene with an ether-like oxygen atom between carbon atoms. Examples include -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2C(CH3)2CH2-, -C(CH3)2CH2CH2C(CH3)2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH(CH3)CH2OCH2CH(CH3)-, and -C6H4-.

[1194] Examples of compounds represented by formula (M3) include (CH3O)3Si(CH2)2Si(OCH3)3, (C2H5O)3Si(CH2)2Si(OC2H5)3, (OCN)3Si(CH2)2Si(NCO)3, Cl3Si(CH2)2SiCl3, (CH3O)3Si(CH2)6Si(OCH3)3, and (C2H5O)3Si(CH2)6Si(OC2H5)3.

[1195] The content of other components that may be included in the surface treatment agent is preferably 10% by mass or less, more preferably 1% by mass or less, relative to the total amount of the surface treatment agent. When the surface treatment agent contains a specific metal compound, the content of the specific metal compound relative to the total amount of the surface treatment agent is preferably 0.01 to 30% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.05 to 5% by mass.

[1196] The total content of the specific silane compound and other components (hereinafter also referred to as "solid component concentration") relative to the total amount of the surface treatment agent is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass. The solid component concentration of the surface treatment agent is a value calculated from the mass before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[1197] As for surface treatments that use surface treatment agents, examples include dry coating and wet coating.

[1198] Examples of dry coating methods include vacuum evaporation, CVD, PVD, and sputtering. From the viewpoints of suppressing compound decomposition and the simplicity of the apparatus, vacuum evaporation is preferred as a dry coating method. During vacuum evaporation, granular materials containing the disclosed compound can be used to impregnate porous metals such as iron or steel. Alternatively, granular materials containing the disclosed compound can be impregnated into porous metals such as iron or steel by impregnating them with a composition containing the disclosed compound and a liquid medium, and then the liquid medium is dried.

[1199] Examples of wet coating methods include spin coating, wiping coating, spray coating, scraper coating, dip coating, mold coating, inkjet coating, flow coating, roller coating, casting, Langmuir-Blodgett coating, and gravure coating.

[1200] To improve the wear resistance of the surface treatment layer, operations can be performed as needed to promote the reaction between compounds having chain-like organo(poly)siloxane residues and reactive silyl groups and the substrate layer. Examples of such operations include heating, humidification, and light irradiation.

[1201] For example, a substrate with a surface-treated layer can be heated in a humid atmosphere to promote the hydrolysis of hydrolytic groups, the reaction of hydroxyl groups on the substrate surface with silanol groups, and the formation of siloxane bonds caused by the condensation reaction of silanol groups.

[1202] After surface treatment, other compounds or compounds not chemically bonded to the substrate layer can be removed from the surface treatment layer as needed. Examples of removal methods include pouring solvent into the surface treatment layer or wiping with a cloth soaked in solvent.

[1203] The items disclosed herein may be optical materials having a surface-treated layer on the outermost layer.

[1204] As optical materials, in addition to optical materials related to displays, a wide variety of optical materials are preferred.

[1205] As optical materials, examples include cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent tubes (VFDs), field emission displays (FEDs), and other displays or protective plates for these displays, or those on which anti-reflective coatings have been applied.

[1206] The items disclosed herein are preferably optical components. Examples of optical components include car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car stereos, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, endoscopes and other medical devices, copiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and anti-reflective films.

[1207] In addition, as optical components, examples include the front protective plate, anti-reflective plate, polarizing plate, and anti-glare plate of displays such as PDP and LCD; the disc surface of Blu-ray (Blu-ray disc, DVD disc, CD-R, MO disc, etc.); optical fiber; and the display surface of clocks and watches.

[1208] In particular, the items disclosed herein are preferably displays or touch panels.

[1209] The items disclosed herein can also be medical devices or medical materials. Additionally, the items disclosed herein can be automotive interior and exterior components. Examples of exterior materials include windows, lamp covers, and exterior camera covers. Examples of interior materials include dashboard covers, navigation system touch panels, and interior trim materials.

[1210] When the disclosed article is an optical component, the material constituting the surface of the substrate is a material used for optical components, such as glass or transparent plastic. Furthermore, when the disclosed article is an optical component, functional layers such as a hard coating or an anti-reflective layer can be formed on the surface (outermost layer) of the substrate. The anti-reflective layer can be either a single-layer anti-reflective layer or a multi-layer anti-reflective layer.

[1211] Examples of inorganic materials that can be used in antireflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials can be used alone or in combination of two or more (e.g., as a mixture). In the case of a multilayer antireflective layer, SiO2 and / or SiO are preferably used in the outermost layer. When the disclosed article is an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, can be provided on a portion of the surface of the substrate (glass). In addition, the substrate can have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a frosting film layer, a hard coating layer, a polarizing film, a retardation film, a liquid crystal display module, etc., depending on its specific specifications.

[1212] [How to make the item]

[1213] The method for manufacturing articles disclosed herein uses a surface treatment agent to surface treat a substrate to manufacture an article having a surface treatment layer formed on the substrate. The surface roughness Sdr of the surface treatment layer is 30% or more in any measured area ranging from 5 to 50 μm square. The surface treatment agent contains a compound having chain groups and reactive silyl groups.

[1214] In one embodiment, the method of manufacturing the article disclosed herein preferably uses a surface treatment agent to surface treat a substrate to manufacture an article having a surface treatment layer formed on the substrate, wherein the surface roughness Sdr of the surface treatment layer is 30% or more in any measured area of ​​5 to 50 μm square, and the surface treatment agent comprises a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

[1215] The method for achieving a surface roughness Sdr of 30% or more within any measurement area of ​​5-50 μm square of the surface treatment layer is as described above.

[1216] From the viewpoint that the surface roughness Sdr of the surface treatment layer is 30% or more in any measurement area of ​​5 to 50 μm square, the substrate is preferably a substrate with a surface roughness Sdr of 30% or more in any measurement area of ​​5 to 50 μm square.

[1217] Details of the surface treatment agent are as described above.

[1218] In addition, the surface treatment method using surface treatment agents is as described above.

[1219] Example

[1220] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[1221] [Synthesis of Compound 11B]

[1222] Under a nitrogen atmosphere, 5.0 g of carboxylic acid-terminated polydimethylsiloxane (average n = 16, alkylene oxide linked to the carboxylic acid having 10 carbon atoms; manufactured by Gelest, product number: MCR-B12), dichloromethane (20 mL), and oxaloyl chloride (1.3 g) were added to a 100 mL flask and stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by vacuum distillation, 2.3 g of 2-(undec-10-en-1-yl)dedec-12-en-1-amine (2.3 g), dichloromethane (20 mL), and triethylamine (0.70 g) were added and stirred at 25 °C for 2 hours. After removing the solvent and low-boiling components by vacuum distillation, rapid column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was performed to obtain 2.8 g of compound 11A. The structure of compound 11A was confirmed by the following NMR data. In compound 11A, the average n10 value is 16. It should be noted that in formula (11A), n-Bu represents n-butyl (CH3CH2CH2CH2-) and Me represents methyl (CH3-). The same applies below.

[1223]

[1224] 1 H-NMR (400 MHz, CDCl3) δ 5.74 (ddt, J = 16.9, 10.2, 6.7 Hz, 2H), 5.24 (t, J = 5.7 Hz, 1H), 5.04-4.76 (m, 4H), 3.11 (t, J = 6.0 Hz, 2H), 2.17‐2.04 (m, 2H), 2.04‐1.87 (m, 4H), 1.61‐1.51 (m, 2H), 1.47‐1.04 (m, 51H), 0.93‐0.75 (m, 3H), 0.55‐0.36 (m, 4H), 0.07 (s, 102H).

[1225] In a 20 mL flask, 2.0 mL of 1,3-bis(trifluoromethylbenzene) and 1.0 g of compound 11A were added and stirred at 25 °C. Next, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 15 μL), aniline (4.8 μL), and trimethoxysilane (0.31 g) were added, and the mixture was stirred at 40 °C for 2 hours. The solvent was removed by vacuum distillation, yielding 1.1 g of compound 11B. The structure of compound 11B was confirmed by the following NMR data. In compound 11B, the average n10 value is 16.

[1226]

[1227] 1 H-NMR (400 MHz, CDCl3) δ 5.31-5.16 (m, 1H), 3.50 (s, 18H), 3.11 (t, J= 6.0 Hz, 2H), 2.15-2.02 (m, 2H), 1.66-0.89 (m, 61H), 0.90-0.73 (m, 3H), 0.66-0.52 (m, 4H), 0.46 (ddd, J = 12.6, 7.0, 3.2 Hz, 4H), 0.07 (s, 102H).

[1228] [Synthesis of compound 12F]

[1229] Compound 12A was obtained according to the method described in International Publication No. 2021 / 054413.

[1230]

[1231] Compound 12B was obtained according to the method described in Japanese Patent Application Publication No. 2017-119849.

[1232]

[1233] Under a nitrogen atmosphere, 2,3,4,5,6-pentafluorophenol (6.8 g), THF (tetrahydrofuran, 42 mL), and triethylamine (5.1 g) were added to a 100 mL flask and stirred at 25 °C. Then, 10-undecenoic chloride (5.0 g) was added dropwise, and the mixture was stirred at 25 °C for 1 hour. The reaction mixture was filtered, and the solvent and low-boiling components were removed by vacuum distillation. Rapid column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was then performed to obtain 7.9 g of compound 12C. The structure of compound 12C was confirmed by the following NMR data.

[1234]

[1235] 1 H-NMR (400 MHz, CDCl3) δ5.74 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.05 -4.77 (m, 2H), 2.59 (t, J = 7.4 Hz, 2H), 1.97 (q, J = 7.1 Hz, 2H), 1.70 (p, J =7.4 Hz, 2H), 1.42 - 1.08 (m, 10H).

[1236] Under a nitrogen atmosphere, compound 12C (5.6 g), THF (5.0 mL), and dimethylchlorosilane (2.3 g) were added to a 200 mL flask and stirred at 25 °C. Next, a xylene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 0.10 mL) was added, and the mixture was stirred at 25 °C for 2 hours. The solvent and low-boiling components were removed by vacuum distillation, yielding 7.2 g of compound 12D. The structure of compound 12D was confirmed by the following NMR data.

[1237]

[1238] 1 H-NMR (400 MHz, CDCl3) δ 2.63 (t,J = 7.4Hz, 2H), 1.74 (p, J = 7.4 Hz, 2H), 1.46 - 1.17 (m, 14H), 0.90 - 0.69 (m, 2H), 0.37 (s, 6H).

[1239] Under a nitrogen atmosphere, tris(trimethylsiloxy)silanol (1.3 g) and THF (20 mL) were added to a 100 mL three-necked flask and stirred at 25 °C. The mixture was then cooled to 0 °C, and a hexane solution of n-butyllithium (1.6 M, 2.4 mL) was added dropwise. Next, a THF solution of hexamethylcyclotrisiloxane (1.1 M, 4.0 mL) was added dropwise, followed by another THF solution of hexamethylcyclotrisiloxane (1.1 M, 22 mL), and the mixture was stirred for 7 hours. Then, compound 12D (3.6 g) was added, and the mixture was stirred at 25 °C for 1 hour. Then, compound 12A (3.2 g) was added, and the mixture was stirred for 1 hour. Hexane and deionized water were added sequentially to the reaction mixture, and the mixture was separated, with the organic layer collected. After removing the solvent and low-boiling components by vacuum distillation, rapid column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was performed to obtain 0.98 g of compound 12E. The structure of compound 12E was confirmed by the following NMR data. In compound 12E, the average value of n10 is 21.

[1240]

[1241] 1H-NMR (400 MHz, CDCl3) δ 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz, 2H), 5.31 (d, J = 4.8 Hz, 1H), 5.08 - 4.84 (m, 4H), 3.19 (t, J = 6.0 Hz, 2H), 2.31 - 2.11 (m, 2H), 2.08 - 1.92 (m, 4H), 1.63 (t, J = 7.3 Hz, 2H), 1.28 (d, J = 9.6 Hz, 47H), 0.53 (t, J = 7.7 Hz, 2H), 0.09 (s, 159H).

[1242] In a 50 mL flask, 10 g of dichloromethane and 0.80 g of compound 12E were added and stirred at 25 °C. Next, a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 4.1 mg), aniline (2.6 mg), and trimethoxysilane (0.40 g) were added, and the mixture was stirred at 25 °C for 2 hours. The solvent was removed by vacuum distillation, yielding 0.69 g of compound 12F. The structure of compound 12F was confirmed by the following NMR data. In compound 12F, the average value of n10 is 21.

[1243]

[1244] 1 H-NMR (400 MHz, CDCl3) δ 5.31 (d, J = 4.8 Hz, 1H), 3.57 (s, 18H), 3.18 (t, J = 6.0Hz, 2H), 2.31 - 2.11 (m, 2H), 1.64 - 1.25 (m, 57H), 0.64 (m, 4H), 0.52 (t, J = 7.7 Hz, 2H), 0.09 (s, 159H).

[1245] [Synthesis of Compound 13D]

[1246] Under a nitrogen atmosphere, 2,3,4,5,6-pentafluorophenol (6.8 g), THF (42 mL), and triethylamine (5.1 g) were added to a 100 mL flask and stirred at 25 °C. Then, 10-undecenoic chloride (5.0 g) was added dropwise, and the mixture was stirred at 25 °C for 1 hour. The reaction mixture was filtered, and the solvent and low-boiling components were removed by vacuum distillation. Rapid column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was then performed to obtain 7.9 g of compound 13A. The structure of compound 13A was confirmed by the following NMR data.

[1247]

[1248] 1 H-NMR (400 MHz, CDCl3) δ5.74 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.05-4.77 (m, 2H), 2.59 (t, J = 7.4 Hz, 2H), 1.97 (q, J = 7.1 Hz, 2H), 1.70 (p, J =7.4 Hz, 2H), 1.42-1.08 (m, 10H).

[1249] Under a nitrogen atmosphere, compound 13A (5.6 g), THF (5.0 mL), and dimethylchlorosilane (2.3 g) were added to a 200 mL flask and stirred at 25 °C. Next, a xylene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 0.10 mL) was added, and the mixture was stirred at 25 °C for 2 hours. The solvent and low-boiling components were removed by vacuum distillation, yielding 7.2 g of compound 13B. The structure of compound 13B was confirmed by the following NMR data.

[1250]

[1251] 1 H-NMR (400 MHz, CDCl3) δ 2.63 (t,J = 7.4 Hz, 2H), 1.74 (p, J = 7.4 Hz, 2H), 1.46 - 1.17 (m, 14H), 0.90 - 0.69 (m, 2H), 0.37 (s, 6H).

[1252] Under a nitrogen atmosphere, tert-butyldimethylsilanol (2.5 g) and THF (92 mL) were added to a 500 mL three-necked flask and stirred at 25 °C. The mixture was then cooled to 0 °C, and a hexane solution of n-butyllithium (1.6 M, 11 mL) was added dropwise. Next, a THF solution of hexamethylcyclotrisiloxane (1.1 M, 19 mL) was added dropwise, followed by another THF solution of hexamethylcyclotrisiloxane (1.1 M, 100 mL). The mixture was stirred at 0 °C for 7 hours. Then, compound 13B (15 g) was added, and the mixture was stirred at 0 °C for 1 hour. Finally, 2-(undec-10-en-1-yl)dedec-12-en-1-amine (15 g) was added, and the mixture was stirred at 0 °C for 1 hour. Hexane and deionized water were added sequentially to the reaction mixture, and the organic layer was separated. After removing the solvent and low-boiling components by vacuum distillation, rapid column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was performed to obtain 4.5 g of compound 13C. The structure of compound 13C was confirmed by the following NMR data. In compound 13C, the average n10 value is 23.

[1253]

[1254] 1 H-NMR (400 MHz, CDCl3) δ 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz, 2H), 5.24 (t, J = 5.7 Hz, 1H), 5.08-4.84 (m, 4H), 3.19 (t, J = 6.0 Hz, 2H), 2.31-2.11 (m, 2H), 2.08-1.92 (m, 4H), 1.63 (t, J = 7.3 Hz, 2H), 1.46-0.98 (m, 47H), 0.80 (s, 9H), 0.53 (t, J = 7.7 Hz, 2H), 0.09 (s, 144H).

[1255] In a 20 mL flask, 1.5 g of dichloromethane and 1.0 g of compound 13C were added and stirred at 25 °C. Next, a toluene solution of a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 7.7 mg), aniline (1.2 mg), and trimethoxysilane (0.12 g) were added, and the mixture was stirred at 25 °C for 2 hours. The solvent was removed by vacuum distillation, yielding 0.69 g of compound 13D. The structure of compound 13D was confirmed by the following NMR data. In compound 13D, the average n10 value is 23.

[1256]

[1257] 1 H-NMR (400 MHz, CDCl3) δ 5.24 (t, J = 5.7Hz, 1H), 3.57 (s, 18H), 3.18 (t, J = 6.0 Hz, 2H), 2.31-2.11 (m, 2H), 1.64-1.25 (m, 57H), 0.80 (s, 9H), 0.63-0.46 (m, 4H), 0.52 (t, J = 7.7Hz, 2H), 0.09 (s, 144H).

[1258] [Compound 14]

[1259] Compound 14 was synthesized with reference to Example 1 of International Publication No. 2023 / 017830. In compound 14, the average value of n10 is 19.

[1260]

[1261] [Preparation of substrate]

[1262] As a glass substrate, Dragontrail Pro (manufactured by AGC Corporation) is prepared.

[1263] Clean the glass substrate in the following order.

[1264] First, the glass substrate was ultrasonically cleaned for 15 minutes using an aqueous solution containing PK-LCG23 manufactured by PARKER CORPORATION as an alkaline detergent.

[1265] Next, the glass substrate was ultrasonically cleaned with ultrapure water for 15 minutes.

[1266] Finally, the glass substrate is subjected to 15 minutes of ozone cleaning.

[1267] Next, the surface (first surface) of the cleaned glass substrate, measuring 50 mm in length and 50 mm in width, was etched using a processing gas. A mixture of nitrogen and hydrogen fluoride gas was used as the processing gas. The concentration of hydrogen fluoride gas, the flow rate of the processing gas, and the processing time were set as described in Table 1. It should be noted that the etching temperature is as described in Table 1.

[1268] After etching, ultrasonic cleaning was performed for 10 minutes using a 10% hydrochloric acid solution.

[1269] For the obtained substrate, the surface roughness Sdr is measured within an arbitrary measurement area of ​​5~50 μm square.

[1270] -Methods for measuring surface roughness Sdr-

[1271] The shape image of the glass substrate was measured using an atomic force microscope (product name "AFM-5500M", manufactured by Hitachi High-Tech Co., Ltd.). Based on the data of the obtained shape image, the Sdr was calculated using AFM analysis software (Mountains SPIP (registered trademark)).

[1272] The measurement results are shown in Table 1.

[1273] [Wet coating method]

[1274] 30g of silicon dioxide was placed on a copper furnace cylinder inside a vacuum evaporation apparatus (ULVAC KIKO, Inc. VTR-350M) as the evaporation source. A substrate was placed inside the vacuum evaporation apparatus, and the air inside the apparatus was evaporated to a pressure of 5×10⁻⁶. -3 A pressure below Pa is applied. The furnace cylinder is heated to approximately 2,000°C, causing silicon oxide to be vacuum-deposited onto the surface of the substrate. This forms a silicon oxide layer with a thickness of approximately 20 nm on the substrate.

[1275] A substrate with a silicon oxide layer is placed on the sample stage of a spray coating machine (API-90RS, Apeiros Co., Ltd.) with the silicon oxide layer as the surface. Next, 13g of a 0.2% by mass heptane solution of each compound is added to the syringe inside the spray coating machine, and spraying is performed at an atomization pressure of 130kPa, a nozzle-sample surface distance of 50mm, and a scanning speed of 300mm / s. Afterward, the coated substrate is heat-treated at 140°C for 30 minutes. This yields an article with a surface treatment layer on the surface of the silicon oxide layer.

[1276] For the surface treatment layer of an article obtained by wet coating, the surface roughness Sdr is measured within an arbitrary measurement area of ​​5 to 50 μm square.

[1277] In addition, the liquid repellency of the obtained items was evaluated.

[1278] Liquid repellency

[1279] Oil was applied to the surface treatment layer of the item, and the oil contact angle was measured using a contact angle measuring device (product name "DM-500", manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five points on the surface treatment layer, and the average value was calculated. It should be noted that the 2θ method was used to calculate the oil contact angle. The evaluation criteria are as follows. A and B represent levels that are practically sound.

[1280] A: The oil contact angle is 70° or higher.

[1281] B: The oil contact angle is greater than 60° and less than 70°.

[1282] C: Oil contact angle is less than 60°.

[1283] The evaluation results are shown in Table 1. Examples 1-4 are exemplary cases, and Examples 5-12 are comparative cases.

[1284] [Table 1]

[1285]

[1286] As shown in Table 1, in Examples 1 to 4, the surface roughness Sdr of the surface treatment layer in any measurement area of ​​5 to 50 μm square is more than 30%, indicating excellent liquid repellency.

[1287] Industrial availability

[1288] The disclosed articles can be applied, for example, to display devices such as touch panel displays, optical components, semiconductor components, building materials, automotive parts, and nanoimprint technology. Furthermore, the disclosed articles can be used in the bodies, windows (front, side, and rear windows), reflectors, and bumpers of transportation equipment such as trams, automobiles, ships, and airplanes. Moreover, the surface treatment agent can be used on outdoor items such as building exteriors, tents, solar power modules, sound insulation panels, and concrete; fishing nets, insect nets, and sinks. Additionally, the surface treatment agent can be used in kitchens, bathrooms, washbasins, mirrors, and toilet peripheral components; chandeliers, ceramics such as tiles; artificial marble, air conditioners, and various indoor equipment. Furthermore, the surface treatment agent can also be used for antifouling treatment of fixtures, interior walls, and piping in factories. Additionally, the surface treatment agent can be applied to goggles, eyeglasses, helmets, marbles, fibers, umbrellas, toys, and soccer balls. Finally, the disclosed articles can be applied to various packaging materials such as food packaging materials, cosmetic packaging materials, and the interior of cans. In addition, the items disclosed herein can be used in car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, endoscopes and other medical devices, copiers, PCs, displays (such as liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films and anti-reflective films and other optical components.

[1289] (Postscript)

[1290] This disclosure includes the following methods.

[1291] <1>

[1292] An article comprising a substrate and a surface treatment layer, the surface treatment layer being disposed on the substrate and surface-treated with a surface treatment agent.

[1293] The surface roughness Sdr of the surface treatment layer is above 30% within any measurement area of ​​5~50μm square.

[1294] The surface treatment agent contains a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

[1295] <2>

[1296] according to <1> The article wherein the reactive silane is represented by the following formula (S1).

[1297] -Si(R) 2 ) n L 3-n …(S1)

[1298] In formula (S1),

[1299] R 2 Each is an independent hydrocarbon group.

[1300] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1301] n is an integer between 0 and 2.

[1302] <3>

[1303] according to <1> or <2> The article wherein the chain-like organo(poly)siloxane residues are represented by the following formula (B1).

[1304]

[1305] In formula (B1),

[1306] R 3 Each is an independent hydrocarbon group.

[1307] k1 is a number greater than or equal to 1.

[1308] This refers to the bonding site with adjacent atoms.

[1309] <4>

[1310] according to <1> ~ <3> The article of any one of the following, wherein the aforementioned compound having chain-like organo(poly)siloxane residues and reactive silyl groups is represented by the following formula (C) or the following formula (D).

[1311]

[1312] In formula (C),

[1313] T 11 It is a monovalent group that does not contain reactive silyl groups.

[1314] B can be independently -O- or -C (=O)-.

[1315] r can be 0 or 1 independently.

[1316] R 3 Each is an independent hydrocarbon group.

[1317] k1 are each an independent number greater than or equal to 1.

[1318] p1 is an integer greater than or equal to 1.

[1319] A 11 It is a (p1+q1) valence linker.

[1320] q1 is an integer greater than or equal to 1.

[1321] R 2 Each is an independent hydrocarbon group.

[1322] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1323] n is an independent integer from 0 to 2.

[1324]

[1325] In equation (D),

[1326] R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -,

[1327] T 11 Each is an independent monovalent group.

[1328] B can be independently -O- or -C (=O)-.

[1329] r can be 0 or 1 independently.

[1330] R 3 Each is an independent hydrocarbon group.

[1331] k1 are each an independent number greater than or equal to 1.

[1332] A 12 Each is an independent (q1+1) valence linker.

[1333] Each q1 is an independent integer greater than or equal to 1.

[1334] R 2 Each is an independent hydrocarbon group.

[1335] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1336] n is an independent integer from 0 to 2.

[1337] <5>

[1338] according to <4> The items mentioned above, wherein,

[1339] In equation (C), k1 is a number between 3 and 500.

[1340] In equation (D), k1 is a number between 3 and 500.

[1341] <6>

[1342] according to <4> or <5> The items mentioned above, wherein,

[1343] In equation (C), q1 is an integer from 1 to 4.

[1344] In equation (D), q1 is an integer from 1 to 4.

[1345] <7>

[1346] according to <1> ~ <6> The article described in any one of the following statements, wherein the substrate is glass.

[1347] <8>

[1348] according to <1> ~ <7> The article described in any one of the following is an optical component.

[1349] <9>

[1350] according to <1> ~ <8> The article mentioned in any one of these examples is a display or a touch panel.

[1351] <10>

[1352] A method for manufacturing an article, wherein a surface treatment agent is used to treat a substrate to produce an article having a surface treatment layer formed on the substrate.

[1353] The surface roughness Sdr of the surface treatment layer is above 30% within any measurement area of ​​5~50μm square.

[1354] The surface treatment agent contains a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

[1355] <11>

[1356] according to <10> The method for manufacturing the article, wherein the substrate is a substrate with a surface roughness Sdr of 30% or more in any measured area ranging from 5 to 50 μm square.

[1357] <12>

[1358] according to <10> or <11> The method for manufacturing the article, wherein the reactive silane is represented by the following formula (S1).

[1359] -Si(R) 2 ) n L 3-n …(S1)

[1360] In formula (S1),

[1361] R 2 Each is an independent hydrocarbon group.

[1362] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1363] n is an integer between 0 and 2.

[1364] <13>

[1365] according to <10> ~ <12> The method of manufacturing the article according to any one of the following methods, wherein the chain-like organo(poly)siloxane residues are represented by the following formula (B1).

[1366]

[1367] In formula (B1),

[1368] R 3 Each is an independent hydrocarbon group.

[1369] k1 is a number greater than or equal to 1.

[1370] This refers to the bonding site with adjacent atoms.

[1371] <14>

[1372] according to <10> ~ <13> The method of manufacturing the article, wherein the compound having chain-like organo(poly)siloxane residues and reactive silyl groups is represented by the following formula (C) or the following formula (D).

[1373]

[1374] In formula (C),

[1375] T 11 It is a monovalent group that does not contain reactive silyl groups.

[1376] B can be independently -O- or -C (=O)-.

[1377] r can be 0 or 1 independently.

[1378] R 3 Each is an independent hydrocarbon group.

[1379] k1 are each an independent number greater than or equal to 1.

[1380] p1 is an integer greater than or equal to 1.

[1381] A 11 It is a (p1+q1) valence linker.

[1382] q1 is an integer greater than or equal to 1.

[1383] R 2 Each is an independent hydrocarbon group.

[1384] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1385] n is an independent integer from 0 to 2.

[1386]

[1387] In equation (D),

[1388] R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -,

[1389] T 11 Each is an independent monovalent group.

[1390] B can be independently -O- or -C (=O)-.

[1391] r can be 0 or 1 independently.

[1392] R 3 Each is an independent hydrocarbon group.

[1393] k1 are each an independent number greater than or equal to 1.

[1394] A 12 Each is an independent (q1+1) valence linker.

[1395] Each q1 is an independent integer greater than or equal to 1.

[1396] R 2 Each is an independent hydrocarbon group.

[1397] L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently.

[1398] n is an independent integer from 0 to 2.

[1399] The disclosure of Japanese Patent Application No. 2023-174764, filed on October 6, 2023, is incorporated herein by reference in its entirety. All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as those specifically described and separately incorporated herein by reference.

Claims

1. An article comprising a substrate and a surface treatment layer, the surface treatment layer being disposed on the substrate and surface-treated with a surface treatment agent. The surface roughness Sdr of the surface treatment layer is greater than 30% within any measured area of ​​5-50 μm square. The surface treatment agent comprises a compound having chain-like groups and reactive silyl groups.

2. The article according to claim 1, wherein, The compound having chain-like groups and reactive silyl groups is a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

3. The article according to claim 1, wherein, The reactive silane is represented by the following formula (S1) or formula (S3). -And (R) 2 ) n IT 3-n …(S1) -[Yes(L 2 )2-P] r1 -Yes(L 2 )3…(S3) In formula (S1), R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n is an integer between 0 and 2. In formula (S3), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an integer from 1 to 3.

4. The article according to claim 2, wherein, The chain-like organo(poly)siloxane residues are represented by the following formula (B1), In formula (B1), R 3 Each is an independent hydrocarbon group. k1 is a number greater than or equal to 1. This refers to the bonding site with adjacent atoms.

5. The article according to claim 1, wherein, The compound having chain-like groups and reactive silyl groups is represented by the following formulas (C), (C2), (D), (D2), (E), or (E2). In formula (C), T 11 It is a monovalent group that does not contain reactive silyl groups. B can be independently -O- or -C (=O)-. r can be 0 or 1 independently. R 3 Each is an independent hydrocarbon group. k1 are each an independent number greater than or equal to 1. p1 is an integer greater than or equal to 1. A 11 It is a (p1+q1) valence linker. q1 is an integer greater than or equal to 1. R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n are independent integers from 0 to 2. In formula (C2), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an integer from 1 to 3. T 11 B, r, R 3 k1, p1, A 11 The definition of q1 is the same as that in equation (C). In equation (D), R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -, T 11 Each is an independent monovalent group. B can be independently -O- or -C (=O)-. r can be 0 or 1 independently. R 3 Each is an independent hydrocarbon group. k1 are each an independent number greater than or equal to 1. A 12 Each is an independent (q1+1) valence linker. Each q1 is an independent integer greater than or equal to 1. R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n are independent integers from 0 to 2. In equation (D2), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an independent integer from 1 to 3. R 4 k1, A 12 The definition of q1 is the same as that in equation (D). In formula (E), B 11 It is a monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups; or it is a monovalent group comprising a branched alkyl group. u1 is an integer greater than or equal to 1. A 13 It is a (q1+u1) valence linker. q1 is an integer greater than or equal to 1. R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n are independent integers from 0 to 2. In formula (E2), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an independent integer from 1 to 3. B 11 u1, A 13 The definitions of q1 and q1 are the same as those in equation (E).

6. The article according to claim 5, wherein, In equations (C) and (C2), k1 is a number between 3 and 500. In equations (D) and (D2), k1 is a number ranging from 3 to 500.

7. The article according to claim 5, wherein, In equations (C), (C2), (E), and (E2), q1 is an integer from 1 to 4. In equations (D) and (D2), q1 is an integer from 1 to 4, each independently.

8. The article according to claim 1, wherein, The substrate is glass.

9. The article according to claim 1, wherein it is an optical component.

10. The article of claim 1, wherein it is a display or a touch panel.

11. A method for manufacturing an article, wherein, An article having a surface-treated layer formed on a substrate is manufactured by using a surface-treatment agent to treat the substrate. The surface roughness Sdr of the surface treatment layer is greater than 30% within any measured area of ​​5-50 μm square. The surface treatment agent comprises a compound having chain-like groups and reactive silyl groups.

12. The method of manufacturing the article according to claim 11, wherein, The compound having chain-like groups and reactive silyl groups is a compound having chain-like organo(poly)siloxane residues and reactive silyl groups.

13. The method of manufacturing the article according to claim 11, wherein, The substrate is a substrate with a surface roughness Sdr of 30% or more in any measured area ranging from 5 to 50 μm square.

14. The method of manufacturing an article according to claim 11, wherein, The reactive silane is represented by the following formula (S1) or formula (S3). -And (R) 2 ) n IT 3-n …(S1) -[Yes(L 2 )2-P] r1 -Yes(L 2 )3…(S3) In formula (S1), R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n is an integer between 0 and 2. In formula (S3), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an integer from 1 to 3.

15. The method of manufacturing an article according to claim 12, wherein, The chain-like organo(poly)siloxane residues are represented by the following formula (B1), In formula (B1), R 3 Each is an independent hydrocarbon group. k1 is a number greater than or equal to 1. This refers to the bonding site with adjacent atoms.

16. The method of manufacturing an article according to claim 11, wherein, The compound having a chain-like group and a reactive silyl group is represented by the following formula (C), (C2), (D), (D2), (E), or (E2). In formula (C), T 11 It is a monovalent group that does not contain reactive silyl groups. B can be independently -O- or -C (=O)-. r can be 0 or 1 independently. R 3 Each is an independent hydrocarbon group. k1 are each an independent number greater than or equal to 1. p1 is an integer greater than or equal to 1. A 11 It is a (p1+q1) valence linker. q1 is an integer greater than or equal to 1. R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n are independent integers from 0 to 2. In formula (C2), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an integer from 1 to 3. T 11 B, r, R 3 k1, p1, A 11 The definition of q1 is the same as that in equation (C). In equation (D), R 4 Each is independently a hydrocarbon group or a T group 11 -B r -(SiR) 3 2-O) k1 -, T 11 Each is an independent monovalent group. B can be independently -O- or -C (=O)-. r can be 0 or 1 independently. R 3 Each is an independent hydrocarbon group. k1 are each an independent number greater than or equal to 1. A 12 Each is an independent (q1+1) valence linker. Each q1 is an independent integer greater than or equal to 1. R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n are independent integers from 0 to 2. In equation (D2), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an independent integer from 1 to 3. R 4 k1, A 12 The definition of q1 is the same as that in equation (D). In formula (E), B 11 It is a monovalent group comprising at least one of the group consisting of Si, Ge, and Sn, which are not directly bonded to hydroxyl or hydrolyzable groups; or it is a monovalent group comprising a branched alkyl group. u1 is an integer greater than or equal to 1. A 13 It is a (q1+u1) valence linker. q1 is an integer greater than or equal to 1. R 2 Each is an independent hydrocarbon group. L can be a hydrolyzable group, a group with a hydrolyzable group, or a hydroxyl group, each independently. n are independent integers from 0 to 2. In formula (E2), L 2 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. L 2 At least 4 L in 2 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Each P is an oxygen atom or an organic group having one carbon atom bonded to the two adjacent Si atoms. r1 is an independent integer from 1 to 3. B 11 u1, A 13 The definitions of q1 and q1 are the same as those in equation (E).

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