Surface treatment agent

Abstract

To provide a surface preparation agent containing a fluoro(poly)ether group-containing silane compound, capable of forming a layer having high friction durability.SOLUTION: A surface preparation agent contains at least one kind of fluoropolyether group-containing compound expressed by following formula (1) or (2) [in the formula, each symbol has the same meaning as the description in the specification], and chloride ion. In the surface preparation agent, a chloride ion concentration in the surface preparation agent is 0.1 mass ppm or more and 1.0 mass ppm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a surface treatment agent. [Background technology]

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

[0003] As such fluorine-containing compounds, perfluoropolyether group-containing silane compounds are known, which have a perfluoropolyether group in the molecular main chain and hydrolyzable groups bonded to Si atoms at the molecular terminals or terminal parts (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-218639 [Patent Document 2] Japanese Patent Publication No. 2017-082194 [Overview of the project] [Problems that the invention aims to solve]

[0005] Layers obtained from surface treatment agents containing perfluoropolyether group-containing silane compounds can exhibit functions such as water repellency, oil repellency, and stain resistance even in thin films, making them suitable for use in optical components such as eyeglasses and touch panels where light transmittance and transparency are required. In particular, these applications require friction resistance so that these functions can be maintained even after repeated friction.

[0006] The present disclosure aims to provide a surface treatment agent comprising a fluoro(poly)ether group-containing silane compound capable of forming a layer having high friction durability.

Means for Solving the Problems

[0007] The present disclosure includes the following aspects. [1] The following formula (1) or (2):

Chemical formula

[10] A surface treatment agent according to any of [1] to [9] above, wherein the chloride ion concentration in the surface treatment agent is 0.2 to 0.8 ppm by mass.

[11] The surface treatment agent according to any of [1] to

[10] above, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts.

[12] A surface treatment agent according to any of [1] to

[11] above, further comprising a solvent.

[13] A surface treatment agent according to any of [1] to

[12] above, used as an antifouling or waterproofing coating agent.

[14] A surface treatment agent for vacuum deposition, as described in any of [1] to

[13] above.

[15] Pellets containing any of the surface treatment agents described in [1] to

[14] above.

[16] An article comprising a base material and a layer formed on the surface of the base material from any of the surface treatment agents described in [1] to

[14] above.

[17] The article described in

[16] above, which is an optical component. [Effects of the Invention]

[0008] The surface treatment agent disclosed herein can form a surface treatment layer with excellent friction resistance by setting the chloride ion concentration in the range of 0.1 ppm by mass to 1.0 ppm by mass. [Modes for carrying out the invention]

[0009] In this specification, "monovalent organic group" means a monovalent group containing carbon. A monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at the end or in the molecular chain of a hydrocarbon group. When simply referred to as "organic group," it means a monovalent organic group. Furthermore, "2-10valent organic group" means a 2-10valent group containing carbon. Such 2-10valent organic groups are not particularly limited, but may include 2-10valent groups obtained by removing 1 to 9 more hydrogen atoms from an organic group. For example, a divalent organic group is not particularly limited, but may include a divalent group obtained by removing 1 more hydrogen atom from an organic group.

[0010] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing one hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not limited to, but may be substituted with one or more substituents, C 1-20 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures.

[0011] In the use herein, the substituents of the "hydrocarbon group" are not particularly limited, but may be, for example, a halogen atom, or a hydrocarbon group that is substituted with one or more halogen atoms. 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0012] In this specification, "hydrolyzable group" means, as used herein, a group that can undergo hydrolysis, that is, a group that can be removed from the main skeleton of a compound by hydrolysis. Examples of hydrolyzable groups include -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 Examples include (showing an alkyl group).

[0013] The surface treatment agent disclosed herein is based on the following formula (1) or (2): [ka] The surface treatment agent contains at least one fluoropolyether group-containing compound represented by [formula], and the chloride ion concentration in the surface treatment agent is 0.1 ppm by mass or more and 1.0 ppm by mass or less.

[0014] In the above equation (1), R F1 Each occurrence is independent of Rf 1 -R F -O q - is

[0015] In equation (2) above, R F2 -Rf 2 p -R F -O q - is

[0016] In the above formula, Rf 1 C may be independently substituted by one or more fluorine atoms in each occurrence. 1-16It is an alkyl group.

[0017] C may be substituted with one or more fluorine atoms as described above. 1-16 "C" in alkyl groups 1-16 The alkyl group may be linear or branched, preferably linear or branched C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group, more preferably a linear C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0018] The above Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1-16 It is an alkyl group, more preferably CF2H-C 1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0019] C above 1-16 The perfluoroalkyl group may be linear or branched, preferably linear or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 These are perfluoroalkyl groups, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0020] In the above formula, Rf 2 C may be substituted with one or more fluorine atoms. 1-6 It is an alkylene group.

[0021] C may be substituted with one or more fluorine atoms as described above. 1-6 "C" in the alkylene group 1-6 The alkylene group may be linear or branched, preferably linear or branched C 1-3An alkylene group, more preferably a linear C group 1-3 It is an alkylene group.

[0022] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1-6 It is an alkylene group, and more C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0023] C above 1-6 The perfluoroalkylene group may be linear or branched, preferably linear or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 These are perfluoroalkyl groups, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0024] In the above equation, p is either 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0025] In the above equation, q is either 0 or 1 independently in each occurrence. In one embodiment, q is 0. In another embodiment, q is 1.

[0026] In the above equations (1) and (2), R F Each instance is independently a divalent fluoropolyether group.

[0027] R F Preferably, the formula is: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers between 0 and 200, and their sum is 1 or greater. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary within the expression. It is a base represented by .

[0028] R Fa Preferably, it is a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0029] a, b, c, d, e, and f may preferably be independent integers between 0 and 100.

[0030] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0031] These repeating units may be linear or branched. For example, the above repeating unit is -(OC6F 12 )- may also be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10)- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(that is, in the above formula, R Fa (where is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0032] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, frictional durability, etc., of the surface treatment layer can be improved.

[0033] In one embodiment, the repeating unit is branched and chain-like. By making the repeating unit branched and chain-like, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0034] In one embodiment, R F Each occurrence is independent of the following equations (f1)~(f5): -(OC3F6) d - (f1) [In the formula, d is an integer between 1 and 200.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are independent integers between 0 and 30, and e and f are independent integers between 1 and 200.] The sum of c, d, e, and f is 2 or greater. The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 It is either OCF2 or OC2F4, R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. ]; or -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) [In the formula, e is an integer between 1 and 200, a, b, c, d, and f are each independent integers between 0 and 200, the sum of a, b, c, d, e, and f is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, f is an integer between 1 and 200, a, b, c, d, and e are each independent integers between 0 and 200, the sum of a, b, c, d, e, and f is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] It is a base represented by .

[0035] In the above formula (f1), d is preferably an integer between 5 and 200, more preferably between 10 and 100, and even more preferably between 15 and 50, for example between 25 and 35. The above formula (f1) is preferably -(OCF2CF2CF2) d -or-(OCF(CF3)CF2) d - is a group represented by -, more preferably -(OCF2CF2CF2). d It is a base represented by -.

[0036] In the above formula (f2), e and f are each an integer, preferably between 5 and 200, more preferably between 10 and 200. The sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f - is the base represented by -. In another embodiment, formula (f2) is -(OC2F4) e -(OCF2) f It may also be represented as a base by -.

[0037] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably, a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 is not particularly limited, but examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The chain may be either linear or branched, and is preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g - is

[0038] In the above formula (f4), e is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0039] In the above formula (f5), f is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0040] In one embodiment, the above R F This is the group represented by the above formula (f1).

[0041] In one embodiment, the above R F This is the group represented by the above formula (f2).

[0042] In one embodiment, the above R F This is the group represented by the above formula (f3).

[0043] In one embodiment, the above R F This is the group represented by the above formula (f4).

[0044] In one embodiment, the above R F This is the group represented by the above formula (f5).

[0045] The above R F In this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the e / f ratio to 10 or less, the slipperiness, frictional durability, and chemical resistance (e.g., resistance to artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the better the slipperiness and frictional durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The larger the e / f ratio, the better the stability of the compound.

[0046] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0047] In one embodiment, from the viewpoint of heat resistance, the above e / f ratio is preferably 1.0 or higher, and more preferably 1.0 to 2.0.

[0048] In the above fluoropolyether group-containing compound, R F1 and R F2 The number-average molecular weight of the part is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, R F1 and R F2 The number-average molecular weight is, 19 The value shall be measured by 1F-NMR.

[0049] In another embodiment, R F1 and R F2 The number-average molecular weight of the part may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.

[0050] In another embodiment, R F1 and R F2 The number-average molecular weight of the part may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0051] In the above equations (1) and (2), R Si Each occurrence is independently a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group bonded to a Si atom, and at least one R Si This is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0052] In a preferred embodiment, R Si This is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0053] In a preferred embodiment, R Si This is expressed by the following equations (S1), (S2), (S3), or (S4): [ka] It is a base represented by .

[0054] In the above formula, R 11 Each instance is independently either a hydroxyl group or a hydrolyzable group.

[0055] R 11 Preferably, each occurrence is independently hydrolyzable.

[0056] R 11 Preferably, in each occurrence, independently, -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , or halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR h (That is, an alkoxy group). h Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h This is an ethyl group.

[0057] In the above formula, R 12 Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0058] R 12 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0059] In the above formula, n1 is (SiR11 n1 R 12 3-n1 Each unit is an independent integer between 0 and 3. However, R Si If the group is represented by formula (S1) or (S2), then the terminal R of formulas (1) and (2) Si In the part (hereinafter also simply referred to as the "terminal part" of equations (1) and (2)), n1 is 1 to 3 (SiR 11 n1 R 12 3-n1 There is at least one unit. That is, in such terminal parts, not all n1s are 0 at the same time. In other words, in the terminal parts of equations (1) and (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0060] n1 is (SiR 11 n1 R 12 3-n1 Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0061] In the above formula, X 11 Each instance is independently either a single bond or a divalent organic group. Such a divalent organic group is preferably C 1-20 It is an alkylene group. 1-20 The alkylene group may be linear or branched, but is preferably linear.

[0062] In a preferred embodiment, X 11 Each instance independently involves a single bond or a linear chain of C. 1-6 An alkylene group, preferably a single bond or a linear C bond. 1-3 Alkylene group, more preferably a single bond or linear carbon 1-2 An alkylene group, more preferably a linear carbon group. 1-2 It is an alkylene group.

[0063] In the above formula, R 13Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably C 1-20 It is an alkyl group. 1-20 The alkyl group may be linear or branched, but is preferably linear.

[0064] In a preferred embodiment, R 13 Each instance independently represents a hydrogen atom or a linear C atom. 1-6 It is an alkyl group, preferably a hydrogen atom or a linear C 1-3 The alkyl group is preferably a hydrogen atom or a methyl group.

[0065] In the above formula, t is an integer between 2 and 10, independently in each occurrence.

[0066] In a preferred embodiment, t is an integer between 2 and 6, independently in each occurrence.

[0067] In the above formula, R 14 In each occurrence, R is independently a hydrogen atom or a halogen atom. Such halogen atoms are preferably iodine, chlorine, or fluorine atoms, and more preferably fluorine atoms. In a preferred embodiment, R 14 This is a hydrogen atom.

[0068] In the above formula, R a1 In each occurrence, -Z is independent. 1 -SiR 21 p1 R 22 q1 R 23 r1 That is the case.

[0069] The above Z 1 Each instance independently represents either an oxygen atom or a divalent organic group. (Note: Z follows) 1 The structure described as follows is (SiR 21 p1 R 22 q1 R23 r1 ) joins.

[0070] In a preferred embodiment, Z 1 It is a divalent organic group.

[0071] In a preferred embodiment, Z 1 is, Z 1 It does not contain any elements that form a siloxane bond with the Si atom to which it is bonded. That is, in formula (S3), (Si-Z 1 -Si) does not contain a siloxane bond.

[0072] The above Z 1 Preferably, C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2 is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3 -Phenylene-(CH2) z4 -(wherein z3 is an integer from 0 to 6, for example, an integer from 1 to 6, and z4 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0073] In a preferred embodiment, Z 1 C 1-6 Alkylene group or -(CH2) z3 -Phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 - is Z 1 If the group is such that it can have higher light resistance, especially UV resistance.

[0074] In another preferred embodiment, the above Z 1 C 1-3 It is an alkylene group. In one embodiment, Z 1 This could be -CH2CH2CH2-. In another embodiment, Z 1 It can be -CH2CH2-.

[0075] The above R 21 In each occurrence, -Z is independent. 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ That is the case.

[0076] The above Z 1’ Each instance independently represents either an oxygen atom or a divalent organic group. (Note: Z follows) 1’ The structure described as follows is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) joins.

[0077] In a preferred embodiment, Z 1’ It is a divalent organic group.

[0078] In a preferred embodiment, Z 1’ is, Z 1’ It does not contain any elements that form a siloxane bond with the Si atom to which it is bonded. That is, in formula (S3), (Si-Z 1’ -Si) does not contain a siloxane bond.

[0079] The above Z 1’ Preferably, C 1-6 Alkylene group, -(CH2) z1’ -O-(CH2) z2’ -(wherein z1' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3’ -Phenylene-(CH2) z4’-(wherein z3' is an integer between 0 and 6, for example between 1 and 6, and z4' is an integer between 0 and 6, for example between 1 and 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0080] In a preferred embodiment, Z 1’ C 1-6 Alkylene group or -(CH2) z3’ -Phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ - is Z 1’ If the group is such that it can have higher light resistance, especially UV resistance.

[0081] In another preferred embodiment, the above Z 1’ C 1-3 It is an alkylene group. In one embodiment, Z 1’ This could be -CH2CH2CH2-. In another embodiment, Z 1’ It can be -CH2CH2-.

[0082] The above R 21’ In each occurrence, -Z is independent. 1” -SiR 22” q1” R 23” r1” That is the case.

[0083] The above Z 1” Each instance independently represents either an oxygen atom or a divalent organic group. (Note: Z follows) 1” The structure described as follows is (SiR 22” q1” R 23” r1” ) joins.

[0084] In a preferred embodiment, Z 1” It is a divalent organic group.

[0085] In a preferred embodiment, Z 1” is, Z 1” It does not contain any elements that form a siloxane bond with the Si atom to which it is bonded. That is, in formula (S3), (Si-Z 1” -Si) does not contain a siloxane bond.

[0086] The above Z 1” Preferably, C 1-6 Alkylene group, -(CH2) z1” -O-(CH2) z2” -(wherein z1'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3” -Phenylene-(CH2) z4” -(wherein z3'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z4'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0087] In a preferred embodiment, Z 1” C 1-6 Alkylene group or -(CH2) z3” -Phenylene-(CH2) z4” -, preferably -phenylene-(CH2) z4” - is Z 1” If the group is such that it can have higher light resistance, especially UV resistance.

[0088] In another preferred embodiment, the above Z 1” C 1-3 It is an alkylene group. In one embodiment, Z1” This could be -CH2CH2CH2-. In another embodiment, Z 1” It can be -CH2CH2-.

[0089] The above R 22” Each instance is independently either a hydroxyl group or a hydrolyzable group.

[0090] The above R 22” Preferably, each occurrence is independently hydrolyzable.

[0091] The above R 22” Preferably, in each occurrence, independently, -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , or halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR h (That is, an alkoxy group). h Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h This is an ethyl group.

[0092] The above R 23” Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0093] The above R 23” In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0094] The above q1'' is an integer between 0 and 3, independently in each occurrence, and the above r1'' is an integer between 0 and 3, independently in each occurrence. Note that the sum of q1'' and r1'' is (SiR 22” q1” R 23” r1” In units of 3, it is 3.

[0095] The above q1'' is (SiR 22” q1” R 23” r1” Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0096] The above R 22’ Each instance is independently either a hydroxyl group or a hydrolyzable group.

[0097] R 22’ Preferably, each occurrence is independently hydrolyzable.

[0098] R 22’ Preferably, in each occurrence, independently, -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , or halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR h (That is, an alkoxy group). h Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R hThis is an ethyl group.

[0099] The above R 23’ Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0100] R 23’ In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0101] The above p1' is an integer between 0 and 3, independently of each occurrence; q1' is an integer between 0 and 3, independently of each occurrence; and r1' is an integer between 0 and 3, independently of each occurrence. Note that the sum of p', q1', and r1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ In units of 3, it is 3.

[0102] In one embodiment, p1' is 0.

[0103] In one embodiment, p1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1' is 3.

[0104] In one embodiment, q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0105] In one embodiment, p1' is 0 and q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0106] The above R 22 Each instance is independently either a hydroxyl group or a hydrolyzable group.

[0107] R 22 Preferably, each occurrence is independently hydrolyzable.

[0108] R 22 Preferably, in each occurrence, independently, -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , or halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR h (That is, an alkoxy group). h Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h This is an ethyl group.

[0109] The above R 23 Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0110] R 23In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0111] The above p1 is an integer between 0 and 3, independently of each occurrence; q1 is an integer between 0 and 3, independently of each occurrence; and r1 is an integer between 0 and 3, independently of each occurrence. Note that the sum of p1, q1, and r1 is (SiR 21 p1 R 22 q1 R 23 r1 In units of 3, it is 3.

[0112] In one embodiment, p1 is 0.

[0113] In one embodiment, p1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1 is 3.

[0114] In one mode, q1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0115] In one embodiment, p1 is 0 and q1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0116] In the above formula, R b1 Each instance is independently either a hydroxyl group or a hydrolyzable group.

[0117] The above R b1 Preferably, each occurrence is independently hydrolyzable.

[0118] The above R b1 Preferably, in each occurrence, independently, -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , or halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR h (That is, an alkoxy group). h Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h This is an ethyl group.

[0119] In the above formula, R c1 Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0120] The above R c1 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0121] The above k1 is an integer between 0 and 3, independently in each occurrence; l1 is an integer between 0 and 3, independently in each occurrence; and m1 is an integer between 0 and 3, independently in each occurrence. Note that the sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 In units of 3, it is 3.

[0122] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1 Each unit is an integer between 1 and 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0123] In the above equations (1) and (2), R Si When is a group represented by formula (S3), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0124] In a preferred embodiment, the group represented by formula (S3) is -Z 1 -SiR 22 q1 R 23 r1 (In the formula, q1 is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1 is an integer between 0 and 2.) -Z 1’ -SiR 22’ q1’ R 23’ r1’ (wherein q1' is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1' is an integer between 0 and 2.) or -Z 1” -SiR 22” q1” R 23” r1”(wherein the formula, q1'' is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1'' is an integer between 0 and 2.)

[0125] In a preferred embodiment, in formula (S3), R 21’ If present, at least one, preferably all R 21’ In this, q1'' is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0126] In a preferred embodiment, in formula (S3), R 21 If present, at least one, preferably all R 21 In this case, p1' is 0, and q1' is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0127] In a preferred embodiment, in formula (S3), R a1 If present, at least one, preferably all R a1 In this case, p1 is 0, and q1 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0128] In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

[0129] R d1 In each occurrence, -Z is independent. 2 -CR 31 p2 R 32 q2 R 33 r2 That is the case.

[0130] Z 2 Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 2 The structure described as follows is (CR) on the right side. 31 p2 R 32q2 R 33 r2 ) joins.

[0131] In a preferred embodiment, Z 2 It is a divalent organic group.

[0132] The above Z 2 Preferably, C 1-6 Alkylene group, -(CH2) z5 -O-(CH2) z6 -(wherein z5 is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6 is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7 -Phenylene-(CH2) z8 -(wherein z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0133] In a preferred embodiment, Z 2 C 1-6 Alkylene group or -(CH2) z7 -Phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 - is Z 2 If the group is such that it can have higher light resistance, especially UV resistance.

[0134] In another preferred embodiment, the above Z 2 C 1-3 It is an alkylene group. In one embodiment, Z 2 This could be -CH2CH2CH2-. In another embodiment, Z 2 It can be -CH2CH2-.

[0135] R 31 In each occurrence, -Z is independent. 2’ -CR 32’ q2’ R 33’ r2’ That is the case.

[0136] Z 2’ Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 2’ The structure described as follows is (CR) on the right side. 32’ q2’ R 33’ r2’ ) joins.

[0137] The above Z 2’ Preferably, C 1-6 Alkylene group, -(CH2) z5’ -O-(CH2) z6’ -(wherein z5' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7’ -Phenylene-(CH2) z8’ -(wherein z7' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0138] In a preferred embodiment, Z 2’ C 1-6 Alkylene group or -(CH2) z7’ -Phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ - is Z 2’If the group is such that it can have higher light resistance, especially UV resistance.

[0139] In another preferred embodiment, the above Z 2’ C 1-3 It is an alkylene group. In one embodiment, Z 2’ This could be -CH2CH2CH2-. In another embodiment, Z 2’ It can be -CH2CH2-.

[0140] The above R 32’ In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 That is the case.

[0141] The above Z 3 Each instance independently consists of a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 3 The structure described as follows is (SiR 34 n2 R 35 3-n2 ) joins.

[0142] In one embodiment, Z 3 It is an oxygen atom.

[0143] In one embodiment, Z 3 It is a divalent organic group.

[0144] The above Z 3 Preferably, C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein z5'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7” -Phenylene-(CH2) z8” -(wherein z7'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0145] In a preferred embodiment, Z 3 C 1-6 Alkylene group or -(CH2) z7” -Phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” - is Z 3 If the group is such that it can have higher light resistance, especially UV resistance.

[0146] In another preferred embodiment, the above Z 3 C 1-3 It is an alkylene group. In one embodiment, Z 3 This could be -CH2CH2CH2-. In another embodiment, Z 3 It can be -CH2CH2-.

[0147] The above R 34 Each instance is independently either a hydroxyl group or a hydrolyzable group.

[0148] R 34 Preferably, each occurrence is independently hydrolyzable.

[0149] R 34 Preferably, in each occurrence, independently, -OR h , -OCOR h , -ON=CR h 2. -NR h 2, -NHR h , or halogen (in these formulas, R h C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR h(That is, an alkoxy group). h Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h This is an ethyl group.

[0150] The above R 35 Each instance is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0151] The above R 35 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0152] In the above formula, n2 is (SiR 34 n2 R 35 3-n2 Each unit is an independent integer between 0 and 3. However, R Si If is a group represented by formula (S4), then in the terminal parts of formulas (1) and (2), n2 is 1 to 3 (SiR 34 n2 R 35 3-n2 There is at least one unit. That is, in such terminal parts, not all n2s are 0 at the same time. In other words, in the terminal parts of equations (1) and (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0153] n2 is (SiR 34 n2 R 35 3-n2Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0154] The above R 33’ Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0155] The above R 33’ In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0156] In one embodiment, R 33’ This is a hydroxyl group.

[0157] In another embodiment, R 33’ The monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0158] The above q2' is an integer between 0 and 3, independently of each occurrence, and the above r2' is an integer between 0 and 3, independently of each occurrence. Note that the sum of q2' and r2' is (CR 32’ q2’ R 33’ r2’ In units of 3, it is 3.

[0159] q2' is (CR 32’ q2’ R 33’ r2’ Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0160] R 32 In each occurrence, -Z is independent. 3 -SiR 34 n2 R 353-n2 This is the case. 3 -SiR 34 n2 R 35 3-n2 The above R 32’ This is equivalent to the description in [the relevant section].

[0161] The above R 33 Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0162] The above R 33 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0163] In one embodiment, R 33 This is a hydroxyl group.

[0164] In another embodiment, R 33 The monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0165] The above p2 is an integer between 0 and 3, independently of each occurrence; q2 is an integer between 0 and 3, independently of each occurrence; and r2 is an integer between 0 and 3, independently of each occurrence. Note that the sum of p2, q2, and r2 is (CR 31 p2 R 32 q2 R 33 r2 In units of 3, it is 3.

[0166] In one embodiment, p2 is 0.

[0167] In one embodiment, p2 is (CR 31 p2 R 32 q2 R33 r2 Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p2' is 3.

[0168] In one embodiment, q2 is (CR 31 p2 R 32 q2 R 33 r2 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0169] In one embodiment, p2 is 0 and q2 is (CR 31 p2 R 32 q2 R 33 r2 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0170] The above R e1 In each occurrence, -Z is independent. 3 -SiR 34 n2 R 35 3-n2 This is the case. 3 -SiR 34 n2 R 35 3-n2 The above R 32’ This is equivalent to the description in [the relevant section].

[0171] The above R f1 Each instance is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0172] The above R f1 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0173] In one embodiment, R f1 This is a hydroxyl group.

[0174] In another embodiment, R f1 The monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0175] The above k2 is an integer between 0 and 3, independently in each occurrence; l2 is an integer between 0 and 3, independently in each occurrence; and m2 is an integer between 0 and 3, independently in each occurrence. Note that the sum of k2, l2, and m2 is (CR d1 k2 R e1 l2 R f1 m2 In units of 3, it is 3.

[0176] In one embodiment, R Si When is a group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 The units are present in two or more units at each terminal portion of formula (1) and formula (2), for example, 2 to 27 units, preferably 2 to 9 units, more preferably 2 to 6 units, even more preferably 2 to 3 units, and particularly preferably 3 units.

[0177] In a preferred embodiment, in formula (S4), R 32’ If present, at least one, preferably all R 32’ In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0178] In a preferred embodiment, in formula (S4), R 32 If present, at least one, preferably all R 32 In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0179] In a preferred embodiment, in formula (S4), R e1 If present, at least one, preferably all R a1 In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0180] In a preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0181] In one embodiment, R Si This refers to a group represented by formula (S2), (S3), or (S4). These compounds can form a surface treatment layer with high surface slipperiness.

[0182] In one embodiment, R Si These are groups represented by formulas (S1), (S3), or (S4). Because these compounds have multiple hydrolyzable groups at one end, they can form a surface treatment layer that adheres strongly to the substrate and has high friction resistance.

[0183] In one embodiment, R Si This refers to a group represented by formula (S3) or (S4). Since these compounds may have multiple hydrolyzable groups branched from a single Si or C atom at one end, they can form a surface treatment layer with even higher friction resistance.

[0184] In one embodiment, R Si This is a base represented by equation (S1).

[0185] In one embodiment, R Si This is a base represented by equation (S2).

[0186] In one embodiment, R Si This is a base represented by formula (S3).

[0187] In one embodiment, R Si This is a base represented by formula (S4).

[0188] In the above equations (1) and (2), X A The fluoropolyether portion (R) primarily provides water repellency and surface slipperiness. F1 and R F2 ) and the part that provides bonding ability to the substrate (R Si It is understood to be a linker that connects ) and . Therefore, the X A The group may be a single bond or any other group, as long as the compounds represented by formulas (1) and (2) can exist stably.

[0189] In equation (1) above, α is an integer from 1 to 9, and β is an integer from 1 to 9. These α and β are X A It can change depending on the valence of α. The sum of α and β is X A It is the same as the valence of X. For example, X A If is a 10-valent organic group, the sum of α and β is 10, and for example, α can be 9 and β 1, α can be 5 and β 5, or α can be 1 and β 9. Also, X A If it is a divalent organic group, then α and β are 1.

[0190] In equation (2) above, γ is an integer from 1 to 9. γ is X A It can change depending on the valence of X. That is, γ is X A This is the value obtained by subtracting 1 from the valence of [the element].

[0191] X A Each of these is independently a single bond or a 2-10 valent organic group;

[0192] The above X A The 2-10 valent organic group in is preferably a 2-8 valent organic group. In one embodiment, such a 2-10 valent organic group is preferably a 2-4 valent organic group, and more preferably a 2 valent organic group. In another embodiment, such a 2-10 valent organic group is preferably a 3-8 valent organic group, and more preferably a 3-6 valent organic group.

[0193] In one embodiment, X A It is a single-bonded or divalent organic group, where α is 1 and β is 1.

[0194] In one embodiment, X A It is a single bond or a divalent organic group, and γ is 1.

[0195] In one embodiment, X A is a 3- to 6-valent organic group, with α being 1 and β being 2- to 5.

[0196] In one embodiment, X A γ is a 3- to 6-valent organic group, and γ is 2- to 5.

[0197] In one embodiment, X A It is a trivalent organic group, with α being 1 and β being 2.

[0198] In one embodiment, X A It is a trivalent organic group, and γ is 2.

[0199] X A However, when the organic group is single-bonded or divalent, formulas (1) and (2) are represented by the following formulas (1') and (2'). [ka]

[0200] In one embodiment, X A It is a single bond.

[0201] In another embodiment, X A It is a divalent organic group.

[0202] In one embodiment, X A For example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In formula: R 51 This is a single bond, -(CH2) s5 - or o-, m- or p-phenylene group, preferably -(CH2) s5 -and, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2. X 51 is, -(X 52 ) l5 - represents, X 52 In each instance, these independently include -O-, -S-, o-, m- or p-phenylene groups, -C(O)O-, and -Si(R 53 )2-,-(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -, -O-CONR 54 -, -NR 54 -and-(CH2) n5 - Represents a group selected from the group consisting of, R 53 In each appearance, independently, a phenyl group and C are present. 1-6 Alkyl or C 1-6 Represents an alkoxy group, preferably a phenyl group or C 1-6 It is an alkyl group, more preferably a methyl group, R 54 Each instance independently comprises a hydrogen atom, a phenyl group, or C. 1-6 Represents an alkyl group (preferably a methyl group), In each occurrence, m5 is an integer between 1 and 100, preferably between 1 and 20, independently. n5 is, in each occurrence, independently an integer between 1 and 20, preferably an integer between 1 and 6, more preferably an integer between 1 and 3. l5 is an integer between 1 and 10, preferably between 1 and 5, more preferably between 1 and 3. p5 is either 0 or 1. q5 is either 0 or 1. Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary. Examples thereof include divalent organic groups represented by. Here, X A (Typically, the hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred embodiment, X A is not substituted with these groups.

[0203] In a preferred embodiment, the above X A is each independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -. R 52 represents a single bond, -(CH2) t5 -, or an o-, m-, or p-phenylene group, preferably -(CH2) t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Here, R 52 (Typically, the hydrogen atom of R 52 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred embodiment, R 56 is not substituted with these groups.

[0204] Preferably, the above X A is each independently a single bond, -C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 5 - [In the formula, R 51 and R52 This is synonymous with the above, X 53 teeth, -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -Si(R 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-, -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54 -(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-,or -CONR 54 -(o-, m- or p-phenylene)-Si(R 53 )2- (In the formula, R 53 , R 54 And m5 is synonymous with the above, u5 represents an integer between 1 and 20, preferably between 2 and 6, more preferably between 2 and 3. X 54 teeth, -S-, -C(O)O-, -CONR 54 -、 -O-CONR 54 -、 -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-、 -CONR 54 -(CH2) u5 -N(R 54 )-、or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (In the formula, each symbol has the same meaning as described above.) represents. It can be.

[0205] More preferably, the above X A are each independently a single bond, -C 1-20 an alkylene group, -(CH2) s5 -X 53 -、 -(CH2) s5 -X 53 -(CH2) t5 - -X 54 -、or -X 54 -(CH2) t5 - [In the formula, X 53 , X 54 , s5 and t5 have the same meaning as described above.) is.

[0206] More preferably, the above X A are each independently a single bond, -C 1-20 an alkylene group, -(CH2) s5 -X 53 -(CH2) t5 ​ -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as above.] It is possible.

[0207] In a preferred embodiment, the above X A Each of them operates independently. single bond -C 1-20 Alkylene group, -(CH2) s5 -X 53 -,or -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 -O-, -CONR 54 -, or -O-CONR 54 -and, R 54 Each instance independently comprises a hydrogen atom, a phenyl group, or C. 1-6 Represents an alkyl group, s5 is an integer between 1 and 20. t5 is an integer between 1 and 20. It is possible.

[0208] In one embodiment, the above X A Each of them operates independently. single bond, -C 1-20 Alkylene group, -(CH2) s5 -O-(CH2) t5 -, -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53)2-(CH2) t5 -,or -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [In the formula, R 53 m5, s5, t5, and u5 are equivalent to those described above, and v5 is an integer from 1 to 20, preferably from 2 to 6, more preferably from 2 to 3. That is the case.

[0209] In the above formula, -(C v H 2v )- may be a linear or branched chain, and may be, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0210] The above X A These are, independently, a fluorine atom and a carbon atom. 1-3 Alkyl and C 1-3 Fluoroalkyl groups (preferably C 1-3 It may be substituted with one or more substituents selected from perfluoroalkyl groups. In one embodiment, X A This is a non-substitution.

[0211] Furthermore, the above X A In each equation, the left side is R F1 or R F2 Combined, the right side is R Si Combine.

[0212] In one embodiment, X A These are, independently, -OC 1-6 It may be a group other than an alkylene group.

[0213] In another embodiment, X A Examples include the following bases: [ka] [ka] [In the formula, R 41 Each of these independently consists of a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 An alkoxy group, preferably a methyl group; D is -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), and [ka] (In the formula, R 42 These are, independently, hydrogen atoms and C 1-6 alkyl group or C 1-6 (This represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.) It is a base selected from, E is -(CH2) n -(n is an integer from 2 to 6), D is the R of the molecular backbone. F1 or R F2 E is bonded to R Si [Combine with...]

[0214] The above X A Specific examples include: single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-、 -CF2-CH2-O-CH2-、 -CF2-CH2-O-(CH2)2-、 -CF2-CH2-O-(CH2)3-、 -CF2-CH2-O-(CH2)6-、 -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2- -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2- -CH2OCF2CHFOCF2-、 -CH2OCF2CHFOCF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-、 -CH2OCH2CF2CF2OCF2-、 -CH2OCH2CF2CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2- -CH2- -(CH2)2- -(CH2)3- -(CH2)4- -(CH2)5- -(CH2)6- -CF2-CH2- -CF2-(CH2)2- -CF2-(CH2)3- -CF2-(CH2)4- -CF2-(CH2)5- -CF2-(CH2)6- -CO- -CONH- -CONH-CH2- -CONH-(CH2)2- -CONH-(CH2)3- -CONH-(CH2)4- -CONH-(CH2)5- -CONH-(CH2)6-, -CF2CONHCH2-, -CF2CONH(CH2)2-, -CF2CONH(CH2)3-, -CF2CONH(CH2)4-, -CF2CONH(CH2)5-, -CF2CONH(CH2)6-, -CON(CH3)-CH2-, -CON(CH3)-(CH2)2-, -CON(CH3)-(CH2)3-, -CON(CH3)-(CH2)4-, -CON(CH3)-(CH2)5-, -CON(CH3)-(CH2)6-, -CON(Ph)-CH2- (where Ph represents phenyl), -CON(Ph)-(CH2)2- (wherein Ph means phenyl), -CON(Ph)-(CH2)3-(wherein Ph represents phenyl), -CON(Ph)-(CH2)4-(wherein Ph represents phenyl), -CON(Ph)-(CH2)5-(wherein Ph represents phenyl), -CON(Ph)-(CH2)6-(wherein Ph represents phenyl), -CF2-CON(CH3)-(CH2)3-, -CF2-CON(Ph)-(CH2)3-(wherein Ph represents phenyl), -CF2-CON(CH3)-(CH2)6-, -CF2-CON(Ph)-(CH2)6-(wherein Ph represents phenyl), -CONH-(CH2)2NH(CH2)3-, -CONH-(CH2)6NH(CH2)3-, -CH2O-CONH-(CH2)3-, -CH2O-CONH-(CH2)6-, -S-(CH2)3-, -(CH2)2S(CH2)3-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -C(O)O-(CH2)3-、 -C(O)O-(CH2)6-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、 -OCH_{2}-、 -O(CH_{2})_{3}-、 -OCFHCF_{2}-、

Chem.

[0215] ]> In yet another aspect, X A is, independently of each other, of the formula: -(R 16 )<t x1 -(CFR 17 ) y1 -(CH2) Note: In the translation, for chemical formula-related content, it is presented in a more standard chemical notation style in English. For example, "-(CH2)2S(CH2)3-" is translated as "-(CH₂)₂S(CH₂)₃-", "Si(CH3)2" is translated as "Si(CH₃)₂", etc. Also, "

化

Chem.

[0216] In the above formula, R 16 In each appearance, the oxygen atom, phenylene, carbasoliene, and -NR appear independently. 18 -(In the formula, R 18 R represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, 18 This is an oxygen atom or a divalent polar group.

[0217] The above-mentioned "divalent polar group" is not particularly limited, but includes -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 -(In these formulas, R 19 Examples include a hydrogen atom or a lower alkyl group. The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.

[0218] In the above formula, R 17 Each instance is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0219] In yet another embodiment, X A Examples include the following bases: [ka] [In the formula, R 41Each of these independently consists of a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 The alkoxy group is preferably a methyl group; each X A In the base, any some of T are R of the molecular backbone. F1 or R F2 The following groups that bind to them: -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), or [ka] [In the formula, R 42 These are, independently, hydrogen atoms and C 1-6 alkyl group or C 1-6 This represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. And some of the other T's are R's of the molecular backbone. Si If bonded, the remaining T, if present, independently consists of a methyl group, a phenyl group, and C. 1-6 It is an alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.

[0220] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, but examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.

[0221] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, but examples include residues of benzotriazoles, hydroxybenzophenones, substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0222] In a preferred embodiment, preferred radical scavenging groups or UV absorbing groups include: [ka] These are some examples.

[0223] In this embodiment, X A Each of these can independently be a 3- to 10-valent organic group.

[0224] In yet another embodiment, X A Examples include the following bases: [ka] [In the formula, R 25 , R 26 and R 27 These are each independently 2-6 valent organic groups, R 25 is at least one R F1 Combined with R 26 and R 27 Each of these has at least one R Si [Combine with...]

[0225] In one embodiment, the above R 25 C is a single bond. 1-20 Alkylene group, C 3-20 Cycloalkylene group, C 5-20 Arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 - is the case. Above, R57 and R 59 Each of them is independently a single bond, C 1-20 Alkylene group, C 3-20 Cycloalkylene group, or C 5-20 It is an arylene group. 58 These are -O-, -S-, -CO-, -O-CO-, or -COO-.

[0226] In one embodiment, the above R 26 and R 27 Each is independently a hydrocarbon, or a group having at least one atom selected from N, O, and S in the end or main chain of a hydrocarbon, preferably C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2- are examples. Here, R 36 Each of these is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. 37 R is N, O, or S, preferably N or O. 38 is, -R 45 -R 46 -R 45 -, -R 46 -R 45 -or -R 45 -R 46 - is the case. Here, R 45 Each of these is an alkyl group having 1 to 6 carbon atoms. 46 is N, O, or S, and is preferably O.

[0227] In this embodiment, X A Each of these can independently be a 3- to 10-valent organic group.

[0228] The fluoropolyether group-containing compound represented by formula (1) or formula (2) above is not particularly limited, but is 5 × 10 2 ~1 × 10 5It may have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, from the viewpoint of friction durability. Note that this "average molecular weight" refers to the number average molecular weight, and "average molecular weight" refers to the number average molecular weight. 19 The value shall be measured by 1F-NMR.

[0229] In one embodiment, the fluoropolyether group-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (1).

[0230] In another embodiment, the fluoropolyether group-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (2).

[0231] In another embodiment, the fluoropolyether group-containing silane compounds in the surface treatment agents of the present disclosure are the compound represented by formula (1) and the compound represented by formula (2).

[0232] In the surface treatment agent of this disclosure, the compound represented by formula (2) is preferably 0.1 mol% or more and 35 mol% or less relative to the total amount of the compound represented by formula (1) and the compound represented by formula (2). The lower limit of the content of the compound represented by formula (2) relative to the total amount of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, even more preferably 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, and especially possibly 5 mol%. The upper limit of the content of the compound represented by formula (2) relative to the total amount of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol%, even more preferably 20 mol%, and even more preferably 15 mol% or 10 mol%. The amount of the compound represented by formula (2) relative to the sum of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, even more preferably 0.2 mol% to 10 mol%, even more preferably 0.5 mol% to 10 mol%, and particularly preferably 1 mol% to 10 mol%, for example, 2 mol% to 10 mol% or 5 mol% to 10 mol%. By setting the compound represented by formula (2) within this range, frictional durability can be further improved.

[0233] The compounds represented by formula (1) or (2) above can be obtained, for example, by the methods described in Patent Document 1, Patent Document 2, etc.

[0234] The fluoropolyether group-containing silane compound contained in the surface treatment agent of this disclosure is produced, for example, by reacting a trichlorosilane derivative with a compound capable of introducing a hydrolyzable group, such as methanol, when introducing a hydrolyzable group to a Si atom. When produced in this manner, a certain amount of chloride ions may be present in the surface treatment agent. The inventors have noticed that the chloride ions contained in the surface treatment agent affect the function of the surface treatment agent. In particular, if the chloride ion content in the surface treatment agent exceeds 1.0 ppm by mass, the stability of the silane portion having a hydrolyzable group decreases, the reaction sites with the substrate decrease, and the frictional durability of the resulting surface treatment layer may decrease. Furthermore, there is a concern about metal corrosion due to the presence of chloride ions. Moreover, if the chloride ion content in the surface treatment agent is less than 0.1 ppm by mass, the catalytic effect of the chloride ions is not sufficiently obtained, the adhesion of the resulting surface treatment agent decreases, and the frictional durability may decrease. Therefore, the inventors have found that the above problems can be avoided by adjusting the chloride ion concentration in the surface treatment agent to a predetermined range of 0.1 ppm by mass or more and 1.0 ppm by mass, and have invented the surface treatment agent of this disclosure.

[0235] The surface treatment agent disclosed herein has a chloride ion concentration of 0.1 ppm by mass or more and 1.0 ppm by mass or less. By setting the chloride ion concentration to 1.0 ppm by mass or less, the frictional durability of the resulting surface treatment layer can be increased. Furthermore, it is advantageous for storage and can suppress adverse effects on equipment during processing, such as corrosion of metal parts. In addition, by setting the chloride ion concentration to 0.1 ppm by mass or more, the frictional durability of the resulting surface treatment layer can be increased.

[0236] The above chloride ion concentration may be 1.0 ppm by mass or less, preferably 0.80 ppm by mass or less, and more preferably 0.70 ppm by mass or less.

[0237] The above chloride ion concentration may be 0.1 ppm by mass or more, more preferably 0.2 ppm by mass or more.

[0238] In one embodiment, the chloride ion concentration may preferably be 0.20 to 0.80 ppm by mass, for example, 0.20 to 0.70 ppm by mass, 0.30 to 0.80 ppm by mass, or 0.30 to 0.70 ppm by mass.

[0239] The chloride ion concentration contained in the surface treatment agent of this disclosure can be measured by ion chromatography. Specifically, the chloride ion concentration can be measured by ion chromatography, for example, by measuring chloride ions using an ion chromatograph and determining the chloride ion concentration by an external standard method. A sample for ion concentration measurement can be prepared, for example, by diluting the sample with a hydrofluoroether such as HFE7300, and then adding ultrapure water to extract the chloride ions into the aqueous layer. Examples of apparatus and conditions are as follows. Device name: Dionex ICS-2100 (Themo SCIENTIFIC) Column: Dionex IonPac AS20 Temperature: 30℃ Flow rate: 1.0mL / min Detector: Electrical conductivity

[0240] The chloride ion concentration contained in the surface treatment agent of this disclosure can be adjusted to the chloride ion concentration in the surface treatment agent of this disclosure by purifying a composition with a high chloride ion concentration, or by adding a compound that generates chlorine or chloride ions (e.g., HCl, a compound having a -SiCl3 group).

[0241] Examples of the purification methods mentioned above include adding a metal or metal compound to a composition with a high chloride ion concentration and heating it, washing with an excess amount of alcohol, treating with a metal alkoxide, or applying it to an anionic exchange resin.

[0242] Examples of the above-mentioned metals include zinc, magnesium, and aluminum.

[0243] Examples of the above-mentioned metal compounds include organometallic compounds, preferably organozinc compounds, such as dimethylzinc and zinc octonate.

[0244] The above-mentioned metals and metal compounds are preferably used in powder form.

[0245] Examples of the alcohols mentioned above include hydrocarbon alcohols such as ethanol and propanol.

[0246] Examples of the above-mentioned metal alkoxides include basic metal alkoxides such as sodium methoxide and potassium ethoxide.

[0247] The surface treatment agents disclosed herein may include a solvent, a non-reactive fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"), a non-reactive silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like.

[0248] Examples of the above solvents include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl-2-hydroxybutyrate. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene Glycol ethers such as propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Examples include fluorine-containing solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeolora H, HFE7100, HFE7200, HFE7300, etc. Alternatively, mixed solvents of two or more of these are also possible.

[0249] Fluorine-containing oils are not particularly limited, but examples include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ...(3) In the formula, Rf 5 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1―16 Rf represents a perfluoroalkyl group. 6 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1-16 Rf represents a perfluoroalkyl group, a fluorine atom, or a hydrogen atom. 5 and Rf 6 More preferably, each independently, C 1-3 It is a perfluoroalkyl group. a', b', c', and d' represent the number of repeating units of the four types of perfluoro(poly)ether that constitute the main backbone of the polymer, and are independent integers between 0 and 300, with the sum of a', b', c', and d' being at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscripts a', b', c', or d' is arbitrary in the formula. Of these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0250] Examples of perfluoro(poly)ether compounds represented by the above general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one or a mixture of two or more). Rf 5 -(OCF2CF2CF2) b” -Rf 6 ...(3a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 ...(3b) In these equations, Rf 5 and Rf 6As stated above, in equation (3a), b'' is an integer between 1 and 100; in equation (3b), a'' and b'' are independently integers between 0 and 30, and c'' and d'' are independently integers between 1 and 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a'', b'', c'', and d'' is arbitrary within the equation.

[0251] From another perspective, fluorine-containing oils have the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented as a perfluoroalkyl group. It may also be a chlorotrifluoroethylene oligomer.

[0252] The above-mentioned fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0253] Fluorine-containing oil may be present in the composition of the Disclosure in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass. In one embodiment, the composition of the Disclosure is substantially free of fluorine-containing oil. Substantially free of fluorine-containing oil means that it is either completely free of fluorine-containing oil or contains trace amounts of fluorine-containing oil.

[0254] In one embodiment, the average molecular weight of the fluorine-containing oil may be greater than the average molecular weight of the fluoropolyether group-containing compound. By using such an average molecular weight, better frictional durability and surface lubricity can be obtained, especially when forming a surface treatment layer by vacuum deposition.

[0255] In one embodiment, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluoropolyether group-containing compound. By using such an average molecular weight, it is possible to form a cured product with high frictional durability and high surface slipperiness while suppressing a decrease in the transparency of the surface treatment layer obtained from such a compound.

[0256] Fluorine-containing oils contribute to improving the surface slipperiness of layers formed by the compositions of this disclosure.

[0257] As the silicone oil mentioned above, for example, a linear or cyclic silicone oil with 2,000 or fewer siloxane bonds may be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0258] In the compositions of the present disclosure (e.g., surface treatment agents), such silicone oil may be included in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the fluoropolyether group-containing silane compounds of the present disclosure (the sum of two or more if there are two or more, and the same applies hereinafter).

[0259] Silicone oil contributes to improving the surface lubricity of the surface-treated layer.

[0260] Examples of catalysts include acids (e.g., acetic acid, trifluoroacetic acid, etc.), bases (e.g., ammonia, triethylamine, diethylamine, etc.), and transition metals (e.g., Ti, Ni, Sn, etc.).

[0261] The catalyst promotes the hydrolysis and dehydration condensation of the fluoropolyether group-containing silane compound of the Disclosure, thereby promoting the formation of a layer formed by the composition of the Disclosure (e.g., a surface treatment agent).

[0262] Other components besides those listed above include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0263] The compositions disclosed herein can be used as surface treatment agents for surface treatment of substrates.

[0264] The surface treatment agent disclosed herein can be formed into pellets by impregnating porous materials, such as porous ceramic materials, or metal fibers, such as steel wool compressed into a cotton-like form. These pellets can be used, for example, in vacuum deposition.

[0265] The articles of this disclosure are described below.

[0266] The articles of this disclosure include a substrate and a layer (surface treatment layer) formed on the surface of the substrate from a surface treatment agent containing a fluoropolyether group-containing silane compound of this disclosure.

[0267] The substrates usable in this disclosure may consist of any suitable material, such as glass, resin (natural or synthetic resin, such as common plastic materials, which may be in the form of sheets, films, or other forms), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (textiles, nonwovens, etc.), fur, leather, wood, ceramics, stone, building materials, etc.

[0268] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate may be an optical component material, such as glass or transparent plastic. Also, if the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. If the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on a portion of the surface of the substrate (glass). Furthermore, depending on its specific specifications, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module.

[0269] The shape of the substrate is not particularly limited. Furthermore, the surface area of ​​the substrate on which the surface treatment layer is to be formed only needs to be at least a part of the substrate surface and can be appropriately determined according to the intended use and specific specifications of the article to be manufactured.

[0270] Such a substrate may consist of a material that originally contains hydroxyl groups, at least on its surface. Examples of such materials include glass, as well as metals (especially base metals) on which a native oxide film or thermal oxide film is formed on the surface, ceramics, semiconductors, etc. Alternatively, if the material does not have enough hydroxyl groups, such as resins, or if it does not originally contain hydroxyl groups, the substrate can be pretreated to introduce or increase hydroxyl groups on its surface. Examples of such pretreatment include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface and can also be suitably used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is formed in the form of a monolayer on the substrate surface by the LB method (Langmuir-Bludget method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen or nitrogen.

[0271] Alternatively, such a substrate may consist of a material in which at least its surface portion is made of another reactive group, such as a silicone compound having one or more Si-H groups, or an alkoxysilane.

[0272] Next, a layer of the surface treatment agent of the present disclosure is formed on the surface of the substrate, and this layer is post-treated as necessary, thereby forming a layer from the surface treatment agent of the present disclosure.

[0273] Layer formation of the surface treatment agent of this disclosure can be carried out by applying the above composition to the surface of a substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating methods can be used.

[0274] Examples of wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

[0275] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0276] Furthermore, coating using the atmospheric pressure plasma method is also possible.

[0277] When using a wet coating method, the surface treatment agents of the present disclosure may be diluted with a solvent before being applied to the substrate surface. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F 13CH2CH3 (e.g., AsahiClean® AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeolora® H manufactured by Nippon Zeon Co., Ltd.); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Limited), - Alkyl perfluoroalkyl ethers such as fluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Co., Ltd.) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or as a mixture of two or more. Among these, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0278] When using the dry coating method, the surface treatment agent of this disclosure may be subjected to the dry coating method as is, or it may be diluted with the solvent described above before being subjected to the dry coating method.

[0279] The layer formation of the surface treatment agent is preferably carried out such that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. For convenience, in the case of a wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent, and the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent of the present disclosure with the catalyst added may be directly vapor-deposited (usually by vacuum deposition), or a pelletized material in which the surface treatment agent of the present disclosure with the catalyst added may be impregnated, such as iron or copper, may be vapor-deposited (usually by vacuum deposition).

[0280] Any suitable acid or base can be used as a catalyst. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0281] As described above, a layer derived from the surface treatment agent of the present disclosure is formed on the surface of the substrate, and an article of the present disclosure is manufactured. The resulting layer has both high surface slipperiness and high friction resistance. In addition to high friction resistance, the layer may also have water repellency, oil repellency, stain resistance (for example, preventing the adhesion of dirt such as fingerprints), waterproofness (preventing water from entering electronic components, etc.), and surface slipperiness (or lubricity, for example, ease of wiping away dirt such as fingerprints and excellent tactile feel to the fingers), depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0282] In other words, this disclosure also relates to an optical material having the above-mentioned surface treatment layer as its outermost layer.

[0283] As optical materials, a wide variety of optical materials are preferred, in addition to optical materials related to displays, as exemplified below: for example, displays such as cathode ray tubes (CRTs; e.g., PC monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), or protective plates for such displays, or materials on which an anti-reflective coating has been applied to their surface.

[0284] Articles having layers obtained by this disclosure may be optical components, but are not limited to these. Examples of optical components include: lenses such as those found in eyeglasses; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces of watches.

[0285] Furthermore, articles having the layer obtained by this disclosure may be medical devices or medical materials.

[0286] The thickness of the above layer is not particularly limited. In the case of optical components, the thickness of the above layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, frictional durability, and antifouling properties.

[0287] The above describes in detail articles obtained using the compositions of this disclosure (e.g., surface treatment agents). However, the uses, methods of use, and methods of manufacturing articles of the fluoropolyether group-containing silane compounds or compositions containing fluoropolyether group-containing silane compounds of this disclosure are not limited to those exemplified above. [Examples]

[0288] The surface treatment agent of the present invention will be described in more detail through the following examples, but the present invention is not limited to these examples. In these examples, all chemical formulas shown below represent the average composition, and the order of existence of each repeating unit constituting the perfluoropolyether is arbitrary.

[0289] In the following, the chloride ion concentration was measured using the analytical method described below. ·Analysis method Ion chromatography The chloride ion concentration was analyzed by measuring chloride ions using an ion chromatograph and determining the concentration using the external standard method. Device name: Dionex ICS-2100 (Themo SCIENTIFIC) Column: Dionex IonPac AS20 Temperature: 30℃ Flow rate: 1.0mL / min Detector: Electrical conductivity Ion concentration samples were prepared by diluting a perfluoropolyether group-containing silane compound to 10 wt% using a Novec HFE7300 filter, followed by the addition of ultrapure water and extraction of chloride ions into the aqueous layer.

[0290] Synthesis Example 1 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 20 g of a perfluoropolyether group-containing trichlorosilane compound (A) having trichlorosilane at the end, and 20 g of 1,3-bis(trifluoromethyl)benzene were charged and stirred at 5°C for 30 minutes under a nitrogen stream. Subsequently, 35.2 ml of a diethyl ether solution containing 0.7 mol / L allyl magnesium bromide was added, and the mixture was heated to room temperature and stirred at this temperature for 10 hours. After that, it was cooled to 5°C, 5 ml of methanol was added, and the mixture was heated to room temperature and the insoluble matter was filtered off. Subsequently, volatile components were removed under reduced pressure, and the non-volatile components were diluted with perfluorohexane. A methanol washing operation (more specifically, an operation in which the fluoro compounds are maintained in the perfluorohexane phase (fluorus phase) and the non-fluoro compounds are separated and removed in the methanol phase (organic phase)) was performed three times using a separatory funnel. Next, by distilling off volatile components under reduced pressure, 18 g of product (B) containing the following perfluoropolyether group-containing allyl derivative (B) having an allyl group at the terminal was obtained. Perfluoropolyether group-containing trichlorosilane compound (A): CF3O(CF2CF2O) 15 (CF2O) 16 CF2CH2OCH2CH2CH2SiCl3 Perfluoropolyether group-containing allyl derivative (B): CF3O(CF2CF2O) 15 (CF2O) 16 CF2CH2OCH2CH2CH2Si(CH2CH=CH2)3

[0291] Synthesis Example 2 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 15 g of product (B), containing the perfluoropolyether group-containing allyl compound (B) synthesized in Synthesis Example 1 with an allyl group at the end, 15 g of 1,3-bis(trifluoromethyl)benzene, 0.05 g of triacetoxymethylsilane, and 4.2 g of trichlorosilane were charged and stirred at 5°C for 30 minutes under a nitrogen stream. Subsequently, 0.15 ml of xylene solution containing 2% of the Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the temperature was raised to 60°C, where it was stirred for 5 hours. After that, volatile components were removed under reduced pressure to obtain 16 g of product (C), containing the perfluoropolyether group-containing trichlorosilane compound (C) shown below, which has trichlorosilane at the end. Perfluoropolyether group-containing trichlorosilane compounds (C): CF3O(CF2CF2O) 15 (CF2O) 16 CF2CH2OCH2CH2CH2Si(CH2CH2CH2SiCl3)3

[0292] Synthesis Example 3 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 16 g of product (C), containing the perfluoropolyether group-containing trichlorosilane compound (C) synthesized in Synthesis Example 2 with a trichlorosilane group at the end, and 16 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50°C for 30 minutes under a nitrogen stream. Subsequently, a mixed solution of 1.04 g methanol and 48 g trimethyl orthoformate was added, and the temperature was raised to 65°C, where it was stirred for 3 hours. After that, the mixture was cooled to room temperature, insoluble matter was filtered off, and volatile components were removed under reduced pressure to obtain 16 g of product (D), containing the perfluoropolyether group-containing silane compound (D) with a trimethylsilyl group at the end. Perfluoropolyether group-containing silane compounds (D): CF3O(CF2CF2O) 15 (CF2O) 16 CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 (Note that the average composition contained 0.17 repeating units of (CF2CF2CF2CF2O) and 0.18 repeating units of (CF2CF2CF2O), but these were omitted due to their trace amounts.)

[0293] Synthesis Example 4 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 21 g of a perfluoropolyether group-containing trichlorosilane compound (E) having a trichlorosilane group at the end, and 21 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50°C for 30 minutes under a nitrogen stream. Subsequently, a mixed solution of 1.34 g methanol and 64 g trimethyl orthoformate was added, and the temperature was raised to 65°C, where it was stirred for 3 hours. After cooling to room temperature, insoluble matter was filtered off, and volatile components were removed under reduced pressure to obtain 21 g of product (F) containing the perfluoropolyether group-containing silane compound (F) having a trimethylsilyl group at the end. Perfluoropolyether group-containing trichlorosilane compound (E): CF3O(CF2CF2OCF2CF2CF2CF2O)3CF2CF2OCF2CF2CF2CONHCH2C(CH2CH2CH2SiCl3)3 Perfluoropolyether group-containing silane compounds (F): CF3O(CF2CF2OCF2CF2CF2CF2O)3CF2CF2OCF2CF2CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[0294] Synthesis Example 5 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 16 g of the perfluoropolyether group-containing trichlorosilane compound (G) having a trichlorosilane group at the end, and 16 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50°C for 30 minutes under a nitrogen stream. Subsequently, a mixed solution of 1.04 g methanol and 48 g trimethyl orthoformate was added, and the temperature was raised to 65°C, where it was stirred for 3 hours. After cooling to room temperature, insoluble matter was filtered off, and volatile components were removed under reduced pressure to obtain 16 g of product (H) containing the perfluoropolyether group-containing silane compound (H) having a trimethylsilyl group at the end. Perfluoropolyether group-containing trichlorosilane compound (G): CF3O(CF2CF2O) 15 (CF2O) 16 CF2C(OCH2CH2CH2SiCl3)(CH2CH2CH2SiCl3)2 Perfluoropolyether group-containing silane compounds (H): CF3O(CF2CF2O) 15 (CF2O) 16 CF2C[OCH2CH2CH2Si(OCH3)3][CH2CH2CH2Si(OCH3)3]2 (Note that the average composition contained 0.17 repeating units of (CF2CF2CF2CF2O) and 0.18 repeating units of (CF2CF2CF2O), but these were omitted due to their trace amounts.)

[0295] Example 1 5.0 g of product (D), containing the perfluoropolyether group-containing silane compound (D) obtained in Synthesis Example 3, was diluted with 13 g of perfluorohexane, 1.5 g of methanol was added, and the washing operation was performed three times. Subsequently, the lower phase was concentrated to obtain 4.0 g of perfluoropolyether group-containing silane composition (D'). Analysis of the obtained composition (D') by the above ion chromatography showed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was 0.3 ppm by mass.

[0296] Example 2 1.0 g of product (D), containing the perfluoropolyether group-containing silane compound (D) obtained in Synthesis Example 3, was diluted with 4.0 g of perfluorohexane, followed by the addition of 3 wt% metallic zinc powder, and the mixture was stirred at room temperature for 2 hours. The solids were then filtered, and the non-volatile components obtained by concentration were diluted with 9.0 g of HFE7300 from NOVEC, and 3 wt% of activated carbon Shirasagi A from Osaka Gas Chemical Co., Ltd. was added, and the mixture was stirred at room temperature for 2 hours. The solids were then filtered, and the mixture was concentrated to obtain 1.0 g of perfluoropolyether group-containing silane composition (D”). Analysis of the obtained composition (D”) by the above ion chromatography showed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was 0.7 ppm by mass.

[0297] Example 3 5.0 g of product (F), which contains the perfluoropolyether group-containing silane compound (F) obtained in Synthesis Example 4, was washed with methanol in the same manner as in Example 1. Analysis of the obtained composition (F') by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was 0.2 ppm by mass.

[0298] Example 4 1.0 g of product (F), which contains the perfluoropolyether group-containing silane compound (F) obtained in Synthesis Example 4, was treated with metallic zinc powder and activated carbon in the same manner as in Example 2. Analysis of the obtained composition (F) by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was 0.7 ppm by mass.

[0299] Example 5 5.0 g of product (H) containing the perfluoropolyether group-containing silane compound (H) obtained in Synthesis Example 5 was washed with methanol in the same manner as in Example 1. Analysis of the obtained composition (H') by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was 0.2 ppm by mass.

[0300] Example 6 1.0 g of product (H) containing the perfluoropolyether group-containing silane compound (H) obtained in Synthesis Example 5 was treated with metallic zinc powder and activated carbon in the same manner as in Example 2. Analysis of the obtained composition (H) by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was 0.8 ppm by mass.

[0301] [Table 1]

[0302] Comparative Example 1 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, add 15 g of product (B) containing the allyl compound (B) with an allyl group at the end of a perfluoropolyether group synthesized in Synthesis Example 1, 15 g of 1,3-bis(trifluoromethyl)benzene, 3.0 g of trimethoxysilane, and 1.5 × 10⁻¹ of a toluene solution of the chloroplatinic acid / vinylsiloxane complex. -2 The mixture was charged and stirred at 80°C for 12 hours under a nitrogen atmosphere. Subsequently, volatile components were removed by distillation under reduced pressure to obtain 15 g of product (P) containing the following perfluoropolyether group-containing silane compound (D) having a trimethylsilyl group at the terminal end. Analysis of the obtained product (P) by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was less than 0.1 ppm by mass.

[0303] Comparative Example 2 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, add the following: 10 g of allyl(I) perfluoropolyether group-containing allyl compound having an allyl group at the end, 10 g of 1,3-bis(trifluoromethyl)benzene, 2.0 g of trimethoxysilane, and 1.0 × 10⁻¹⁵ toluene solution of chloroplatinic acid / vinylsiloxane complex. -2The mixture was charged and stirred at 80°C for 12 hours under a nitrogen atmosphere. Subsequently, volatile components were removed by distillation under reduced pressure to obtain 15 g of product (Q), which contains the following perfluoropolyether group-containing silane compound (F) having a trimethylsilyl group at the terminal end. Analysis of the obtained product (Q) by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was less than 0.1 ppm by mass. Perfluoropolyether group-containing allyl derivative (I): CF3O(CF2CF2OCF2CF2CF2CF2O)3CF2CF2OCF2CF2CF2CONHCH2C(CH2CH=CH2)3

[0304] Comparative Example 3 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, add the following: 10 g of perfluoropolyether-containing allyl compound (J) with an allyl group at the end, 10 g of 1,3-bis(trifluoromethyl)benzene, 2.0 g of trimethoxysilane, and 1.0 × 10⁻¹⁵ toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 The mixture was charged and stirred at 80°C for 12 hours under a nitrogen atmosphere. Subsequently, volatile components were removed by distillation under reduced pressure to obtain 15 g of product (R) containing the following perfluoropolyether group-containing silane compound (H) having a trimethylsilyl group at the terminal end. Analysis of the obtained product (R) by the above ion chromatography revealed that the chloride ion concentration in a 10 wt% diluted solution of HFE7300 was less than 0.1 ppm by mass. Perfluoropolyether group-containing allyl derivative (J): CF3O(CF2CF2O) 15 (CF2O) 16 CF2C(OCH2CH=CH2)(CH2CH=CH2)2

[0305] Comparative Example 4 An untreated sample of product (D) obtained in Synthesis Example 3 was prepared. The chloride ion concentration of the untreated product (D) was measured by the above ion chromatography and was found to be 6.7 ppm by mass in a 10 wt% diluted solution of HFE7300.

[0306] Comparative Example 5 An untreated sample of product (F) obtained in Synthesis Example 4 was prepared. The chloride ion concentration of the untreated product (F) was measured by the above ion chromatography and was found to be 5.5 ppm by mass in a 10 wt% diluted solution of HFE7300.

[0307] Comparative Example 6 An untreated sample of product (H) obtained in Synthesis Example 5 was prepared. The chloride ion concentration of the untreated product (H) was measured by the above ion chromatography and found to be 8.7 ppm by mass in a 10 wt% diluted solution of HFE7300.

[0308] [Table 2]

[0309] (Example test) • Friction durability evaluation A surface treatment layer was formed using a 10 wt% diluted solution of the perfluoropolyether group-containing silane compounds from Examples 1-6 and Comparative Examples 1-3 in HFE7300 as a surface treatment agent. Specifically, the surface treatment agent was vacuum deposited onto chemically strengthened glass (Corning "Gorilla" glass, 0.7 mm thick). The vacuum deposition conditions were a pressure of 3.0 × 10⁻⁶. -3 A 7 nm silicon dioxide film was formed on the surface of the chemically strengthened glass, and then 2 mg of a surface treatment agent (i.e., containing 0.2 mg of a perfluoropolyether group-containing silane compound) was deposited onto each sheet of chemically strengthened glass (55 mm × 100 mm). After that, the chemically strengthened glass with the deposited film was left to stand for 24 hours in an atmosphere of 20°C and 65% humidity.

[0310] As described above, the friction durability of the surface treatment layer formed on the substrate surface was evaluated by an eraser friction durability test. Specifically, a sample item with the surface treatment layer was placed horizontally, and an eraser (Kokuyo Co., Ltd., KESHI-70, planar dimensions 1cm x 1.6cm) was brought into contact with the surface of the surface treatment layer. A load of 500gf was applied, and then the eraser was moved back and forth at a speed of 20mm / second while the load was applied. The static contact angle (degrees) of water was measured every 500 reciprocations. The evaluation was stopped when the measured contact angle fell below 100 degrees. The number of reciprocations at which the final contact angle exceeded 100 degrees is shown in Tables 3 to 5.

[0311] • Perfluoropolyether group-containing silane compounds (D) [Table 3]

[0312] • Perfluoropolyether group-containing silane compound (F) [Table 4]

[0313] • Perfluoropolyether group-containing silane compounds (H) [Table 5]

[0314] From the above results, it was confirmed that higher friction durability can be obtained when a composition with a chloride ion concentration within the range of this disclosure is used. This disclosure is not bound by any theory, but it is thought that when the chloride ion concentration exceeds 1.0 ppm by mass, the stability of the methoxysilane portion decreases, the reaction sites with the substrate decrease, and the friction durability of the surface treatment layer decreases. When the chloride ion concentration is between 0.1 and 1.0 ppm by mass, it is thought that the trace amount of chloride ion component acts as a catalyst during the reaction with the glass, improving adhesion and increasing friction durability. Furthermore, when the chloride ion concentration is less than 0.1 ppm by mass, it is thought that the catalytic effect is not obtained, adhesion decreases, and friction durability decreases. [Industrial applicability]

[0315] The surface treatment agents disclosed herein can be suitably used to form a surface treatment layer on the surface of various substrates, particularly optical components where transparency is required.

Claims

1. The following formulas (1) or (2): 【Chemistry 1】 [In the formula: R Ｆ１ Each occurrence is independent of Rf １ -R Ｆ -O ｑ - and; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ is a C1-16 perfluoroalkyl group; Rf ２ is a C1-6 perfluoroalkylene group; R Ｆ Each occurrence is independent of the following formula: -(OC 4 F 8 ) c - (OC 3 F 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - (f2) [In the formula, c and d are each independent integers between 0 and 30; e and f are each independent integers between 1 and 200; The sum of c, d, e, and f is an integer between 10 and 200; The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. It is a base represented by; p is either 0 or 1; q is either 0 or 1 independently in each occurrence; R Ｓｉ Each instance independently comprises a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a Si atom to which a monovalent organic group is bonded, and is represented by the following formulas (S1), (S2), (S3), or (S4): 【Chemistry 2】 [In the formula: R 11 is, in each instance, independently a hydroxyl group or a hydrolyzable group; R 12 is independently a hydrogen atom or a C1-20 alkyl group in each instance; n1 is an integer between 0 and 3, independently for each unit of (SiR 11 n1 R 12 3-n1); X 11 is, in each instance, independently either a single bond or a C 1-20 alkylene group; R 13 is, in each instance, independently a hydrogen atom or a C1-20 alkyl group; t is an integer between 2 and 10, independently in each occurrence; R 14 is, in each instance, independently either a hydrogen atom or a halogen atom; R a1 is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 in each occurrence; Z1 is, independently in each occurrence, an oxygen atom, a C1-6 alkylene group, -(CH2)z1-O-(CH2)z2- (where z1 is an integer from 0 to 6 and z2 is an integer from 0 to 6), or -(CH2)z3-phenylene-(CH2)z4- (where z3 is an integer from 0 to 6 and z4 is an integer from 0 to 6); R 21 is independently -Z 1' -SiR 21' p1' R 22' q1' R 23' r1' in each occurrence; R 22 is, in each instance, independently either a hydroxyl group or a hydrolyzable group; R 23 is independently a hydrogen atom or a C1-20 alkyl group in each occurrence; p1 is an integer between 0 and 3, independently in each occurrence; q1 is an integer between 0 and 3, independently in each occurrence; r1 is an integer between 0 and 3, independently in each occurrence; Z1' is, in each occurrence, independently a C1-6 alkylene group, -(CH2)z1'-O-(CH2)z2'- (wherein z1' is an integer from 0 to 6 and z2' is an integer from 0 to 6) or -(CH2)z3'-phenylene-(CH2)z4'- (wherein z3' is an integer from 0 to 6 and z4' is an integer from 0 to 6); R 21' is independently -Z 1” -SiR 22” q1” R 23” r1” in each occurrence; R 22' is, in each instance, independently either a hydroxyl group or a hydrolyzable group; R 23' is independently a hydrogen atom or a C1-20 alkyl group in each occurrence; p1' is an integer between 0 and 3, independently in each occurrence; q1' is an integer between 0 and 3, independently in each occurrence; r1' is an integer between 0 and 3, independently in each occurrence; Z1'' is, in each occurrence, independently a C1-6 alkylene group, -(CH2)z1''-O-(CH2)z2''- (where z1'' is an integer from 0 to 6 and z2'' is an integer from 0 to 6) or -(CH2)z3''-phenylene-(CH2)z4''- (where z3'' is an integer from 0 to 6 and z4'' is an integer from 0 to 6); R 22'' is, in each instance, independently a hydroxyl group or a hydrolyzable group; R 23'' is independently a hydrogen atom or a C1-20 alkyl group in each occurrence; q1'' is an integer between 0 and 3, independently in each occurrence; r1'' is an integer between 0 and 3, independently in each occurrence; R b1 is, in each instance, independently either a hydroxyl group or a hydrolyzable group; R c1 is independently a hydrogen atom or a C1-20 alkyl group in each instance; k1 is an integer between 0 and 3, independently in each occurrence; l1 is an integer between 0 and 3, independently in each occurrence; m1 is an integer between 0 and 3, independently in each occurrence; R d1 is independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 in each occurrence; Z2 is, in each occurrence, independently a C1-6 alkylene group, -(CH2)z5-O-(CH2)z6- (where z5 is an integer from 0 to 6 and z6 is an integer from 0 to 6) or -(CH2)z7-phenylene-(CH2)z8- (where z7 is an integer from 0 to 6 and z8 is an integer from 0 to 6); R 31 is independently -Z 2' -CR 32' q2' R 33' r2' in each occurrence; R 32 is independently -Z 3 -SiR 34 n2 R 35 3-n2 in each occurrence; R 33 is, in each instance, independently a hydrogen atom, a hydroxyl group, or a C1-20 alkyl group; p2 is an integer between 0 and 3, independently in each occurrence; q2 is an integer between 0 and 3, independently in each occurrence; r² is an integer between 0 and 3, independently in each occurrence; Z2' is, in each occurrence, independently a C1-6 alkylene group, -(CH2)z5'-O-(CH2)z6'- (where z5' is an integer from 0 to 6 and z6' is an integer from 0 to 6) or -(CH2)z7'-phenylene-(CH2)z8'- (where z7' is an integer from 0 to 6 and z8' is an integer from 0 to 6); R 32' is independently -Z 3 -SiR 34 n2 R 35 3-n2 in each occurrence; R 33' is independently a hydrogen atom, a hydroxyl group, or a C1-20 alkyl group in each occurrence; q2' is an integer between 0 and 3, independently in each occurrence; r²' is an integer between 0 and 3, independently in each occurrence; Z3 is, in each occurrence, independently a C1-6 alkylene group, -(CH2) z5'' -O-(CH2) z6'' - (where z5'' is an integer from 0 to 6, and z6'' is an integer from 0 to 6) or -(CH2) z7'' -phenylene-(CH2) z8'' - (where z7'' is an integer from 0 to 6, and z8'' is an integer from 0 to 6); R 34 is, in each instance, independently either a hydroxyl group or a hydrolyzable group; R 35 is independently a hydrogen atom or a C1-20 alkyl group in each instance; n² is an integer between 0 and 3, independently in each occurrence; Re e1 is independently -Z 3 -SiR 34 n2 R 35 3-n2 in each occurrence; R f1 is independently a hydrogen atom, a hydroxyl group, or a C1-20 alkyl group in each instance; k2 is an integer between 0 and 3, independently in each occurrence; l2 is an integer between 0 and 3, independently in each occurrence; m² is an integer between 0 and 3, independently in each occurrence; The hydrolyzable groups are -OR h, -OCOR h, -O-N=CR h 2, -NR h 2, -NHR h, or halogens (wherein R h represents a substituted or unsubstituted C1-4 alkyl group). It is a base represented by; at least one R Ｓｉ This is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ Each is independent, either as a single bond or as shown in the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In the formula: R 51 is a single bond or -(CH2)s5-; s5 is an integer between 1 and 20; X 51 represents -(X 52) l5 -; X 52 is a group that is independently selected in each occurrence from the group consisting of -O-, -C(O)O-, -CONR 54-, -O-CONR 54-, -NR 54-, and -(CH2)n5-; R 54 is, in each instance, independently a hydrogen atom or a C1-6 alkyl group; n5 is an integer between 1 and 20, independently in each occurrence; l5 is an integer between 1 and 10; p5 is either 0 or 1; q5 is either 0 or 1; Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary. It is a base represented by; α is 1; β is 1; γ is 1. A surface treatment agent comprising at least one fluoropolyether group-containing compound represented by and chloride ions, wherein the chloride ion concentration in the surface treatment agent is 0.1 ppm by mass or more and 1.0 ppm by mass or less.

2. R Ｆ Each occurrence is independent of the following formula: -(OCF ２ CF ２ CF ２ CF ２ ) ｃ -(OCF ２ CF ２ CF ２ ) ｄ -(OCF ２ CF ２ ) ｅ -(OCF ２ ) ｆ - [In the formula, c and d are each independent integers between 0 and 30; e and f are each independent integers between 1 and 200; The sum of c, d, e, and f is an integer between 10 and 200; The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. The surface treatment agent according to claim 1, wherein the group is represented by [the specified group].

3. The surface treatment agent according to claim 2, wherein the ratio of e to f is 0.1 to 10.

4. R Ｆ１ and R Ｆ２ The surface treatment agent according to any one of claims 1 to 3, wherein the number-average molecular weight of the part is 500 to 30,000.

5. X Ａ The surface treatment agent according to any one of claims 1 to 4, wherein the bond is a single bond.

6. A surface treatment agent according to any one of claims 1 to 5, wherein the chloride ion concentration in the surface treatment agent is 0.2 to 0.8 ppm by mass.

7. A surface treatment agent according to any one of claims 1 to 6, further comprising one or more other components selected from a fluorine-containing oil, a silicone oil, and a catalyst.

8. The surface treatment agent according to any one of claims 1 to 7, further comprising a solvent.

9. A surface treatment agent according to any one of claims 1 to 8, used as an antifouling coating agent or a waterproof coating agent.

10. A surface treatment agent according to any one of claims 1 to 9, for use in vacuum deposition.

11. A pellet containing the surface treatment agent according to any one of claims 1 to 10.

12. An article comprising a base material and a layer formed on the surface of the base material from a surface treatment agent according to any one of claims 1 to 10.

13. The article according to claim 12, which is an optical component.

Images